Enhanced reversibility and durability of a solid oxide Fe-air redox battery by carbothermic reaction derived energy storage materials.

PubMed

Zhao, Xuan; Li, Xue; Gong, Yunhui; Huang, Kevin

2014-01-18

The recently developed solid oxide metal-air redox battery is a new technology capable of high-rate chemistry. Here we report that the performance, reversibility and stability of a solid oxide iron-air redox battery can be significantly improved by nanostructuring energy storage materials from a carbothermic reaction.

High energy density redox flow device

DOEpatents

Chiang, Yet-Ming; Carter, W. Craig; Ho, Bryan Y; Duduta, Mihai; Limthongkul, Pimpa

2014-05-13

Redox flow devices are described in which at least one of the positive electrode or negative electrode-active materials is a semi-solid or is a condensed ion-storing electroactive material, and in which at least one of the electrode-active materials is transported to and from an assembly at which the electrochemical reaction occurs, producing electrical energy. The electronic conductivity of the semi-solid is increased by the addition of conductive particles to suspensions and/or via the surface modification of the solid in semi-solids (e.g., by coating the solid with a more electron conductive coating material to increase the power of the device). High energy density and high power redox flow devices are disclosed. The redox flow devices described herein can also include one or more inventive design features. In addition, inventive chemistries for use in redox flow devices are also described.

Redox-Controlled Olefin (Co)Polymerization Catalyzed by Ferrocene-Bridged Phosphine-Sulfonate Palladium Complexes.

PubMed

Chen, Min; Yang, Bangpei; Chen, Changle

2015-12-14

The facile and reversible interconversion between neutral and oxidized forms of palladium complexes containing ferrocene-bridged phosphine sulfonate ligands was demonstrated. The activity of these palladium complexes could be controlled using redox reagents during ethylene homopolymerization, ethylene/methyl acrylate copolymerization, and norbornene oligomerization. Specifically in norbornene oligomerization, the neutral complexes were not active at all whereas the oxidized counterparts showed appreciable activity. In situ switching between the neutral and oxidized forms resulted in an interesting "off" and "on" behavior in norbornene oligomerization. This work provides a new strategy to control the olefin polymerization process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of crosslinked methylcellulose hydrogels for soft tissue augmentation using an ammonium persulfate-ascorbic acid redox system.

PubMed

Gold, Gittel T; Varma, Devika M; Taub, Peter J; Nicoll, Steven B

2015-12-10

Hydrogels composed of methylcellulose are candidate materials for soft tissue reconstruction. Although photocrosslinked methylcellulose hydrogels have shown promise for such applications, gels crosslinked using reduction-oxidation (redox) initiators may be more clinically viable. In this study, methylcellulose modified with functional methacrylate groups was polymerized using an ammonium persulfate (APS)-ascorbic acid (AA) redox initiation system to produce injectable hydrogels with tunable properties. By varying macromer concentration from 2% to 4% (w/v), the equilibrium moduli of the hydrogels ranged from 1.47 ± 0.33 to 5.31 ± 0.71 kPa, on par with human adipose tissue. Gelation time was found to conform to the ISO standard for injectable materials. Cellulase treatment resulted in complete degradation of the hydrogels within 24h, providing a reversible corrective feature. Co-culture with human dermal fibroblasts confirmed the cytocompatibility of the gels based on DNA measurements and Live/Dead imaging. Taken together, this evidence indicates that APS-AA redox-polymerized methylcellulose hydrogels possess properties beneficial for use as soft tissue fillers. Copyright © 2015 Elsevier Ltd. All rights reserved.

A redox beginning: Which came first phosphoryl, acyl, or electron transfer ?. [Abstract only

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

1994-01-01

Thermodynamic and kinetic information available on the synthesis of prebiotic monomers and polymers will be examined in order to illuminate the prebiotic plausibility of polymer syntheses based on (a) phosphoryl transfer that yields phosphodiester polymers, (b) acyl transfer that gives polyamides, and (c) electron transfer that produces polydisulfide or poly(thio)ester polymers. New experimental results on the oxidative polymerization of 2,3-dimercaptopropanol by ferric ions on the surface of ferric hydroxide oxide will be discussed as a chemical model of polymerization by electron transfer. This redox polymerization that yields polymers with a polydisulfide backbone was found to give oligomers up to the 15-mer from 1 mM of 2,3-dimercaptopropanol after one day at 25 C. High pressure liquid chromatography (HPLC) analysis of the oligomers was carried out on an Alltech OH-100 column eluted with acetonitrile-water.

COMBINING ATOM TRANSFER RADICAL POLYMERIZATION AND DISULFIDE /THIOL REDOX CHEMISTRY: A ROUTE TO WELL-DEFINED (BIO)DEGRADABLE POLYMERIC MATERIALS. (R829580)

EPA Science Inventory

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

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

Chiang, Yet-Ming; Carter, Craig W.; Ho, Bryan Y.

Redox flow devices are described in which at least one of the positive electrode or negative electrode-active materials is a semi-solid or is a condensed ion-storing electroactive material, and in which at least one of the electrode-active materials is transported to and from an assembly at which the electrochemical reaction occurs, producing electrical energy. The electronic conductivity of the semi-solid is increased by the addition of conductive particles to suspensions and/or via the surface modification of the solid in semi-solids (e.g., by coating the solid with a more electron conductive coating material to increase the power of the device). Highmore » energy density and high power redox flow devices are disclosed. The redox flow devices described herein can also include one or more inventive design features. In addition, inventive chemistries for use in redox flow devices are also described.« less

Bifunctional redox tagging of carbon nanoparticles

NASA Astrophysics Data System (ADS)

Poon, Jeffrey; Batchelor-McAuley, Christopher; Tschulik, Kristina; Palgrave, Robert G.; Compton, Richard G.

2015-01-01

Despite extensive work on the controlled surface modification of carbon with redox moieties, to date almost all available methodologies involve complex chemistry and are prone to the formation of polymerized multi-layer surface structures. Herein, the facile bifunctional redox tagging of carbon nanoparticles (diameter 27 nm) and its characterization is undertaken using the industrial dye Reactive Blue 2. The modification route is demonstrated to be via exceptionally strong physisorption. The modified carbon is found to exhibit both well-defined oxidative and reductive voltammetric redox features which are quantitatively interpreted. The method provides a generic approach to monolayer modifications of carbon and carbon nanoparticle surfaces.

Synthesis and structure of a ferric complex of 2,6-di(1H-pyrazol-3-yl)pyridine and its excellent performance in the redox-controlled living ring-opening polymerization of ε-caprolactone.

PubMed

Fang, Yang-Yang; Gong, Wei-Jie; Shang, Xiu-Juan; Li, Hong-Xi; Gao, Jun; Lang, Jian-Ping

2014-06-14

The reaction of FeCl3 with a pincer ligand, 2,6-di(1H-pyrazol-3-yl)pyridine (bppyH2), produced a mononuclear Fe(III) complex [Fe(bppyH2)Cl3] (1), which could be reduced to the corresponding Fe(II) dichloride complex [Fe(bppyH2)Cl2] (2) by suitable reducing agents such as Cp2Co or Fe powder. 1 and 2 exhibited a reversible transformation from each other with appropriate redox reagents. 1 could be utilized as a pre-catalyst to initiate the ring-opening polymerization of ε-caprolactone in the presence of alcohol but did not work. The 1/alcohol system displayed characteristics of a well-controlled polymerization with the resulting poly(ε-caprolactone) having low molecular weight distributions, a linear tendency of molecular weight evolution with conversion, and polymer growth observed for the sequential additions of ε-caprolactone monomer to the polymerization reaction. The polymerization was completely turned off by the in situ reduction of the catalytic Fe center via Cp2Co and then turned back upon the addition of [Cp2Fe]PF6. The rate of polymerization was modified by switching in situ between the Fe(III) and Fe(II) species.

Michael Addition Polymerization of Trifunctional Amine and Acrylic Monomer: A Versatile Platform for Development of Biomaterials.

PubMed

Cheng, Weiren; Wu, Decheng; Liu, Ye

2016-10-10

Michael addition polymerizations of amines and acrylic monomers are versatile approaches to biomaterials for various applications. A combinatorial library of poly(β-amino ester)s and diverse poly(amido amine)s from diamines and diacrylates or bis(acrylamide)s have been reported, respectively. Furthermore, novel linear and hyperbranched polymers from Michael addition polymerizations of trifunctional amines and acrylic monomers significantly enrich this category of biomaterials. In this Review, we focus on the biomaterials from Michael addition polymerizations of trifunctional amines and acrylic monomers. First we discuss how the polymerization mechanisms, which are determined by the reactivity sequence of the three types of amines of trifunctional amines, i.e., secondary (2°) amines (original), primary (1°) amines, and 2° amines (formed), are affected by the chemistry of monomers, reaction temperature, and solvent. Then we update how to design and synthesize linear and hyperbranched polymers based on the understanding of polymerization mechanisms. Linear polymers containing 2° amines in the backbones can be obtained from polymerizations of diacrylates or bis(acrylamide)s with equimolar trifunctional amine, and several approaches, e.g., 2A 2 +BB'B″, A 3 +2BB'B', A 2 +BB'B″, to hyperbranched polymers are developed. Further through molecular design of monomers, conjugation of functional species to 2° amines in the backbones of linear polymers and the abundant terminal groups of hyperbranched polymers, the amphiphilicity of polymers can be adjusted, and additional stimuli, e.g., thermal, redox, reactive oxidation species (ROS), and light, responses can be integrated with the intrinsic pH response. Finally we discuss the applications of the polymers for gene/drug delivery and bioimaging through exploring their self-assemblies in various motifs, e.g., micelles, polyplexes particles/nanorings and hydrogels. Redox-responsive hyperbranched polymers can display 300 times higher in vitro gene transfection efficiency and provide a higher in vivo siRNA efficacy than PEI. Also redox-responsive micelle carriers can improve the efficacy of anticancer drug and the bioimaging contrast. Further molecular design and optimization of this category of polymers together with in vivo studies should provide safe and efficient biomaterials for clinical applications.

Selective extraction of metal ions with polymeric extractants by ion exchange/redox

DOEpatents

Alexandratos, Spiro D.

1987-01-01

The specification discloses a method for the extraction of metal ions having a reduction potential of above about +0.3 from an aqueous solution. The method includes contacting the aqueous solution with a polymeric extractant having primary phosphinic acid groups, secondary phosphine oxide groups, or both phosphinic acid and phosphine oxide groups.

Facile preparation of cobaltocenium-containing polyelectrolyte via click chemistry and RAFT polymerization.

PubMed

Yan, Yi; Zhang, Jiuyang; Qiao, Yali; Tang, Chuanbing

2014-01-01

A facile method to prepare cationic cobaltocenium-containing polyelectrolyte is reported. Cobaltocenium monomer with methacrylate is synthesized by copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction between 2-azidoethyl methacrylate and ethynylcobaltocenium hexafluorophosphate. Further controlled polymerization is achieved by reversible addition-fragmentation chain transfer polymerization (RAFT) by using cumyl dithiobenzoate (CDB) as a chain transfer agent. Kinetic study demonstrates the controlled/living process of polymerization. The obtained side-chain cobaltocenium-containing polymer is a metal-containing polyelectrolyte that shows characteristic redox behavior of cobaltocenium. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors.

PubMed

Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre; Zigah, Dodzi; Mehdi, Ahmad; Vioux, André; Freunberger, Stefan A; Favier, Frédéric; Fontaine, Olivier

2017-04-01

Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

Molecular Syntheses of Extended Materials

NASA Astrophysics Data System (ADS)

Paley, Daniel W.

Bottom-up molecular synthesis is a route to chemically and crystallographically uniform polymers and solid-state materials. Through the use of molecular precursors, we gain atomic-level control of functionality and fine-tuning of the collective properties of materials. This dissertation presents two studies that demonstrate this approach. Ring-opening alkyne metathesis polymerization is a possible approach to monodisperse conjugated polymers, but its applications have been limited by difficult syntheses and high air sensitivity of known organometallic ROAMP initiators. We designed a dimeric, air-stable molybdenum alkylidyne with a tris(phenolate) supporting ligand. The precatalyst is activated by addition of methanol and polymerizes cyclooctynes with excellent chemical selectivity and functional group tolerance. The Nuckolls and Roy groups have introduced a new family of solid-state compounds synthesized from cobalt chalcogenide clusters Co6Q 8(PR3)6 and fullerenes. The first examples of these materials crystallized in superatom lattices with the symmetry of simple inorganic solids CdI2 (P-3m1) and NaCl (Fm-3m). This dissertation reveals that further members of the family feature extraordinary diversity of structure, including a pseudo-trigonal array of fulleride dimers in [Co 6Te8(PEt3)6]2[C140 ][C70]2 and a heterolayered van der Waals cocrystal [Co6Se8(PEt2phen)6][C 60]5. In addition to these unusual crystal structures, this dissertation presents a method for assigning redox states from crystallographic data in Co6Q8 clusters. Finally, a detailed guide to the collection and solution of single-crystal X-ray data is presented. The guide is intended for independent study by new crystallographers.

Thiol-Ene functionalized siloxanes for use as elastomeric dental impression materials

PubMed Central

Cole, Megan A.; Jankousky, Katherine C.; Bowman, Christopher N.

2014-01-01

Objectives Thiol- and allyl-functionalized siloxane oligomers are synthesized and evaluated for use as a radical-mediated, rapid set elastomeric dental impression material. Thiol-ene siloxane formulations are crosslinked using a redox-initiated polymerization scheme, and the mechanical properties of the thiol-ene network are manipulated through the incorporation of varying degrees of plasticizer and kaolin filler. Formulations with medium and light body consistencies are further evaluated for their ability to accurately replicate features on both the gross and microscopic levels. We hypothesize that thiol-ene functionalized siloxane systems will exhibit faster setting times and greater detail reproduction than commercially available polyvinylsiloxane (PVS) materials of comparable consistencies. Methods Thiol-ene functionalized siloxane mixtures formulated with varying levels of redox initiators, plasticizer, and kaolin filler are made and evaluated for their polymerization speed (FTIR), consistency (ISO4823.9.2), and surface energy (goniometer). Feature replication is evaluated quantitatively by SEM. The Tg, storage modulus, and creep behavior are determined by DMA. Results Increasing redox initiation rate increases the polymerization rate but at high levels also limits working time. Combining 0.86 wt% oxidizing agent with up to 5 wt% plasticizer gave a working time of 3 min and a setting time of 2 min. The selected medium and light body thiol-ene formulations also achieved greater qualitative detail reproduction than the commercial material and reproduced micrometer patterns with 98% accuracy. Significance Improving detail reproduction and setting speed is a primary focus of dental impression material design and synthesis. Radical-mediated polymerizations, particularly thiol-ene reactions, are recognized for their speed, reduced shrinkage, and ‘click’ nature. PMID:24553250

Conducting polymer actuator based on chemically deposited polypyrrole and polyurethane-based solid polymer electrolyte working in air

NASA Astrophysics Data System (ADS)

Choi, Hwa-Jeong; Song, Young-Min; Chung, Ildoo; Ryu, Kwang-Sun; Jo, Nam-Ju

2009-02-01

Conducting polymers (CPs), such as polypyrrole, polythiophene, and polyaniline, are unique in that they have switchable properties due to their two or more mechanically stable oxidation states. Thus, their films or coatings can be easily switched by the application of a small voltage and current to change their volume during electrochemical redox processes. In particular, polypyrrole (PPy) has been studied most extensively because of its high electrical conductivity and good environmental stability under ambient conditions. In this work, we have studied a new CP actuator, fully polymeric, assembled with two PPy film electrodes and a solid polymer electrolyte (SPE), polyurethane/Mg(ClO4)2. Polyurethanes (PUs) were synthesized from 4,4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (1,4-BD) and three types of polyol: poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), and PPG-block-PEG-block-PPG (PPG-co-PEG). The chemical polymerization of PPy by immersion in Py monomer aqueous solution and oxidant aqueous solution is an adequate method to prepare PU/PPy composite film as an actuator. To find the proper thickness of the PPy coating layer for actuation, we measured the displacements of the actuators according to the thickness of the PPy coating layer. The displacement of all actuators is discussed in connection with the properties of the SPE and PPy. All the results obtained in this work show the feasibility of electrochemomechanical devices based on PPy and SPE film being able to work in air.

K4[Fe(CN)6] immobilized anion sensitive protonated amine functionalized polysilsesquioxane films for ultra-low electrochemical detection of dsDNA.

PubMed

Silambarasan, Krishnamoorthy; Narendra Kumar, Alam Venugopal; Joseph, James

2016-03-14

Charge transport in polymeric films bound by redox reagents is a topic of current interest. The dynamics of electroinactive ions across the interface is studied by immobilizing ferrocyanide anion in a polysilsesquioxanes (PSQs) modified electrode. Redox reagents can stay in the polymeric film by either physical forces or electrostatic binding. The present work describes the immobilization of ferro/ferricyanide redox couples in PSQ films possessing protonated amine functional groups by electrostatic interactions. Charge transport in [Fe(CN)6](4-)-PSQs film was found to be anion dependent, and its formal potential value varied with the relative hydrophilic or hydrophobic nature of the anion used in the supporting electrolyte, unlike the observed dependence on solution cation for electrodes modified with metal hexacyanoferrates (Prussian Blue analogues). The [Fe(CN)6](4-) bound PSQs films were extensively characterized by varying different supporting electrolytes anions using cyclic voltammetry. The redox peak currents were linearly proportional to the square root of the scan rate, implying that the transport of charge carriers is accompanied with redox ion diffusion and electron hopping in a confined space. dsDNA molecules were found to interact with this polymer matrix through anionic phosphate groups. Both voltammetry and A.C. impedance spectroscopy studies revealed that these interactions could be exploited for the determination of ultra-low level (0.5 attomolar) of dsDNA present in aqueous solution.

Polymer-modified opal nanopores.

PubMed

Schepelina, Olga; Zharov, Ilya

2006-12-05

The surface of nanopores in opal films, assembled from 205 nm silica spheres, was modified with poly(acrylamide) brushes using surface-initiated atom transfer radical polymerization. The colloidal crystal lattice remained unperturbed by the polymerization. The polymer brush thickness was controlled by polymerization time and was monitored by measuring the flux of redox species across the opal film using cyclic voltammetry. The nanopore size and polymer brush thickness were calculated on the basis of the limiting current change. Polymer brush thickness increased over the course of 26 h of polymerization in a logarithmic manner from 1.3 to 8.5 nm, leading to nanopores as small as 7.5 nm.

Ferrocene bound poly(vinyl chloride) as ion to electron transducer in electrochemical ion sensors.

PubMed

Pawlak, Marcin; Grygolowicz-Pawlak, Ewa; Bakker, Eric

2010-08-15

We report here on the synthesis of poly(vinyl chloride) (PVC) covalently modified with ferrocene groups (FcPVC) and the electrochemical behavior of the resulting polymeric membranes in view of designing all solid state voltammetric ion sensors. The Huisgen cycloaddition ("click chemistry") was found to be a simple and efficient method for ferrocene attachment. A degree of PVC modification with ferrocene groups between 1.9 and 6.1 mol % was achieved. The chemical modification of the PVC backbone does not significantly affect the ion-selective properties (selectivity, mobility, and solvent casting ability) of potentiometric sensing membranes applying this polymer. Importantly, the presence of such ferrocene groups may eliminate the need for an additional redox-active layer between the membrane and the inner electric contact in all solid state sensor designs. Electrochemical doping of this system was studied in a symmetrical sandwich configuration: glassy carbon electrode |FcPVC| glassy carbon electrode. Prior electrochemical doping from aqueous solution, resulting in a partial oxidation of the ferrocene groups, was confirmed to be necessary for the sandwich configuration to pass current effectively. The results suggest that only approximately 2.3 mol % of the ferrocene groups are electrochemically accessible, likely due to surface confined electrochemical behavior in the polymer. Indeed, cyclic voltammetry of aqueous hexacyanoferrate (III) remains featureless at cathodic potentials (down to -0.5 V). This indicates that the modified membrane is not responsive to redox-active species in the sample solution, making it possible to apply this polymer as a traditional, single membrane. Yet, the redox capacity of the electrode modified with this type of membrane was more than 520 microC considering a 20 mm(2) active electrode area, which appears to be sufficient for numerous practical ion voltammetric applications. The electrode was observed to operate reproducibly, with 1% standard deviation, when applying pulsed amperometric techniques.

The effects of three commonly used extraction methods on the redox properties of extracellular polymeric substances from activated sludge.

PubMed

Lu, Qin; Chang, Ming; Yu, Zhen; Zhou, Shungui

2015-01-01

Recently, the redox properties of extracellular polymeric substances (EPS) have attracted the attention of scientists due to their associated environmental significance, such as organic pollutant (e.g. nitroaromatics and substituted nitrobenzenes) degradation and heavy metal (e.g. Cr(VI) and U(VI)) detoxification. Although the separation of EPS from bacterial cells is more often the first step in studies on EPS, and studies have demonstrated that extraction procedures can influence the sorption properties of EPS, few attempts have been made to investigate how separation methods affect the redox properties of the obtained EPS. In this study, three common extraction approaches, that is, centrifugation, formaldehyde+NaOH and ethylene diamine tetra-acetic acid (EDTA), were employed to extract EPS from activated sludge, and the obtained EPS were evaluated for their redox properties using electrochemical means, including cyclic voltammetry and chronoamperometry. In addition, spectroscopic techniques were utilized to explore the structural characteristics and composition of EPS. The results indicated that EPS extracted by EDTA clearly displayed reversible oxidation-reduction peaks in cyclic voltammograms and significantly higher electron-accepting capacity compared with EPS extracted using the other two approaches. Fourier transform infrared spectra and three-dimensional excitation-emission matrix spectra suggested that the EPS extracted with EDTA presented better redox properties because of the effective and efficient extraction of the humic substances, which are important components of the EPS of activated sludge. Therefore, extraction method has an impact on the composition and redox properties of EPS and should be chosen according to research purpose and EPS source.

Ring-opening polymerization of 19-electron [2]cobaltocenophanes: a route to high-molecular-weight, water-soluble polycobaltocenium polyelectrolytes.

PubMed

Mayer, Ulrich F J; Gilroy, Joe B; O'Hare, Dermot; Manners, Ian

2009-08-05

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

Reconstituted Polymeric Materials Derived From Post-Consumer Waste, Industrial Scrap And Virgin Resins Made By Solid State Shear Pulverizat

DOEpatents

Khait, Klementina

2005-02-01

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state pulverization

DOEpatents

Khait, K.

1998-09-29

A method of making polymeric particulates is described wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatible agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product. 29 figs.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state shear pulverization

DOEpatents

Khait, Klementina

2001-01-30

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

Reconstituted polymeric materials derived from post-consumer waste, industrial scrap and virgin resins made by solid state pulverization

DOEpatents

Khait, Klementina

1998-09-29

A method of making polymeric particulates wherein polymeric scrap material, virgin polymeric material and mixtures thereof are supplied to intermeshing extruder screws which are rotated to transport the polymeric material along their length and subject the polymeric material to solid state shear pulverization and in-situ polymer compatibilization, if two or more incompatible polymers are present. Uniform pulverized particulates are produced without addition of a compatibilizing agent. The pulverized particulates are directly melt processable (as powder feedstock) and surprisingly yield a substantially homogeneous light color product.

Electrochemical Properties of Poly(Anthraquinonyl Sulfide)/Graphene Sheets Composites as Electrode Materials for Electrochemical Capacitors.

PubMed

Lee, Wonkyun; Suzuki, Shinya; Miyayama, Masaru

2014-07-30

Poly(anthraquinonyl sulfide) (PAQS)/graphene sheets (GSs) composite was synthesized through in situ polymerization to evaluate its performance as an electrode material for electrochemical capacitors. PAQS was successfully synthesized in the presence of GSs with uniform distribution. PAQS/GSs showed a pair of reversible redox peaks at around 0 V ( vs. Ag/AgCl). The specific capacitance of PAQS/GSs was 349 F·g -1 (86 mAh·g -1 ) at a current density of 500 mA·g -1 , and a capacitance of 305 F·g -1 was maintained even at a high current density of 5000 mA·g -1 . The in situ polymerization of PAQS with GSs facilitated their interaction and enabled faster charge transfer and redox reaction, resulting in enhanced electrode properties.

Fundamentally Addressing Bromine Storage through Reversible Solid-State Confinement in Porous Carbon Electrodes: Design of a High-Performance Dual-Redox Electrochemical Capacitor.

PubMed

Yoo, Seung Joon; Evanko, Brian; Wang, Xingfeng; Romelczyk, Monica; Taylor, Aidan; Ji, Xiulei; Boettcher, Shannon W; Stucky, Galen D

2017-07-26

Research in electric double-layer capacitors (EDLCs) and rechargeable batteries is converging to target systems that have battery-level energy density and capacitor-level cycling stability and power density. This research direction has been facilitated by the use of redox-active electrolytes that add faradaic charge storage to increase energy density of the EDLCs. Aqueous redox-enhanced electrochemical capacitors (redox ECs) have, however, performed poorly due to cross-diffusion of soluble redox couples, reduced cycle life, and low operating voltages. In this manuscript, we propose that these challenges can be simultaneously met by mechanistically designing a liquid-to-solid phase transition of oxidized catholyte (or reduced anolyte) with confinement in the pores of electrodes. Here we demonstrate the realization of this approach with the use of bromide catholyte and tetrabutylammonium cation that induces reversible solid-state complexation of Br 2 /Br 3 - . This mechanism solves the inherent cross-diffusion issue of redox ECs and has the added benefit of greatly stabilizing the reactive bromine generated during charging. Based on this new mechanistic insight on the utilization of solid-state bromine storage in redox ECs, we developed a dual-redox EC consisting of a bromide catholyte and an ethyl viologen anolyte with the addition of tetrabutylammonium bromide. In comparison to aqueous and organic electric double-layer capacitors, this system enhances energy by factors of ca. 11 and 3.5, respectively, with a specific energy of ∼64 W·h/kg at 1 A/g, a maximum power density >3 kW/kg, and cycling stability over 7000 cycles.

Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

DOE PAGES

Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...

2015-11-02

Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10 -3 S cm -1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

Redox-Responsive Biomimetic Polymeric Micelle for Simultaneous Anticancer Drug Delivery and Aggregation-Induced Emission Active Imaging.

PubMed

Hu, Jun; Zhuang, Weihua; Ma, Boxuan; Su, Xin; Yu, Tao; Li, Gaocan; Hu, Yanfei; Wang, Yunbing

2018-05-10

Intelligent polymeric micelles have been developed as potential nanoplatforms for efficient drug delivery and diagnosis. Herein, we successfully prepared redox-sensitive polymeric micelles combined aggregation-induced emission (AIE) imaging as an outstanding anticancer drug carrier system for simultaneous chemotherapy and bioimaging. The amphiphilic copolymer TPE-SS-PLAsp- b-PMPC could self-assemble into spherical micelles, and these biomimetic micelles exhibited great biocompatibility and remarkable ability in antiprotein adsorption, showing great potential for biomedical application. Anticancer drug doxorubicin (DOX) could be encapsulated during the self-assembly process, and these drug-loaded micelles showed intelligent drug release and improved antitumor efficacy due to the quick disassembly in response to high levels of glutathione (GSH) in the environment. Moreover, the intracellular DOX release could be traced through the fluorescent imaging of these AIE micelles. As expected, the in vivo antitumor study exhibited that these DOX-carried micelles showed better antitumor efficacy and less adverse effects than that of free DOX. These results strongly indicated that this smart biomimetic micelle system would be a prominent candidate for chemotherapy and bioimaging.

A Review of RedOx Cycling of Solid Oxide Fuel Cells Anode

PubMed Central

Faes, Antonin; Hessler-Wyser, Aïcha; Zryd, Amédée; Van Herle, Jan

2012-01-01

Solid oxide fuel cells are able to convert fuels, including hydrocarbons, to electricity with an unbeatable efficiency even for small systems. One of the main limitations for long-term utilization is the reduction-oxidation cycling (RedOx cycles) of the nickel-based anodes. This paper will review the effects and parameters influencing RedOx cycles of the Ni-ceramic anode. Second, solutions for RedOx instability are reviewed in the patent and open scientific literature. The solutions are described from the point of view of the system, stack design, cell design, new materials and microstructure optimization. Finally, a brief synthesis on RedOx cycling of Ni-based anode supports for standard and optimized microstructures is depicted. PMID:24958298

Electrochemical Properties of Poly(Anthraquinonyl Sulfide)/Graphene Sheets Composites as Electrode Materials for Electrochemical Capacitors

PubMed Central

Lee, Wonkyun; Suzuki, Shinya; Miyayama, Masaru

2014-01-01

Poly(anthraquinonyl sulfide) (PAQS)/graphene sheets (GSs) composite was synthesized through in situ polymerization to evaluate its performance as an electrode material for electrochemical capacitors. PAQS was successfully synthesized in the presence of GSs with uniform distribution. PAQS/GSs showed a pair of reversible redox peaks at around 0 V (vs. Ag/AgCl). The specific capacitance of PAQS/GSs was 349 F·g−1 (86 mAh·g−1) at a current density of 500 mA·g−1, and a capacitance of 305 F·g−1 was maintained even at a high current density of 5000 mA·g−1. The in situ polymerization of PAQS with GSs facilitated their interaction and enabled faster charge transfer and redox reaction, resulting in enhanced electrode properties. PMID:28344238

Thio-amide functionalized polymers via polymerization or post-polymerization modification

NASA Astrophysics Data System (ADS)

Ozcam, Ali; Henke, Adam; Stibingerova, Iva; Srogl, Jiri; Genzer, Jan

2011-03-01

Decreasing supplies of fresh water and increasing population necessitates development of advanced water cleaning technologies, which would facilitate the removal of water pollutants. Amongst the worst of such contaminants are heavy metals and cyanides, infamous for their high toxicity. To assist the water purification processes, we aim to synthesize functionalized macromolecules that would contribute in the decontamination processes by scavenging detrimental chemicals. Epitomizing this role thio-amide unit features remarkable chemical flexibility that facilitates reversible catch-release of the ions, where the behavior controlled by subtle red-ox changes in the environment. Chemical tunability of the thio-amide moiety enables synthesis of thio-amide based monomers and post-polymerization modification agents. Two distinct synthetic pathways, polymerization and post-polymerization modification, have been exploited, leading to functional thioamide-based macromolecules: thioamide-monomers were copolymerized with N-isopropylacrylamide and post-polymerization modifications of poly(dimethylaminoethyl methacrylate) and poly(propargyl methacrylate) were accomplished via quarternization and ``click'' reactions, respectively.

Polymeric Beads for Organic Coatings

DTIC Science & Technology

1982-10-31

Clear Solid Polymeric Beads A solid polymeric bead is comprised of a sol id mass of polymerized unsaturated polyester/styrene resin mixture . 2. lear...than the current unsaturated polyester resin . For example, a bead male from acrylic resin could be more trans- - parent, more durable and provide more...0.44 Isopropyl Alcohol I 11.26 I 1 .73 60% Wt. Alkyd Resin - Volume I 251.26 i 30.52 " Sol ids 51% 1 I Anti.-Skinning Agent I 0.90 I 0.12 Mineral

Iodine/iodide-free dye-sensitized solar cells.

PubMed

Yanagida, Shozo; Yu, Youhai; Manseki, Kazuhiro

2009-11-17

Dye-sensitized solar cells (DSSCs) are built from nanocrystalline anatase TiO(2) with a 101 crystal face (nc-TiO(2)) onto which a dye is absorbed, ruthenium complex sensitizers, fluid I(-)/I(3)(-) redox couples with electrolytes, and a Pt-coated counter electrode. DSSCs have now reached efficiencies as high as 11%, and G24 Innovation (Cardiff, U.K.) is currently manufacturing them for commercial use. These devices offer several distinct advantages. On the basis of the electron lifetime and diffusion coefficient in the nc-TiO(2) layer, DSSCs maintain a diffusion length on the order of several micrometers when the dyed-nc-TiO(2) porous layer is covered by redox electrolytes of lithium and/or imidazolium iodide and their polyiodide salts. The fluid iodide/iodine (I(-)/I(3)(-)) redox electrolytes can infiltrate deep inside the intertwined nc-TiO(2) layers, promoting the mobility of the nc-TiO(2) layers and serving as a hole-transport material of DSSCs. As a result, these materials eventually give a respectable photovoltaic performance. On the other hand, fluid I(-)/I(3)(-) redox shuttles have certain disadvantages: reduced performance control and long-term stability and incompatibility with some metallic component materials. The I(-)/I(3)(-) redox shuttle shows a significant loss in short circuit current density and a slight loss in open circuit voltage, particularly in highly viscous electrolyte-based DSSC systems. Iodine can also act as an oxidizing agent, corroding metals, such as the grid metal Ag and the Pt mediator on the cathode, especially in the presence of water and oxygen. In addition, the electrolytes (I(-)/I(3)(-)) can absorb visible light (lambda = approximately 430 nm), leading to photocurrent loss in the DSSC. Therefore, the introduction of iodide/iodine-free electrolytes or hole-transport materials (HTMs) could lead to cost-effective alternatives to TiO(2) DSSCs. In this Account, we discuss the iodide/iodine-free redox couple as a substitute for the fluid I(-)/I(3)(-) redox shuttle. We also review the adaptation of solid-state HTMs to the iodide/iodine-free solid-state DSSCs with an emphasis on their pore filling and charge mobility in devices and the relationship of those values to the performance of the resulting iodide/iodine-free DSSCs. We demonstrate how the structures of the sensitizing dye molecules and additives of lithium or imidazolium salts influence device performance. In addition, the self-organizing molecular interaction for electronic contact of HTMs to dye molecules plays an important role in unidirectional charge diffusion at interfaces. The poly(3,4-ethylenedioxythiophene) (PEDOT)-based DSSCs, which we obtain through photoelectrochemical polymerization (PEP) using 3-alkylthiophen-bearing ruthenium dye, HRS-1, and bis-EDOT, demonstrates the importance of nonbonding interface contact (e.g., pi-pi-stacking) for the successful inclusion of HTMs.

Composition and method of preparation of solid state dye laser rods

DOEpatents

Hermes, Robert E.

1992-01-01

The present invention includes solid polymeric-host laser rods prepared using bulk polymerization of acrylic acid ester comonomers which, when admixed with dye(s) capable of supporting laser oscillation and polymerized with a free radical initiator under mild thermal conditions, produce a solid product having the preferred properties for efficient lasing. Unsaturated polymerizable laser dyes can also be employed as one of the comonomers. Additionally, a method is disclosed which alleviates induced optical stress without having to anneal the polymers at elevated temperatures (>85.degree. C.).

Extracellular Polymeric Substances from Shewanella sp. HRCR-1 Biofilms: Characterization by Infrared Spectroscopy and Proteomics

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

Cao, Bin; Shi, Liang; Brown, Roslyn N.

This study characterizes the composition of extracellular polymeric substances (EPS) from Shewanella sp. HRCR-1 biofilms to provide insight into potential interactions of EPS with redox-active metals and radionuclides. Both bound and loosely associated EPS were extracted from Shewanella sp. HRCR-1 biofilms prepared using a hollow-fiber membrane biofilm reactor (HfMBR). FTIR spectra revealed the presence of proteins, polysaccharides, nucleic acids, membrane lipids, and fatty acids in both bound and loosely associated EPS. Using a global proteomic approach, a total of 58 extracellular and outer membrane proteins were identified in the EPS. These included homologues of multiple S. oneidensis MR-1 proteins thatmore » potentially contribute to key physiological biofilm processes, such as biofilm-promoting protein BpfA, surface-associated serine protease, nucleotidases (CpdB and UshA), an extracellular lipase, and oligopeptidases (PtrB and a M13 family oligopeptidase lipoprotein). In addition, 20 redox proteins were found in extracted EPS. Among the detected redox proteins were the homologues of two S. oneidensis MR-1 c-type cytochromes, MtrC and OmcA, which have been implicated in extracellular electron transfer. Given their detection in the EPS of Shewanella sp. HRCR 1 biofilms, c-type cytochromes may contribute to the possible redox activity of the biofilm matrix and play important roles in extracellular electron transfer reactions.« less

High–energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane

PubMed Central

Jia, Chuankun; Pan, Feng; Zhu, Yun Guang; Huang, Qizhao; Lu, Li; Wang, Qing

2015-01-01

Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage. PMID:26702440

High-energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane.

PubMed

Jia, Chuankun; Pan, Feng; Zhu, Yun Guang; Huang, Qizhao; Lu, Li; Wang, Qing

2015-11-01

Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage.

Acrylate intercalation and in situ polymerization in iron-, cobalt-, or manganese-substituted nickel hydroxides.

PubMed

Vaysse, C; Guerlou-Demourgues, L; Duguet, E; Delmas, C

2003-07-28

A chimie douce route based on successive redox and exchange reactions has allowed us to prepare new hybrid organic-inorganic materials, composed of polyacrylate macromolecules intercalated into layered double hydroxides (LDHs), deriving from Ni(OH)(2). Monomer intercalation and in situ polymerization mechanisms have appeared to be strongly dependent upon the nature of the substituting cation in the slabs. In the case of iron-based LDHs, a phase containing acrylate monomeric intercalates has been isolated and identified by X-ray diffraction and infrared spectroscopy. Second, interslab free-radical polymerization of acrylate anions has been successfully initiated using potassium persulfate. In cobalt- or manganese-based LDHs, one-step polymerization has been observed, leading directly to a material containing polyacrylate intercalate.

Conductive cotton prepared by polyaniline in situ polymerization using laccase.

PubMed

Zhang, Ya; Dong, Aixue; Wang, Qiang; Fan, Xuerong; Cavaco-Paulo, Artur; Zhang, Ying

2014-09-01

The high-redox-potential catalyst laccase, isolated from Aspergillus, was first used as a biocatalyst in the oxidative polymerization of water-soluble conductive polyaniline, and then conductive cotton was prepared by in situ polymerization under the same conditions. The polymerization of aniline was performed in a water dispersion of sodium dodecylbenzenesulfonate (SDBS) micellar solution with atmospheric oxygen serving as the oxidizing agent. This method is ecologically clean and permits a greater degree of control over the kinetics of the reaction. The conditions for polyaniline synthesis were optimized. Characterizations of the conducting polyaniline and cotton were carried out using Fourier transform infrared spectroscopy, UV-vis spectroscopy, cyclic voltammetry, the fabric induction electrostatic tester, and the far-field EMC shielding effectiveness test fixture.

A reference electrode based on polyvinyl butyral (PVB) polymer for decentralized chemical measurements.

PubMed

Guinovart, Tomàs; Crespo, Gastón A; Rius, F Xavier; Andrade, Francisco J

2014-04-22

A new solid-state reference electrode using a polymeric membrane of polyvinyl butyral (PVB), Ag/AgCl and NaCl to be used in decentralized chemical measurements is presented. The electrode is made by drop-casting the membrane cocktail onto a glassy carbon (GC) substrate. A stable potential (less than 1 mV dec(-1)) over a wide range of concentrations for the several chemical species tested is obtained. No significant influence to changes in redox potential, light and pH are observed. The response of this novel electrode shows good correlation when compared with a conventional double-junction reference electrode. Also good long-term stability (90±33 μV/h) and a lifetime of approximately 4 months are obtained. Aspects related to the working mechanisms are discussed. Atomic Force Microscopy (AFM) studies reveal the presence of nanopores and channels on the surface, and electrochemical impedance spectroscopy (EIS) of optimized electrodes show low bulk resistances, usually in the kΩ range, suggesting that a nanoporous polymeric structure is formed in the interface with the solution. Future applications of this electrode as a disposable device for decentralized measurements are discussed. Examples of the utilization on wearable substrates (tattoos, fabrics, etc) are provided. Copyright © 2014 Elsevier B.V. All rights reserved.

Redox and pH Dual-Responsive Polymeric Micelles with Aggregation-Induced Emission Feature for Cellular Imaging and Chemotherapy.

PubMed

Zhuang, Weihua; Xu, Yangyang; Li, Gaocan; Hu, Jun; Ma, Boxuan; Yu, Tao; Su, Xin; Wang, Yunbing

2018-05-21

Intelligent polymeric micelles for antitumor drug delivery and tumor bioimaging have drawn a broad attention because of their reduced systemic toxicity, enhanced efficacy of drugs, and potential application of tumor diagnosis. Herein, we developed a multifunctional polymeric micelle system based on a pH and redox dual-responsive mPEG-P(TPE- co-AEMA) copolymer for stimuli-triggered drug release and aggregation-induced emission (AIE) active imaging. These mPEG-P(TPE- co-AEMA)-based micelles showed excellent biocompatibility and emission property, exhibiting great potential application for cellular imaging. Furthermore, the antitumor drug doxorubicin (DOX) could be encapsulated during self-assembly process with high loading efficiency, and a DOX-loaded micelle system with a size of 68.2 nm and narrow size distribution could be obtained. DOX-loaded micelles demonstrated great tumor suppression ability in vitro, and the dual-responsive triggered intracellular drug release could be further traced. Moreover, DOX-loaded micelles could efficiently accumulate at the tumor site because of enhanced permeability and retention effect and long circulation of micelles. Compared with free DOX, DOX-loaded micelles exhibited better antitumor effect and significantly reduced adverse effects. Given the efficient accumulation targeting to tumor tissue, dual-responsive drug release, and excellent AIE property, this polymeric micelle would be a potential candidate for cancer therapy and diagnosis.

Melting line of polymeric nitrogen

NASA Astrophysics Data System (ADS)

Yakub, L. N.

2013-05-01

We made an attempt to predict location of the melting line of polymeric nitrogen using two equations for Helmholtz free energy: proposed earlier for cubic gauche-structure and developed recently for liquid polymerized nitrogen. The P-T relation, orthobaric densities and latent heat of melting were determined using a standard double tangent construction. The estimated melting temperature decreases with increasing pressure, alike the temperature of molecular-nonmolecular transition in solid. We discuss the possibility of a triple point (solid-molecular fluid-polymeric fluid) at ˜80 GPa and observed maximum of melting temperature of nitrogen.

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

Dual pH/redox responsive and CD44 receptor targeting hybrid nano-chrysalis based on new oligosaccharides of hyaluronan conjugates.

PubMed

Chen, Daquan; Dong, Xue; Qi, Mengjiao; Song, Xiaoyan; Sun, Jingfang

2017-02-10

A smart hybrid microenvironment-mediated dual pH/redox-responsive polymeric nanoparticles combined with inorganic calcium phosphate (CaP) was fabricated, which we term as armored nano-chrysalis inspired by butterfly pupa. The nano-chrysalis has an inner core composed of specially designed oligosaccharides of hyaluronan (oHA) targeting CD44 receptor. The inner core has two functions, i.e., the dual pH/redox responsive polymeric conjugate and the fluorescent curcumin-prodrug function. The prepared nano-chrysalis possessed a smaller size (102.5±4.6nm) than the unarmored nano-chrysalis (122.5±6.6nm). Interestingly, while the nano-chrysalis were stable under pH 7.4, when incubated under the tumor acidic conditions (pH 6.5) the outer CaP armor would dissolve in a pH-dependent, sustained manner. Moreover, nano-chrysalis was demonstrated to present the most effective antitumor efficacy than other formulations. This study provides a promising smart nano-carrier platform to enhance the stability, decrease the side effects, and improve the therapeutic efficacy of anticancer drugs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Composite Solid Electrolyte For Lithium Cells

NASA Technical Reports Server (NTRS)

Peled, Emmanuel; Nagasubramanian, Ganesan; Halpert, Gerald; Attia, Alan I.

1994-01-01

Composite solid electrolyte material consists of very small particles, each coated with thin layer of Lil, bonded together with polymer electrolyte or other organic binder. Material offers significant advantages over other solid electrolytes in lithium cells and batteries. Features include high ionic conductivity and strength. Composite solid electrolyte expected to exhibit flexibility of polymeric electrolytes. Polymer in composite solid electrolyte serves two purposes: used as binder alone, conduction taking place only in AI2O3 particles coated with solid Lil; or used as both binder and polymeric electrolyte, providing ionic conductivity between solid particles that it binds together.

Cell for making secondary batteries

DOEpatents

Visco, Steven J.; Liu, Meilin; DeJonghe, Lutgard C.

1992-01-01

The present invention provides all solid-state lithium and sodium batteries operating in the approximate temperature range of ambient to 145.degree. C. (limited by melting points of electrodes/electrolyte), with demonstrated energy and power densities far in excess of state-of-the-art high-temperature battery systems. The preferred battery comprises a solid lithium or sodium electrode, a polymeric electrolyte such as polyethylene oxide doped with lithium triflate (PEO.sub.8 LiCF.sub.3 SO.sub.3), and a solid-state composite positive electrode containing a polymeric organosulfur electrode, (SRS).sub.n, and carbon black, dispersed in a polymeric electrolyte.

Cell for making secondary batteries

DOEpatents

Visco, S.J.; Liu, M.; DeJonghe, L.C.

1992-11-10

The present invention provides all solid-state lithium and sodium batteries operating in the approximate temperature range of ambient to 145 C (limited by melting points of electrodes/electrolyte), with demonstrated energy and power densities far in excess of state-of-the-art high-temperature battery systems. The preferred battery comprises a solid lithium or sodium electrode, a polymeric electrolyte such as polyethylene oxide doped with lithium trifluorate (PEO[sub 8]LiCF[sub 3]SO[sub 3]), and a solid-state composite positive electrode containing a polymeric organosulfur electrode, (SRS)[sub n], and carbon black, dispersed in a polymeric electrolyte. 2 figs.

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

PubMed

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

2017-12-27

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

Spatial Control of Cell Transfection Using Soluble or Solid-Phase Redox Agents and a Redox-Active Ferrocenyl Lipid

PubMed Central

Aytar, Burcu S.; Muller, John P. E.; Kondo, Yukishige; Abbott, Nicholas L.; Lynn, David M.

2013-01-01

We report principles for active, user-defined control over the locations and timing with which DNA is expressed in cells. Our approach exploits unique properties of a ferrocenyl cationic lipid that is inactive when oxidized, but active when chemically reduced. We show that methods that exert spatial control over the administration of reducing agents can lead to local activation of lipoplexes and spatial control over gene expression. The versatility of this approach is demonstrated using both soluble and solid-phase reducing agents. These methods provide control over cell transfection, including methods for remote activation and the patterning of expression using solid-phase redox agents, that are difficult to achieve using conventional lipoplexes. PMID:23965341

Spatial control of cell transfection using soluble or solid-phase redox agents and a redox-active ferrocenyl lipid.

PubMed

Aytar, Burcu S; Muller, John P E; Kondo, Yukishige; Abbott, Nicholas L; Lynn, David M

2013-09-11

We report principles for active, user-defined control over the locations and timing with which DNA is expressed in cells. Our approach exploits unique properties of a ferrocenyl cationic lipid that is inactive when oxidized, but active when chemically reduced. We show that methods that exert spatial control over the administration of reducing agents can lead to local activation of lipoplexes and spatial control over gene expression. The versatility of this approach is demonstrated using both soluble and solid-phase reducing agents. These methods provide control over cell transfection, including methods for remote activation and the patterning of expression using solid-phase redox agents, that are difficult to achieve using conventional lipoplexes.

From dense monomer salt crystals to CO2 selective microporous polyimides via solid-state polymerization.

PubMed

Unterlass, Miriam M; Emmerling, Franziska; Antonietti, Markus; Weber, Jens

2014-01-14

Fully aromatic polyimides are synthesized via solid-state polymerization of the corresponding monomer salts. The crystal structure of salts shows strong hydrogen bonding of the reactive groups and thereby paves the way for solid-state transformations. The polycondensation yields copies of the initial salt crystallite habits, accompanied by the development of a porosity especially suited for CO2.

Design, Synthesis, and Chemical Processing of Hierarchical Ceramic Structures for Aerospace Applications

DTIC Science & Technology

1993-03-30

Massachusetts Institute of Technology, Cambridge, MA 02139I ABSTRACT polysilanes." Pyrolysis of these polymers usually The decomposition of polymeric SiC ...of soluble polymeric solids. Pyrolysis of these polymers in argon yielded The precursors were prepared by adding a TiC/A120 3 composite at 12501C...formation of soluble polymeric solids. Pyrolysis described an approach for synthesizing AI2O/ SiC of these polymers in argon yielded TiC/AI203

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

Impact of redox agents on the extractability of gluten proteins during bread making.

PubMed

Lagrain, Bert; Thewissen, Bert G; Brijs, Kristof; Delcour, Jan A

2007-06-27

The gluten proteins gliadin and glutenin are important for dough and bread characteristics. In the present work, redox agents were used to impact gluten properties and to study gliadin-glutenin interactions in bread making. In control bread making, mixing increased the extractability of glutenin. The level of SDS-extractable glutenin decreased during fermentation and then further in the oven. The levels of extractable alpha- and gamma-gliadin also decreased during bread baking due to gliadin-glutenin polymerization. Neither oxidizing nor reducing agents had an impact on glutenin extractabilities after mixing. The redox additives did not affect omega-gliadin extractabilities during bread making due to their lack of cysteine residues. Potassium iodate (0.82-2.47 micromol/g of protein) and potassium bromate (1.07-3.17 micromol/g of protein) increased both alpha- and gamma-gliadin extractabilities during baking. Increasing concentrations of glutathione (1.15-3.45 micromol/g of protein) decreased levels of extractable alpha- and gamma-gliadins during baking. The work not only demonstrated that, during baking, glutenin and gliadin polymerize through heat-induced sulfhydryl-disulfide exchange reactions, but also demonstrated for the first time that oxidizing agents, besides their effect on dough rheology and hence bread volume, hinder gliadin-glutenin linking during baking, while glutathione increases the degree of covalent gliadin to glutenin linking.

Facile fabrication of redox-responsive thiol-containing drug delivery system via RAFT polymerization.

PubMed

Zhuang, Yuanyuan; Su, Yue; Peng, Yu; Wang, Dali; Deng, Hongping; Xi, Xiaodong; Zhu, Xinyuan; Lu, Yunfeng

2014-04-14

A novel kind of redox-responsive polymeric drug delivery system has been designed and prepared successfully through the coupling of the multithiol branched polymers and thiol-containing drugs. The branched poly((S-(4-vinyl) benzyl S'-propyltrithiocarbonate)-co-(poly(ethylene glycol) methacrylate)) (poly(VBPT-co-PEGMA)) was synthesized by one-pot reaction via reversible addition-fragmentation chain transfer (RAFT) copolymerization. Subsequently, the hydrophobic thiol-containing anticancer drug 6-mercaptopurine (MP) was conjugated to poly(VBPT-co-PEGMA) by thiol-disulfide exchange reaction, resulting in the formation of poly(VBPT-co-PEGMA)-S-S-MP conjugate. Due to its amphiphilicity, poly(VBPT-co-PEGMA)-S-S-MP conjugate self-assembled into amphiphilic micelles in aqueous solution. Under a reductive environment, the disassembly of polymeric micelles resulted in the MP release. Flow cytometry and confocal laser scanning microscopy (CLSM) measurements demonstrated that the poly(VBPT-co-PEGMA)-S-S-MP micelles could be taken up by Raji cells (a Burkitt lymphoma cell line). The viability of the Raji cells incubated with the glutathione (GSH) mediated poly(VBPT-co-PEGMA)-S-S-MP micelles was investigated by Cell Counting Kit-8 (CCK-8) assay. The experimental results showed that the viability of the glutathione monoester (GSH-OEt) pretreated cells was lower than that without pretreatment, while the viability of the buthionine sulfoximine (BSO) pretreated cells was higher than that without pretreatment. The poly(VBPT-co-PEGMA)-S-S-MP micelles could induce the apoptosis of Raji cells, and the apoptosis behavior was dose-dependent. This redox-responsive polymer-drug conjugate provides a promising platform for the delivery of thiol-containing biological molecules.

Redox activity distinguishes solid-state electron transport from solution-based electron transfer in a natural and artificial protein: cytochrome C and hemin-doped human serum albumin.

PubMed

Amdursky, Nadav; Ferber, Doron; Pecht, Israel; Sheves, Mordechai; Cahen, David

2013-10-28

Integrating proteins in molecular electronic devices requires control over their solid-state electronic transport behavior. Unlike "traditional" electron transfer (ET) measurements of proteins that involve liquid environments and a redox cycle, no redox cofactor is needed for solid-state electron transport (ETp) across the protein. Here we show the fundamental difference between these two approaches by macroscopic area measurements, which allow measuring ETp temperature dependence down to cryogenic temperatures, via cytochrome C (Cyt C), an ET protein with a heme (Fe-porphyrin) prosthetic group as a redox centre. We compare the ETp to electrochemical ET measurements, and do so also for the protein without the Fe (with metal-free porphyrin) and without porphyrin. As removing the porphyrin irreversibly alters the protein's conformation, we repeat these measurements with human serum albumin (HSA), 'doped' (by non-covalent binding) with a single hemin equivalent, i.e., these natural and artificial proteins share a common prosthetic group. ETp via Cyt C and HSA-hemin are very similar in terms of current magnitude and temperature dependence, which suggests similar ETp mechanisms via these two systems, thermally activated hopping (with ~0.1 eV activation energy) >190 K and tunneling by superexchange <190 K. Also, ET rates to and from the Fe redox centres (Fe(2+) <=> Fe(3+) + e(-)), measured by electrochemistry of HSA-hemin are only 4 times lower than those for Cyt C. However, while removing the Fe redox centre from the porphyrin ring markedly affects the ET rate, it hardly changes the ETp currents through these proteins, while removing the macrocycle (from HSA, which retains its conformation) significantly reduces ETp efficiency. These results show that solid-state ETp across proteins does not require the presence of a redox cofactor, and that while for ET the Fe ion is the main electron mediator, for ETp the porphyrin ring has this function.

Proton conducting membranes for high temperature fuel cells with solid state water free membranes

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Yen, Shiao-Pin S. (Inventor)

2006-01-01

A water free, proton conducting membrane for use in a fuel cell is fabricated as a highly conducting sheet of converted solid state organic amine salt, such as converted acid salt of triethylenediamine with two quaternized tertiary nitrogen atoms, combined with a nanoparticulate oxide and a stable binder combined with the converted solid state organic amine salt to form a polymeric electrolyte membrane. In one embodiment the membrane is derived from triethylenediamine sulfate, hydrogen phosphate or trifiate, an oxoanion with at least one ionizable hydrogen, organic tertiary amine bisulfate, polymeric quaternized amine bisulfate or phosphate, or polymeric organic compounds with quaternizable nitrogen combined with Nafion to form an intimate network with ionic interactions.

Solid coatings deposited from liquid methyl methacrylate via Plasma Polymerization

NASA Astrophysics Data System (ADS)

Wurlitzer, Lisa; Maus-Friedrichs, Wolfgang; Dahle, Sebastian

2016-09-01

The polymerization of methyl methacrylate via plasma discharges is well known today. Usually, plasma-enhanced chemical vapor deposition (PECVD) is used to deposit polymer coatings. Solid coatings are formed out of the liquid phase from methyl methacrylate via dielectric barrier discharge. The formation of the coating proceeds in the gas and the liquid phase. To learn more about the reactions in the two phases, the coatings from MMA monomer will be compared to those from MMA resin. Finally, attenuated total reflection infrared spectroscopy, confocal laser scanning microscopy and X-ray photoelectron spectroscopy are employed to characterize the solid coatings. In conclusion, the plasma enhanced chemical solution deposition is compared to the classical thermal polymerization of MMA.

Reactivity of bacterial and fungal laccases with lignin under alkaline conditions.

PubMed

Moya, Raquel; Saastamoinen, Päivi; Hernández, Manuel; Suurnäkki, Anna; Arias, Enriqueta; Mattinen, Maija-Liisa

2011-11-01

The ability of Streptomyces ipomoea laccase to polymerize secoisolariciresinol lignan and technical lignins was assessed. The reactivity of S. ipomoea laccase was also compared to that of low redox fungal laccase from Melanocarpus albomyces using low molecular mass p-coumaric, ferulic and sinapic acid as well as natural (acetosyringone) and synthetic 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) mediators as substrates. Oxygen consumption measurement, MALDI-TOF MS and SEC were used to follow the enzymatic reactions at pH 7, 8, 9 and 10 at 30°C and 50°C. Polymerization of lignins and lignan by S. ipomoea laccase under alkaline reaction conditions was observed, and was enhanced in the presence of acetosyringone almost to the level obtained with M. albomyces laccase without mediator. Reactivities of the enzymes towards acetosyringone and TEMPO were similar, suggesting exploitation of the compounds and low redox laccase in lignin valorization under alkaline conditions. The results have scientific impact on basic research of laccases. Copyright © 2011 Elsevier Ltd. All rights reserved.

Cells having cathodes containing polycarbon disulfide materials

DOEpatents

Okamoto, Yoshi; Skotheim, Terje A.; Lee, Hung S.

1995-08-15

The present invention relates to an electric current producing cell which contains an anode, a cathode having as a cathode-active material one or more carbon-sulfur compounds of the formula (CS.sub.x).sub.n, in which x takes values from 1.2 to 2.3 and n is greater or equal to 2, and where the redox process does not involve polymerization and de-polymerization by forming and breaking S--S bonds in the polymer backbone. The cell also contains an electrolyte which is chemically inert with respect to the anode and the cathode.

Enhancing aerobic digestion potential of municipal waste-activated sludge through removal of extracellular polymeric substance.

PubMed

Merrylin, J; Kaliappan, S; Kumar, S Adish; Yeom, Ick-Tae; Banu, J Rajesh

2014-01-01

A protease-secreting bacteria was used to pretreat municipal sewage sludge to enhance aerobic digestion. To enhance the accessibility of the sludge to the enzyme, extracellular polymeric substances were removed using citric acid thereby removing the flocs in the sludge. The conditions for the bacterial pretreatment were optimized using response surface methodology. The results of the bacterial pretreatment indicated that the suspended solids reduction was 18% in sludge treated with citric acid and 10% in sludge not treated with citric acid whereas in raw sludge, suspended solids reduction was 5.3%. Solubilization was 10.9% in the sludge with extracellular polymeric substances removed in contrast to that of the sludge with extracellular polymeric substances, which was 7.2%, and that of the raw sludge, which was just 4.8%. The suspended solids reduction in the aerobic reactor containing pretreated sludge was 52.4% whereas that in the control reactor was 15.3%. Thus, pretreatment with the protease-secreting bacteria after the removal of extracellular polymeric substances is a cost-effective and environmentally friendly method.

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

PubMed Central

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-01-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-12-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g-1 based on solid-state redox reaction of oxide ions.

The autowave modes of solid phase polymerization of metal-containing monomers in two- and three-dimensional fiberglass-filled matrices

NASA Astrophysics Data System (ADS)

Barelko, V. V.; Pomogailo, A. D.; Dzhardimalieva, G. I.; Evstratova, S. I.; Rozenberg, A. S.; Uflyand, I. E.

1999-06-01

The phenomenon of autowave (frontal) solid phase polymerization of metal-containing monomers based on metal-acrylamide complexes is considered. The comparison of the features of autowave processes realized in both the single-component matrices of the monomer and the matrices filled by the fiberglass materials is performed. The unstable regimes of the polymerization wave as well as the conditions for the stabilization of the flat front in the filled matrices are described. The peculiarities of the frontal regimes in the three- and two-dimensional media are studied. Some possibilities for using of autowave polymerization in the fabrication of the polymer-fiberglass composites and composition prepregs are discussed.

Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection

DOEpatents

Richardson, Thomas J.; Ross, Philip N.

1999-01-01

A class of organic redox shuttle additives is described, preferably comprising nitrogen-containing aromatics compounds, which can be used in a high temperature (85.degree. C. or higher) electrochemical storage cell comprising a positive electrode, a negative electrode, and a solid polymer electrolyte to provide overcharge protection to the cell. The organic redox additives or shuttles are characterized by a high diffusion coefficient of at least 2.1.times.10.sup.-8 cm.sup.2 /second and a high onset potential of 2.5 volts or higher. Examples of such organic redox shuttle additives include an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene, and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1,2-dione.

Coordinated pH/redox dual-sensitive and hepatoma-targeted multifunctional polymeric micelle system for stimuli-triggered doxorubicin release: Synthesis, characterization and in vitro evaluation.

PubMed

Wang, Lele; Tian, Baocheng; Zhang, Jing; Li, Keke; Liang, Yan; Sun, Yujie; Ding, Yuanyuan; Han, Jingtian

2016-03-30

Multifunctional polymeric micelles self-assembled from a DOX-conjugated methoxypolyethylene glycols-b-poly (6-O-methacryloyl-D-galactopyranose)-disulfide bond-DOX (mPEG-b-PMAGP-SS-DOX) copolymer were prepared as an antitumor carrier for doxorubicin delivery, of which the chemical modification with disulfide bonds and hydrazone bonds allowed micelles to release doxorubicin (DOX) selectively at acidic pH and high redox conditions. The resulting micelles exhibited coordinated pH/redox dual-sensitive and hepatoma-targeted multifunction with sustaining stability in aqueous media. The multifunctional micelles showed spherical shapes with a mean diameter of 93 ± 2.08 nm, a low polydispersity index (PDI) of 0.21, a low CMC value of 0.095 mg/mL, a high drug grafting degree of 56.9% and a drug content of 39.0%. Remarkably, in vitro drug release studies clearly exhibited a pH and redox dual-sensitive drug release profile with significantly accelerated drug release treated with pH 5.0 and 10mM GSH (88.4% in 72 h) without drug burst release. The tumor proliferation assays indicated that DOX-grafted micelles, along with low cytotoxicity and well biocompatibility to normal cells up to a concentration of 10 μg/mL, inhibited the proliferation of HepG2 cells in a formulation-, time- and concentration-dependent manner in comparison with MCF-7 cells which was similar to free DOX. Anticancer activity releaved that the disulfide-modified micelles possessed much higher anti-hepatoma activity with a low IC50 value of 1.1 μg/mL following a 72 h incubation. Furthermore, the intracellular uptake tested by CLSM and FCM demonstrated that multifunctional polymeric micelles could be more efficiently taken up by HepG2 cells compared with MCF-7 cells, agreed well with MTT assays, suggesting these well-defined micelles provide a potential drug delivery system for dual-responsive controlled drug release and enhanced anti-hepatoma therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Preparation of l-phenylalanine-imprinted solid-phase extraction sorbent by Pickering emulsion polymerization and the selective enrichment of l-phenylalanine from human urine.

PubMed

Li, Ji; Hu, Xiaoling; Guan, Ping; Zhang, Xiaoyan; Qian, Liwei; Zhang, Nan; Du, Chunbao; Song, Renyuan

2016-05-01

A novel l-phenylalanine molecularly imprinted solid-phase extraction sorbent was synthesized by the combination of Pickering emulsion polymerization and ion-pair dummy template imprinting. Compared to other polymerization methods, the molecularly imprinted polymers thus prepared exhibit a high specific surface, large pore diameter, and appropriate particle size. The key parameters for solid-phase extraction were optimized, and the result indicated that the molecularly imprinted polymer thus prepared exhibits a good recovery of 98.9% for l-phenylalanine. Under the optimized conditions of the procedure, an analytical method for l-phenylalanine was well established. By comparing the performance of the molecularly imprinted polymer and a commercial reverse-phase silica gel, the obtained molecularly imprinted polymer as an solid-phase extraction sorbent is more suitable, exhibiting high precision (relative standard deviation 3.2%, n = 4) and a low limit of detection (60.0 ± 1.9 nmol·L(-1) ) for the isolation of l-phenylalanine. Based on these results, the combination of the Pickering emulsion polymerization and ion-pair dummy template imprinting is effective for preparing selective solid-phase extraction sorbents for the separation of amino acids and organic acids from complex biological samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activated microporous materials through polymerization of microemulsion precursors

NASA Astrophysics Data System (ADS)

Venkatesan, Arunkumar

Microemulsions have been well studied for their unique characteristics. They are isotropic, thermodynamically stable and microstructured mixtures of oil and water stabilized by one or more surfactant species. They are formed spontaneously and are thermodynamically stable. Microemulsion precursors can be polymerized to make microporous solids with controlled pore structure and sizes. These polymeric solids have been studied extensively in the past. Although the fundamental properties of the microporous solids have been studied in depth, the development of specific applications that will utilize the unique properties of these solids has not been exhaustively researched. The current work establishes the feasibility of making activated microporous solids from microemulsion precursors, by the use of a ligand that chelates metals and also attaches itself to the polymer monolith. It also uses a novel 'in-situ' incorporation by combining the formulation and incorporation steps into one. The research objectives are, to formulate a microemulsion system that can yield useful microporous solids upon polymerization and activation, to characterize these solids using existing techniques available for analysis of similar microporous solids, to identify and understand the effect of the variables in the system and to study the influence of these variables on the performance characteristics of this material. Characterization techniques like Differential Scanning Calorimetry, Thermogravimetric Analysis and Scanning Electron Microscopy were used. A hydroxyethylmethylmethacrylate/methylmethacrylate/aqueous phase containing 10% SDS' system was chosen as the precursor microemulsion and the corresponding microporous solids were made. A metal chelating ligand, Congo Red, was incorporated onto the microporous polymer using NaOH as a binding agent. The ability of the resultant 'activated' microporous solid to remove metal ions from solution, was evaluated. The metal ion chosen was chromium and the influence of variables such as NaOH loading, Congo Red loading, Cross linker content etc. were studied. It was found that the microporous solids were effective in removing chromium from solution. They outperformed similar polymeric solids with ligands (reported in literature) in chromium removal. A removal of about 1500 micro moles of chromium ions per gram of dry polymer from a solution of 5 mMol/L initial concentration of chromium was observed. This is much more than the removal of 340 micro moles/gram of dry polymer reported in literature for comparable non-microporous systems.

Ultra-high vacuum surface analysis study of rhodopsin incorporation into supported lipid bilayers.

PubMed

Michel, Roger; Subramaniam, Varuni; McArthur, Sally L; Bondurant, Bruce; D'Ambruoso, Gemma D; Hall, Henry K; Brown, Michael F; Ross, Eric E; Saavedra, S Scott; Castner, David G

2008-05-06

Planar supported lipid bilayers that are stable under ambient atmospheric and ultra-high-vacuum conditions were prepared by cross-linking polymerization of bis-sorbylphosphatidylcholine (bis-SorbPC). X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were employed to investigate bilayers that were cross-linked using either redox-initiated radical polymerization or ultraviolet photopolymerization. The redox method yields a more structurally intact bilayer; however, the UV method is more compatible with incorporation of transmembrane proteins. UV polymerization was therefore used to prepare cross-linked bilayers with incorporated bovine rhodopsin, a light-activated, G-protein-coupled receptor (GPCR). A previous study (Subramaniam, V.; Alves, I. D.; Salgado, G. F. J.; Lau, P. W.; Wysocki, R. J.; Salamon, Z.; Tollin, G.; Hruby, V. J.; Brown, M. F.; Saavedra, S. S. J. Am. Chem. Soc. 2005, 127, 5320-5321) showed that rhodopsin retains photoactivity after incorporation into UV-polymerized bis-SorbPC, but did not address how the protein is associated with the bilayer. In this study, we show that rhodopsin is retained in supported bilayers of poly(bis-SorbPC) under ultra-high-vacuum conditions, on the basis of the increase in the XPS nitrogen concentration and the presence of characteristic amino acid peaks in the ToF-SIMS data. Angle-resolved XPS data show that the protein is inserted into the bilayer, rather than adsorbed on the bilayer surface. This is the first study to demonstrate the use of ultra-high-vacuum techniques for structural studies of supported proteolipid bilayers.

Interactions between magnetite and humic substances: redox reactions and dissolution processes.

PubMed

Sundman, Anneli; Byrne, James M; Bauer, Iris; Menguy, Nicolas; Kappler, Andreas

2017-10-19

Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe 3 O 4 ) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

Estimation of degree of polymerization of poly-acrylonitrile-grafted carbon nanotubes using Guinier plot of small angle x-ray scattering

NASA Astrophysics Data System (ADS)

Cho, Hyunjung; Jin, Kyeong Sik; Lee, Jaegeun; Lee, Kun-Hong

2018-07-01

Small angle x-ray scattering (SAXS) was used to estimate the degree of polymerization of polymer-grafted carbon nanotubes (CNTs) synthesized using a ‘grafting from’ method. This analysis characterizes the grafted polymer chains without cleaving them from CNTs, and provides reliable data that can complement conventional methods such as thermogravimetric analysis or transmittance electron microscopy. Acrylonitrile was polymerized from the surface of the CNTs by using redox initiation to produce poly-acrylonitrile-grafted CNTs (PAN-CNTs). Polymerization time and the initiation rate were varied to control the degree of polymerization. Radius of gyration (R g ) of PAN-CNTs was determined using the Guinier plot obtained from SAXS solution analysis. The results showed consistent values according to the polymerization condition, up to a maximum R g = 125.70 Å whereas that of pristine CNTs was 99.23 Å. The dispersibility of PAN-CNTs in N,N-dimethylformamide was tested using ultraviolet–visible-near infrared spectroscopy and was confirmed to increase as the degree of polymerization increased. This analysis will be helpful to estimate the degree of polymerization of any polymer-grafted CNTs synthesized using the ‘grafting from’ method and to fabricate polymer/CNT composite materials.

Estimation of degree of polymerization of poly-acrylonitrile-grafted carbon nanotubes using Guinier plot of small angle x-ray scattering.

PubMed

Cho, Hyunjung; Jin, Kyeong Sik; Lee, Jaegeun; Lee, Kun-Hong

2018-07-06

Small angle x-ray scattering (SAXS) was used to estimate the degree of polymerization of polymer-grafted carbon nanotubes (CNTs) synthesized using a 'grafting from' method. This analysis characterizes the grafted polymer chains without cleaving them from CNTs, and provides reliable data that can complement conventional methods such as thermogravimetric analysis or transmittance electron microscopy. Acrylonitrile was polymerized from the surface of the CNTs by using redox initiation to produce poly-acrylonitrile-grafted CNTs (PAN-CNTs). Polymerization time and the initiation rate were varied to control the degree of polymerization. Radius of gyration (R g ) of PAN-CNTs was determined using the Guinier plot obtained from SAXS solution analysis. The results showed consistent values according to the polymerization condition, up to a maximum R g  = 125.70 Å whereas that of pristine CNTs was 99.23 Å. The dispersibility of PAN-CNTs in N,N-dimethylformamide was tested using ultraviolet-visible-near infrared spectroscopy and was confirmed to increase as the degree of polymerization increased. This analysis will be helpful to estimate the degree of polymerization of any polymer-grafted CNTs synthesized using the 'grafting from' method and to fabricate polymer/CNT composite materials.

Actin filaments-A target for redox regulation.

PubMed

Wilson, Carlos; Terman, Jonathan R; González-Billault, Christian; Ahmed, Giasuddin

2016-10-01

Actin and its ability to polymerize into dynamic filaments is critical for the form and function of cells throughout the body. While multiple proteins have been characterized as affecting actin dynamics through noncovalent means, actin and its protein regulators are also susceptible to covalent modifications of their amino acid residues. In this regard, oxidation-reduction (Redox) intermediates have emerged as key modulators of the actin cytoskeleton with multiple different effects on cellular form and function. Here, we review work implicating Redox intermediates in post-translationally altering actin and discuss what is known regarding how these alterations affect the properties of actin. We also focus on two of the best characterized enzymatic sources of these Redox intermediates-the NADPH oxidase NOX and the flavoprotein monooxygenase MICAL-and detail how they have both been identified as altering actin, but share little similarity and employ different means to regulate actin dynamics. Finally, we discuss the role of these enzymes and redox signaling in regulating the actin cytoskeleton in vivo and highlight their importance for neuronal form and function in health and disease. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Actin filaments – a target for redox regulation

PubMed Central

Wilson, Carlos; Terman, Jonathan R.; González-Billault, Christian; Ahmed, Giasuddin

2016-01-01

Actin and its ability to polymerize into dynamic filaments is critical for the form and function of cells throughout the body. While multiple proteins have been characterized as affecting actin dynamics through non-covalent means, actin and its protein regulators are also susceptible to covalent modifications of their amino acid residues. In this regard, oxidation-reduction (Redox) intermediates have emerged as key modulators of the actin cytoskeleton with multiple different effects on cellular form and function. Here, we review work implicating Redox intermediates in post-translationally altering actin and discuss what is known regarding how these alterations affect the properties of actin. We also focus on two of the best characterized enzymatic sources of these Redox intermediates – the NADPH oxidase NOX and the flavoprotein monooxygenase MICAL – and detail how they have both been identified as altering actin, but share little similarity and employ different means to regulate actin dynamics. Finally, we discuss the role of these enzymes and redox signaling in regulating the actin cytoskeleton in vivo and highlight their importance for neuronal form and function in health and disease. PMID:27309342

Process for impregnating a concrete or cement body with a polymeric material

DOEpatents

Mattus, A.J.; Spence, R.D.

1988-05-04

A process for impregnating cementitious solids with polymeric materials by blending polymeric materials in a grout, allowing the grout to cure, and contacting the resulting solidified grout containing the polymeric materials with an organic mixture containing a monomer, a cross-linking agent and a catalyst. The mixture dissolves the polymerized particles and forms a channel for distributing the monomer throughout the network formed by the polymeric particles. The organic components are then cured to form a substantially water-impermeable mass.

Process for impregnating a concrete or cement body with a polymeric material

DOEpatents

Mattus, Alfred J.; Spence, Roger D.

1989-01-01

A process for impregnating cementitious solids with polymeric materials by blending polymeric materials in a grout, allowing the grout to cure, and contacting the resulting solidified grout containing the polymeric materials with an organic mixture containing a monomer, a cross-linking agent and a catalyst. The mixture dissolves the polymerized particles and forms a channel for distributing the monomer throughout the network formed by the polymeric particles. The organic components are then cured to form a substantially water-impermeable mass.

Characterization of milled solid residue from cypress liquefaction in sub- and super ethanol.

PubMed

Liu, Hua-Min; Liu, Yu-Lan

2014-01-01

Cypress liquefaction in sub- and super ethanol was carried out in an autoclave at various temperatures. Milled solid residue (MSR) was isolated from solid residue remaining from the liquefaction process, and its chemical characteristics was comparatively investigated with milled wood lignin (MWL) of cypress by sugar analysis, elemental analysis, FT-IR analysis, gel permeation chromatography, and NMR analysis. Results showed that there were two reactions (de-polymerization and re-polymerization) during the cypress liquefaction in sub- and super ethanol and the re-polymerization reactions were the main reaction at 220-260°C. Considering the stability of side-chain, the stability of lignin side-chain in cypress during liquefaction process in ethanol could be sequenced as follows: β-5>β-β'>β-O-4'. The MSR were mainly from the decomposition and re-polymerization of lignin. This study suggests that characterization of MSR provides a promising method to investigate the mechanisms of cypress liquefaction in ethanol. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

The autowave modes of solid phase polymerization of metal-containing monomers in two- and three-dimensional fiberglass-filled matrices.

PubMed

Barelko, V. V.; Pomogailo, A. D.; Dzhardimalieva, G. I.; Evstratova, S. I.; Rozenberg, A. S.; Uflyand, I. E.

1999-06-01

The phenomenon of autowave (frontal) solid phase polymerization of metal-containing monomers based on metal-acrylamide complexes is considered. The comparison of the features of autowave processes realized in both the single-component matrices of the monomer and the matrices filled by the fiberglass materials is performed. The unstable regimes of the polymerization wave as well as the conditions for the stabilization of the flat front in the filled matrices are described. The peculiarities of the frontal regimes in the three- and two-dimensional media are studied. Some possibilities for using of autowave polymerization in the fabrication of the polymer-fiberglass composites and composition prepregs are discussed. (c) 1999 American Institute of Physics.

In vitro characterization of a novel polymeric system for preparation of amorphous solid drug dispersions.

PubMed

Mahmoudi, Zahra N; Upadhye, Sampada B; Ferrizzi, David; Rajabi-Siahboomi, Ali R

2014-07-01

Preparation of amorphous solid dispersions using polymers is a commonly used formulation strategy for enhancing the solubility of poorly water-soluble drugs. However, often a single polymer may not bring about a significant enhancement in solubility or amorphous stability of a poorly water-soluble drug. This study describes application of a unique and novel binary polymeric blend in preparation of solid dispersions. The objective of this study was to investigate amorphous solid dispersions of glipizide, a BCS class II model drug, in a binary polymeric system of polyvinyl acetate phthalate (PVAP) and hypromellose (hydroxypropyl methylcellulose, HPMC). The solid dispersions were prepared using two different solvent methods: rotary evaporation (rotavap) and fluid bed drug layering on sugar spheres. The performance and physical stability of the dispersions were evaluated with non-sink dissolution testing, powder X-ray diffraction (PXRD), and modulated differential scanning calorimetry (mDSC). PXRD analysis demonstrated an amorphous state for glipizide, and mDSC showed no evidence of phase separation. Non-sink dissolution testing in pH 7.5 phosphate buffer indicated more than twofold increase in apparent solubility of the drug with PVAP-HPMC system. The glipizide solid dispersions demonstrated a high glass transition temperature (Tg) and acceptable chemical and physical stability during the stability period irrespective of the manufacturing process. In conclusion, the polymeric blend of PVAP-HPMC offers a unique formulation approach for developing amorphous solid dispersions with the flexibility towards the use of these polymers in different ratios and combined quantities depending on drug properties.

Quasi-solid state electrolytes for low-grade thermal energy harvesting using a cobalt redox couple.

PubMed

Taheri, Abuzar; MacFarlane, Douglas; Pozo-Gonzalo, Cristina; Pringle, Jennifer M

2018-06-06

Thermoelectrochemical cells, also known as thermocells, are electrochemical devices for the conversion of thermal energy directly to electricity. They are a promising method for harvesting low-grade waste heat from a variety of different natural and man-made sources. The development of solid or quasi-solid state electrolytes for thermocells could address the possible leakage problems of liquid electrolytes and make this technology more applicable for wearable devices. Here we report the gelation of an organic solvent-based electrolyte system containing a redox couple, for application in thermocell technologies. The effect of gelation of the liquid electrolyte, comprising a cobalt bipyridyl redox couple dissolved in 3-methoxypropionitrile (MPN), on the performance of thermocells was investigated. Polyvinylidene difluoride (PVDF) and poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP) were used for gelation of the electrolyte, and the influence of the different polymers on the mechanical properties was studied. The Seebeck coefficient and diffusivity of the cobalt redox couple were measured in both liquid and gelled electrolytes and the effect of gelation on the thermocell performance is reported. Finally, the cell performance was further improved by optimising the redox couple concentration and the separation between the hot and cold electrode, and the stability of the device over 25 hours of operation is demonstrated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2011-10-05

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

Triggered-release polymeric conjugate micelles for on-demand intracellular drug delivery

NASA Astrophysics Data System (ADS)

Cao, Yanwu; Gao, Min; Chen, Chao; Fan, Aiping; Zhang, Ju; Kong, Deling; Wang, Zheng; Peer, Dan; Zhao, Yanjun

2015-03-01

Nanoscale drug delivery platforms have been developed over the past four decades that have shown promising clinical results in several types of cancer and inflammatory disorders. These nanocarriers carrying therapeutic payloads are maximizing the therapeutic outcomes while minimizing adverse effects. Yet one of the major challenges facing drug developers is the dilemma of premature versus on-demand drug release, which influences the therapeutic regiment, efficacy and potential toxicity. Herein, we report on redox-sensitive polymer-drug conjugate micelles for on-demand intracellular delivery of a model active agent, curcumin. Biodegradable methoxy poly(ethylene glycol)-poly(lactic acid) copolymer (mPEG-PLA) was conjugated with curcumin via a disulfide bond or ester bond (control), respectively. The self-assembled redox-sensitive micelles exhibited a hydrodynamic size of 115.6 ± 5.9 (nm) with a zeta potential of -10.6 ± 0.7 (mV). The critical micelle concentration was determined at 6.7 ± 0.4 (μg mL-1). Under sink conditions with a mimicked redox environment (10 mM dithiothreitol), the extent of curcumin release at 48 h from disulfide bond-linked micelles was nearly three times higher compared to the control micelles. Such rapid release led to a lower half maximal inhibitory concentration (IC50) in HeLa cells at 18.5 ± 1.4 (μg mL-1), whereas the IC50 of control micelles was 41.0 ± 2.4 (μg mL-1). The cellular uptake study also revealed higher fluorescence intensity for redox-sensitive micelles. In conclusion, the redox-sensitive polymeric conjugate micelles could enhance curcumin delivery while avoiding premature release, and achieving on-demand release under the high glutathione concentration in the cell cytoplasm. This strategy opens new avenues for on-demand drug release of nanoscale intracellular delivery platforms that ultimately might be translated into pre-clinical and future clinical practice.

Triggered-release polymeric conjugate micelles for on-demand intracellular drug delivery.

PubMed

Cao, Yanwu; Gao, Min; Chen, Chao; Fan, Aiping; Zhang, Ju; Kong, Deling; Wang, Zheng; Peer, Dan; Zhao, Yanjun

2015-03-20

Nanoscale drug delivery platforms have been developed over the past four decades that have shown promising clinical results in several types of cancer and inflammatory disorders. These nanocarriers carrying therapeutic payloads are maximizing the therapeutic outcomes while minimizing adverse effects. Yet one of the major challenges facing drug developers is the dilemma of premature versus on-demand drug release, which influences the therapeutic regiment, efficacy and potential toxicity. Herein, we report on redox-sensitive polymer-drug conjugate micelles for on-demand intracellular delivery of a model active agent, curcumin. Biodegradable methoxy poly(ethylene glycol)-poly(lactic acid) copolymer (mPEG-PLA) was conjugated with curcumin via a disulfide bond or ester bond (control), respectively. The self-assembled redox-sensitive micelles exhibited a hydrodynamic size of 115.6 ± 5.9 (nm) with a zeta potential of -10.6 ± 0.7 (mV). The critical micelle concentration was determined at 6.7 ± 0.4 (μg mL(-1)). Under sink conditions with a mimicked redox environment (10 mM dithiothreitol), the extent of curcumin release at 48 h from disulfide bond-linked micelles was nearly three times higher compared to the control micelles. Such rapid release led to a lower half maximal inhibitory concentration (IC50) in HeLa cells at 18.5 ± 1.4 (μg mL(-1)), whereas the IC50 of control micelles was 41.0 ± 2.4 (μg mL(-1)). The cellular uptake study also revealed higher fluorescence intensity for redox-sensitive micelles. In conclusion, the redox-sensitive polymeric conjugate micelles could enhance curcumin delivery while avoiding premature release, and achieving on-demand release under the high glutathione concentration in the cell cytoplasm. This strategy opens new avenues for on-demand drug release of nanoscale intracellular delivery platforms that ultimately might be translated into pre-clinical and future clinical practice.

Dense Carbon Monoxide to 160 GPa: Stepwise Polymerization to Two-Dimensional Layered Solid

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

Ryu, Young-Jay; Kim, Minseob; Lim, Jinhyuk

Carbon monoxide (CO) is the first molecular system found to transform into a nonmolecular “polymeric” solid above 5.5 GPa, yet been studied beyond 10 GPa. Here, we show a series of pressure-induced phase transformations in CO to 160 GPa: from a molecular solid to a highly colored, low-density polymeric phase I to translucent, high-density phase II to transparent, layered phase III. The properties of these phases are consistent with those expected from recently predicted 1D P2 1/m, 3D I2 12 12 1, and 2D Cmcm structures, respectively. Thus, the present results advocate a stepwise polymerization of CO triple bonds tomore » ultimately a 2D singly bonded layer structure with an enhanced ionic character.« less

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.

Cells having cathodes containing polycarbon disulfide materials

DOEpatents

Okamoto, Y.; Skotheim, T.A.; Lee, H.S.

1995-08-15

The present invention relates to an electric current producing cell which contains an anode, a cathode having as a cathode-active material one or more carbon-sulfur compounds of the formula (CS{sub x}){sub n}, in which x takes values from 1.2 to 2.3 and n is greater or equal to 2, and where the redox process does not involve polymerization and de-polymerization by forming and breaking S--S bonds in the polymer backbone. The cell also contains an electrolyte which is chemically inert with respect to the anode and the cathode. 5 figs.

Synthesis and characterization of a material derived from 4-mercaptobenzoic acid: A novel platform for oligonucleotide immobilization.

PubMed

Alves, Rafael da Fonseca; da Silva, Amanda Gonçalves; Ferreira, Lucas Franco; Franco, Diego Leoni

2017-04-01

This paper reports the electrochemical modification of pencil carbon graphite electrodes with a polymeric material derived from 4-mercaptobenzoic acid. Acidic solutions (pH 0 and 5.02) yielded an insulating polymeric film with anionic permselective properties. Scanning Electron Microscopy (SEM) analysis showed a complete coverage of the carbon graphite electrodes with a laminar-like polymeric structure. Different characterization studies indicate that the carboxyl group remained unchanged since the absorbance peak and oxidation potential did not change with the increase in pH at the pK a accounting for the carboxyl/carboxylate redox transition. The functionalized matrix was activated using carbodiimide, succinimide and an amine-modified oligonucleotide. The immobilization and hybridization processes were successfully verified using the redox electroactive indicator methylene blue, where better electrochemical signals were obtained when compared with the traditional self-assembled monolayer system. The selectivity of the system was verified using a noncomplementary target where no significant difference in electric current was observed when compared to the system containing only the probe. The method showed a good linear correlation coefficient (r 2 =0.9915), low limit of detection (1.17nmolL -1 ), and an acceptable precision (RSD=2.75%). The proposed method is suitable for further studies using different sequences of oligonucleotides. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of a family of cysteine rich proteins and development of a MaSp1 derived miniature fibroin

NASA Astrophysics Data System (ADS)

Chuang, Tyler Casey

Spider silk displays a unique balance of high tensile strength and extensibility, making it one of the toughest materials on the planet. Dragline silk, also known as the lifeline of the spider, represents one of the best studied fiber types and many labs are attempting to produce synthetic dragline silk fibers for commercial applications. In these studies, we develop a minifibroin for expression studies in bacteria. Using recombinant DNA methodology and protein expression studies, we develop a natural minifibroin that contains the highly conserved N- and C-terminal domains, along with several internal block repeats of MaSp1. We also characterize a family of small cysteine-rich proteins (CRPs) and demonstrate that these factors are present within the spinning dope of the major ampullate gland using MS analysis. Biochemical studies and characterization of one of the family members, CRP1, demonstrate that this factor can self-polymerize into higher molecular weight complexes under oxidizing conditions, but can be converted into a monomeric species under reducing conditions. Self-polymerization of CRP1 is also shown to be independent of pH and salt concentration, two important chemical cues that help fibroin aggregation. Overall, our data demonstrate that the polymerization state of CRP1 is dependent upon redox state, suggesting that the redox environment during fiber extrusion may help regulate the oligomerization of CRP molecules during dragline silk production.

Coating of plasma polymerized film

NASA Technical Reports Server (NTRS)

Morita, S.; Ishibashi, S.

1980-01-01

Plasma polymerized thin film coating and the use of other coatings is suggested for passivation film, thin film used for conducting light, and solid body lubrication film of dielectrics of ultra insulators for electrical conduction, electron accessories, etc. The special features of flow discharge development and the polymerized film growth mechanism are discussed.

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

PubMed

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

2018-05-10

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

Ferrocene adsorbed into the porous octakis(hydridodimethylsiloxy)silsesquioxane after thermolysis in tetrahydrofuran media: An applied surface for ascorbic acid determination

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

Ribeiro do Carmo, Devaney, E-mail: docarmo@dfq.feis.unesp.br; Lataro Paim, Leonardo; Ramos Stradiotto, Nelson

Highlights: Black-Right-Pointing-Pointer Octakis(hydridodimethylsiloxi)silsesquioxane was synthesized and Ferrocene was adsorbed. Black-Right-Pointing-Pointer Polymeric net through electrostatic interactions was observed. Black-Right-Pointing-Pointer The novel materials presents electroacatalytic activity for Ascorbic acid. -- Abstract: Octakis(hydridodimethylsiloxi)silsesquioxane (Q{sub 8}M{sub 8}{sup H}) was synthesized and Ferrocene was adsorbed in a polymeric net through electrostatic interactions, with anion forming after the cleavage of any siloxy groups (ESFc). The nanostructured materials (Q{sub 8}M{sub 8}{sup H} and EsFc) were characterized by Fourier transform infrared spectra (FT-IR), nuclear magnetic resonance (NMR), X-ray diffraction (XRD), Thermogravimetric analyses and Voltammetric technique The cyclic voltammograms of the graphite paste electrode modified with ESFc showed onemore » redox couple with E{sup 0} Prime = 0.320 V (1.0 mol L{sup -1} NaCl, v = 50 mV s{sup -1}), with a diffusion-controlled process and the redox process shows electrocatalytic activity for the oxidation of ascorbic acid.« less

Multistate Redox Switching and Near-Infrared Electrochromism Based on a Star-Shaped Triruthenium Complex with a Triarylamine Core

NASA Astrophysics Data System (ADS)

Tang, Jian-Hong; He, Yan-Qin; Shao, Jiang-Yang; Gong, Zhong-Liang; Zhong, Yu-Wu

2016-10-01

A star-shaped cyclometalated triruthenium complex 2(PF6)n (n = 3 and 4) with a triarylamine core was synthesized, which functions as a molecular switch with five well-separated redox states in both solution and film states. The single-crystal X-ray structure of 2(PF6)3 is presented. This complex displays four consecutive one-electron redox waves at +0.082, +0.31, +0.74, and +1.07 V vs Ag/AgCl. In each redox state, it shows significantly different NIR absorptions with λmax of 1590 nm for 24+, 1400 nm for 25+, 1060 nm for 26+, and 740 nm for 27+, respectively. Complex 24+ shows a single-line EPR signal at g = 2.060, while other redox states are all EPR inactive. The spin density distributions and NIR absorptions in different redox states were rationalized by DFT and TDDFT calculations. A vinyl-substituted triruthenium analogous 3(PF6)4 was prepared, which was successfully polymerized on ITO glass electrode surfaces by reductive electropolymerization. The obtained poly-3n+/ITO film was characterized by FTIR, AFM, and SEM analysis. It shows four well-defined redox couples and reversible multistate NIR electrochromism. In particular, a contrast ratio (ΔT%) up to 63% was achieved at the optic telecommunication wavelength (1550 nm).

MINERALOGICAL PRESERVATION OF SOLID SAMPLES COLLECTED FROM ANOXIC SUBSURFACE ENVIRONMENTS

EPA Science Inventory

Remedial technologies utilized at hazardous waste sites for the treatment of metal and metalloid contaminants often take advantage of reduction-oxidation (redox) processes to reach ground water clean up goals. This is because redox reactions, in many cases, govern the biogeochem...

Plutonium Interactions with Pseudomonas sp. and its Extracellular Polymeric Substances (Sorption and Reduction of Plutonium by Bacterial Extracellular Polymeric Substances)

DOE PAGES

Boggs, Mark A.; Jiao, Yongqin; Dai, Zurong; ...

2016-09-30

Safe and effective nuclear waste disposal, as well as accidental radionuclide releases, necessitates our understanding of the fate of radionuclides in the environment, including their interaction with microorganisms. We examined the sorption of Pu(IV) and Pu(V) toPseudomonassp. strain EPS-1W, an aerobic bacterium isolated from plutonium (Pu) contaminated groundwater collected in the United States at the Nevada National Security Site (NNSS), Nevada. We compared Pu sorption to cells with and without bound extracellular polymeric substances (EPS). Wild type cells with intact EPS sorbed Pu(V) more effectively than cells with EPS removed. In contrast, cells with and without EPS showed the samemore » sorption affinity for Pu(IV).In vitroexperiments with extracted EPS revealed rapid reduction of Pu(V) to Pu(IV). Transmission Electron Microscopy indicated that 2-3 nm nanocrystalline Pu(IV)O 2formed on cells equilibrated with high concentrations of Pu(IV) but not Pu(V). Thus, EPS, while facilitating Pu(V) reduction, inhibit the formation of nanocrystalline Pu(IV) precipitates. ImportanceOur results indicate that EPS are an effective reductant for Pu(V) and sorbent for Pu(IV), and may impact Pu redox cycling and mobility in the environment. Additionally, the resulting Pu morphology associated with EPS will depend on the concentration and initial Pu oxidation state. While our results are not directly applicable to the Pu transport situation at the NNSS, the results suggest that, in general, stationary microorganisms and biofilms will tend to limit the migration of Pu and provide an important Pu retardation mechanism in the environment. In a broader sense, our results along with a growing body of literature highlight the important role of microorganisms as producers of redox-active organic ligands and therefore as modulators of radionuclide redox transformations and complexation in the subsurface.« less

Plutonium Interactions with Pseudomonas sp. and its Extracellular Polymeric Substances (Sorption and Reduction of Plutonium by Bacterial Extracellular Polymeric Substances)

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

Boggs, Mark A.; Jiao, Yongqin; Dai, Zurong

Safe and effective nuclear waste disposal, as well as accidental radionuclide releases, necessitates our understanding of the fate of radionuclides in the environment, including their interaction with microorganisms. We examined the sorption of Pu(IV) and Pu(V) toPseudomonassp. strain EPS-1W, an aerobic bacterium isolated from plutonium (Pu) contaminated groundwater collected in the United States at the Nevada National Security Site (NNSS), Nevada. We compared Pu sorption to cells with and without bound extracellular polymeric substances (EPS). Wild type cells with intact EPS sorbed Pu(V) more effectively than cells with EPS removed. In contrast, cells with and without EPS showed the samemore » sorption affinity for Pu(IV).In vitroexperiments with extracted EPS revealed rapid reduction of Pu(V) to Pu(IV). Transmission Electron Microscopy indicated that 2-3 nm nanocrystalline Pu(IV)O 2formed on cells equilibrated with high concentrations of Pu(IV) but not Pu(V). Thus, EPS, while facilitating Pu(V) reduction, inhibit the formation of nanocrystalline Pu(IV) precipitates. ImportanceOur results indicate that EPS are an effective reductant for Pu(V) and sorbent for Pu(IV), and may impact Pu redox cycling and mobility in the environment. Additionally, the resulting Pu morphology associated with EPS will depend on the concentration and initial Pu oxidation state. While our results are not directly applicable to the Pu transport situation at the NNSS, the results suggest that, in general, stationary microorganisms and biofilms will tend to limit the migration of Pu and provide an important Pu retardation mechanism in the environment. In a broader sense, our results along with a growing body of literature highlight the important role of microorganisms as producers of redox-active organic ligands and therefore as modulators of radionuclide redox transformations and complexation in the subsurface.« less

Shrink wrapping redox-active crystals of polyoxometalate open frameworks with organic polymers via crystal induced polymerisation.

PubMed

Takashima, Yohei; Miras, Haralampos N; Glatzel, Stefan; Cronin, Leroy

2016-06-14

We report examples of crystal surface modification of polyoxometalate open frameworks whereby the use of pyrrole or aniline as monomers leads to the formation of the corresponding polymers via an oxidative polymerization process initiated by the redox active POM scaffolds. Guest-exchange experiments demonstrate that the polymers can finely tune the guest exchange rate and their structural integrity is retained after the surface modifications. In addition, the formation of polyoxometalate-based self-fabricating tubes by the dissolution of Keggin-based network crystals were also modulated by the polymers, allowing a new type of hybrid inorganic polymer with an organic coating to be fabricated.

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.

Iron-Based Redox Polymerization of Acrylic Acid for Direct Synthesis of Hydrogel/Membranes, and Metal Nanoparticles for Water Treatment

PubMed Central

Hernández, Sebastián; Papp, Joseph K.; Bhattacharyya, Dibakar

2014-01-01

Functionalized polymer materials with ion exchange groups and integration of nano-structured materials is an emerging area for catalytic and water pollution control applications. The polymerization of materials such as acrylic acid often requires persulfate initiator and a high temperature start. However, is generally known that metal ions accelerate such polymerizations starting from room temperature. If the metal is properly selected, it can be used in environmental applications adding two advantages simultaneously. This paper deals with this by polymerizing acrylic acid using iron as accelerant and its subsequent use for nanoparticle synthesis in hydrogel and PVDF membranes. Characterizations of hydrogel, membranes and nanoparticles were carried out with different techniques. Nanoparticles sizes of 30–60 nm were synthesized. Permeability and swelling measurements demonstrate an inverse relationship between hydrogel mesh size (6.30 to 8.34 nm) and membrane pores (222 to 110 nm). Quantitative reduction of trichloroethylene/chloride generation by Fe/Pd nanoparticles in hydrogel/membrane platforms was also performed. PMID:24954975

Solids precipitation and polymerization of asphaltenes in coal-derived liquids

DOEpatents

Kydd, Paul H.

1984-01-01

The precipitation and removal of particulate solids from coal-derived liquids by adding a process-derived anti-solvent liquid fraction and continuing the precipitation process at a temperature above the melting point of the mixed liquids for sufficient time to allow the asphaltenes to polymerize and solids to settle at atmospheric pressure conditions. The resulting clarified light hydrocarbon overflow liquid contains less than about 0.02 W % ash and is suitable as turbine fuel or as boiler fuel for burning without particulate emission control equipment. An underflow liquid fraction containing less than about 0.1 W % solids along with low sulfur and nitrogen concentrations is suitable as a boiler fuel with emission control equipment.

Controlled Chemical Doping of Semiconductor Nanocrystals Using Redox Buffers

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

Engel, Jesse H.; Surendranath, Yogesh; Alivisatos, Paul

Semiconductor nanocrystal solids are attractive materials for active layers in next-generation optoelectronic devices; however, their efficient implementation has been impeded by the lack of precise control over dopant concentrations. Herein we demonstrate a chemical strategy for the controlled doping of nanocrystal solids under equilibrium conditions. Exposing lead selenide nanocrystal thin films to solutions containing varying proportions of decamethylferrocene and decamethylferrocenium incrementally and reversibly increased the carrier concentration in the solid by 2 orders of magnitude from their native values. This application of redox buffers for controlled doping provides a new method for the precise control of the majority carrier concentrationmore » in porous semiconductor thin films.« less

Redox-Active Hydrogel Polymer Electrolytes with Different pH Values for Enhancing the Energy Density of the Hybrid Solid-State Supercapacitor.

PubMed

Tang, Xiaohui; Lui, Yu Hui; Merhi, Abdul Rahman; Chen, Bolin; Ding, Shaowei; Zhang, Bowei; Hu, Shan

2017-12-27

To enhance the energy density of solid-state supercapacitors, a novel solid-state cell, made of redox-active poly(vinyl alcohol) (PVA) hydrogel electrolytes and functionalized carbon nanotube-coated cellulose paper electrodes, was investigated in this work. Briefly, acidic PVA-[BMIM]Cl-lactic acid-LiBr and neutral PVA-[BMIM]Cl-sodium acetate-LiBr hydrogel polymer electrolytes are used as catholyte and anolyte, respectively. The acidic condition of the catholyte contributes to suppression of the undesired irreversible reaction of Br - and extension of the oxygen evolution reaction potential to a higher value than that of the redox potential of Br - /Br 3 - reaction. The observed Br - /Br 3 - redox activity at the cathode contributes to enhance the cathode capacitance. The neutral condition of the anolyte helps extend the operating voltage window of the supercapacitor by introducing hydrogen evolution reaction overpotential to the anode. The electrosorption of nascent H on the negative electrode also increases the anode capacitance. As a result, the prepared solid-state hybrid supercapacitor shows a broad voltage window of 1.6 V, with a high Coulombic efficiency of 97.6% and the highest energy density of 16.3 Wh/kg with power density of 932.6 W/kg at 2 A/g obtained. After 10 000 cycles of galvanostatic charge and discharge tests at the current density of 10 A/g, it exhibits great cyclic stability with 93.4% retention of the initial capacitance. In addition, a robust capacitive performance can also be observed from the solid-state supercapacitor at different bending angles, indicating its great potential as a flexible energy storage device.

Recent aspects of self-oscillating polymeric materials: designing self-oscillating polymers coupled with supramolecular chemistry and ionic liquid science.

PubMed

Ueki, Takeshi; Yoshida, Ryo

2014-06-14

Herein, we summarise the recent developments in self-oscillating polymeric materials based on the concepts of supramolecular chemistry, where aggregates of molecular building blocks with non-covalent bonds evolve the temporal or spatiotemporal structure. By utilising the rhythmic oscillation of the association/dissociation of molecular aggregates coupled with the redox oscillation by the BZ reaction, novel soft materials that express similar functions as those of living matter will be achieved. Further, from the viewpoint of materials science, our recent approach to prepare self-oscillating materials that operate long-term under mild conditions will be introduced.

Porous glass membranes for vanadium redox-flow battery application - Effect of pore size on the performance

NASA Astrophysics Data System (ADS)

Mögelin, H.; Yao, G.; Zhong, H.; dos Santos, A. R.; Barascu, A.; Meyer, R.; Krenkel, S.; Wassersleben, S.; Hickmann, T.; Enke, D.; Turek, T.; Kunz, U.

2018-02-01

The improvement of redox-flow batteries requires the development of chemically stable and highly conductive separators. Porous glass membranes can be an attractive alternative to the nowadays most common polymeric membranes. Flat porous glass membranes with a pore size in the range from 2 to 50 nm and a thickness of 300 and 500 μm have been used for that purpose. Maximum values for voltage efficiency of 85.1%, coulombic efficiency of 97.9% and energy efficiency of 76.3% at current densities in the range from 20 to 60 mA cm-2 have been achieved. Furthermore, a maximum power density of 95.2 mW cm-2 at a current density of 140 mA cm-2 was gained. These results can be related to small vanadium crossover, high conductivity and chemical stability, confirming the great potential of porous glass membranes for vanadium redox-flow applications.

Polyhydroquinone-graphene composite as new redox species for sensitive electrochemical detection of cytokeratins antigen 21-1

NASA Astrophysics Data System (ADS)

Wang, Huiqiang; Rong, Qinfeng; Ma, Zhanfang

2016-07-01

Polyhydroquinone-graphene composite as a new redox species was synthesized simply by a microwave-assisted one-pot method through oxidative polymerization of hydroquinone by graphene oxide, which exhibited excellent electrochemical redox activity at 0.124 V and can remarkably promote electron transfer. The as-prepared composite was used as immunosensing substrate in a label-free electrochemical immunosensor for the detection of cytokeratins antigen 21-1, a kind of biomarker of lung cancer. The proposed immunosensor showed wide liner range from 10 pg mL-1 to 200 ng mL-1 with a detection limit 2.3 pg mL-1, and displayed a good stability and selectivity. In addition, this method has been used for the analysis of human serum sample, and the detection results showed good consistence with those of ELISA. The present substrate can be easily extended to other polymer-based nanocomposites.

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.

Evaluation of modified asphalt using chlorinated and maleated waste polymers.

DOT National Transportation Integrated Search

2002-07-01

Asphalt modification using polymeric additives derived from solid wastes, i.e. polyolefins, is reported. Chlorination of polyethylene can be controlled to produce semicrystalline polymeric additives. Differential scanning calorimetry can be used to d...

Synthesis and optoelectronic properties of new polyarylates with 2-naphthyldiphenylamine units

NASA Astrophysics Data System (ADS)

Cai, Wanan; Wu, Xiaotong; Xiao, Tiandi; Niu, Haijun; Bai, Xuduo; Wang, Cheng; Wang, Wen; Zhang, Yanhong

2018-02-01

Herein, five kinds of soluble electrochromic polyarylates were synthesized from the reaction of N,N'-bis(4-carboxyphenyl)-N,N'-di-2-naphthyl-1,4-phenylenediamine with five bisphenols via direct polycondensation process, respectively. These new materials showed no significant decomposition below 400 °C in nitrogen atmosphere. The maximum UV-vis absorption bands of these polyarylates located at 328-348 nm and 327-353 nm for solid films and DMSO solution, respectively. The polyarylate 6a, as an example, exhibited not only aggregation-induced emission (AIE) effect in different fraction tetrahydrofuran/water solution, but also solvatochromism in various polar solvents, markedly. Two reversible pairs of distinct redox peaks were associated with noticeable color changed from original colorless to yellowish orange and green for polymeric film could be observed in the cyclic voltammetry (CV) test. New absorption peaks emerged in near-infrared (NIR) region with increasing voltage in the UV-vis spectra, which indicates these polyarylates can be used as NIR electrochromic materials. These polyarylates performed high contrast of optical transmittance change around 42-53% with the highest coloration efficiency up to 236 cm2C-1.

Sediment phosphorus speciation and mobility under dynamic redox conditions

NASA Astrophysics Data System (ADS)

Parsons, Chris T.; Rezanezhad, Fereidoun; O'Connell, David W.; Van Cappellen, Philippe

2017-07-01

Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O2) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N2), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous- and solid-phase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low ( ˜ 2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl2 and NaHCO3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h-1 kg-1 indicated the potential for rapid mineralization of organic P (Po), in particular during periods of aeration when the activity of phosphomonoesterases was 37 % higher than under N2 sparging. The results emphasize that the magnitude and timing of internal P loading during periods of anoxia are dependent on both P redistribution within sediments and bottom-water nitrate concentrations.

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.

Redox Electrocatalysis of Floating Nanoparticles: Determining Electrocatalytic Properties without the Influence of Solid Supports.

PubMed

Peljo, Pekka; Scanlon, Micheál D; Olaya, Astrid J; Rivier, Lucie; Smirnov, Evgeny; Girault, Hubert H

2017-08-03

Redox electrocatalysis (catalysis of electron-transfer reactions by floating conductive particles) is discussed from the point-of-view of Fermi level equilibration, and an overall theoretical framework is given. Examples of redox electrocatalysis in solution, in bipolar configuration, and at liquid-liquid interfaces are provided, highlighting that bipolar and liquid-liquid interfacial systems allow the study of the electrocatalytic properties of particles without effects from the support, but only liquid-liquid interfaces allow measurement of the electrocatalytic current directly. Additionally, photoinduced redox electrocatalysis will be of interest, for example, to achieve water splitting.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

[Fundamentals of plasma chemistry and its application to drug engineering].

PubMed

Kuzuya, M

1996-04-01

In this review, our novel research works in both low temperature plasma chemistry and solid state plasma chemistry were described. As for low temperature plasma, the ESR study on plasma-induced radicals of several selected conventional polymers was shown including the detailed analyses of the radical structure and the mechanism by which the radicals were formed on typical degradable methacrylic polymers and cross-linkable polystyrene. One of the pharmaceutical applications of the plasma processing for drug delivery system (DDS) was also described, which includes the preparations of double-compressed tablet consisting of drugs as a core material and various types of polymers as a wall material followed by plasma-irradiation on such a tablet. As for solid state plasma, the detailed reaction mechanism of solid state mechanochemical polymerization was shown including the solid state single electron transfer and the special feature of the resulting polymers. The structural criteria for polymerizable monomer derived from the quantum chemical considerations were also established. Based on the above findings, we synthesized various polymeric prodrugs by mechanochemical polymerization and studied the nature of hydrolyses (drug release).

Two Photon Polymerization of Microneedles for Transdermal Drug Delivery

PubMed Central

Gittard, Shaun D.; Ovsianikov, Aleksandr; Chichkov, Boris N.; Doraiswamy, Anand; Narayan, Roger J.

2010-01-01

Importance of the field Microneedles are small-scale devices that are finding use for transdermal delivery of protein-based pharmacologic agents and nucleic acid-based pharmacologic agents; however, microneedles prepared using conventional microelectronics-based technologies have several shortcomings, which have limited translation of these devices into widespread clinical use. Areas covered in this review Two photon polymerization is a laser-based rapid prototyping technique that has been recently used for direct fabrication of hollow microneedles with a wide variety of geometries. In addition, an indirect rapid prototyping method that involves two photon polymerization and polydimethyl siloxane micromolding has been used for fabrication of solid microneedles with exceptional mechanical properties. What the reader will gain In this review, the use of two photon polymerization for fabricating in-plane and out-of-plane hollow microneedle arrays is described. The use of two photon polymerization-micromolding for fabrication of solid microneedles is also reviewed. In addition, fabrication of microneedles with antimicrobial properties is discussed; antimicrobial microneedles may reduce the risk of infection associated with formation of channels through the stratum corneum. Take home message It is anticipated that the use of two photon polymerization as well as two photon polymerization-micromolding for fabrication of microneedles and other microstructured drug delivery devices will increase over the coming years. PMID:20205601

Pressure-induced polymerization of P(CN) 3

DOE PAGES

Gou, Huiyang; Yonke, Brendan L.; Epshteyn, Albert; ...

2015-05-21

Motivated to explore the formation of novel extended carbon-nitrogen solids via well-defined molecular precursor pathways, we studied the chemical reactivity of highly pure phosphorous tricyanide, P(CN) 3, under conditions of high pressure at room temperature. Raman and infrared (IR) spectroscopic measurements reveal a series of phase transformations below 10 GPa, and several low-frequency vibrational modes are reported for the first time. Synchrotron powder Xray diffraction (PXRD) measurements taken during compression show that molecular P(CN) 3 is highly compressible with a bulk modulus of 10.0±0.3 GPa and polymerizes into an amorphous solid above ~10.0 GPa. Raman and infrared (IR) spectra, togethermore » with first-principles molecular-dynamics simulations, show that the amorphization transition is associated with polymerization of the cyanide groups into CN bonds with predominantly sp 2 character, similar to known carbon nitrides, resulting in a novel PCN polymeric phase, which is recoverable to ambient pressure.« less

The [2+2] Cycloaddition-Retroelectrocyclization (CA-RE) Click Reaction: Facile Access to Molecular and Polymeric Push-Pull Chromophores.

PubMed

Michinobu, Tsuyoshi; Diederich, François

2018-03-26

The [2+2] cycloaddition-retroelectrocyclization (CA-RE) reaction between electron-rich alkynes and electron-deficient alkenes is an efficient procedure to create nonplanar donor-acceptor (D-A) chromophores in both molecular and polymeric platforms. They feature attractive properties including intramolecular charge-transfer (ICT) bands, nonlinear optical properties, and redox activities for use in next-generation electronic and optoelectronic devices. This Review summarizes the development of the CA-RE reaction, starting from the initial reports with organometallic compounds to the extension to purely organic systems. The structural requirements for rapid, high-yielding transformations with true click chemistry character are illustrated by examples that include the broad alkyne and alkene substitution modes. The CA-RE click reaction has been successfully applied to polymer synthesis, with the resulting polymeric push-pull chromophores finding many interesting applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of alkyne-TCNQ addition reaction to polymerization.

PubMed

Washino, Yusuke; Michinobu, Tsuyoshi

2011-04-19

The polymerization using a high-yielding addition reaction between electron-rich alkynes and 7,7,8,8-tetracyanoquinodimethane (TCNQ) derivatives is described. The bifunctional monomer containing two TCNQ moieties and the counter comonomer bearing two dialkylaniline (DAA)-substituted alkynes are reacted in 1,2-dichloroethane under mild heating conditions. At the high monomer concentrations, high molecular weight linear polymers are obtained, while the reaction at the low monomer concentrations produces a significant amount of the cyclic compounds. A clear relationship between the monomer concentration and the cyclic compound amount is demonstrated. The obtained polymers feature a sufficient thermal stability with the decomposition temperature exceeding 300  °C as well as strong charge-transfer (CT) bands and redox activities ascribed to the produced donor-acceptor moieties. These features are also used to optimize the polymerization conditions and to estimate the chemical structures. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized β-polytype porous silicon carbide electrodes.

PubMed

Kim, Myeongjin; Yoo, Jeeyoung; Kim, Jooheon

2017-05-23

A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo 2 O 4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo 2 O 4 ) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g -1 at a scan rate of 5 mV s -1 in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe 3 O 4 nanoparticles and SiCF (SiCF/Fe 3 O 4 ) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g -1 at a scan rate of 5 mV s -1 . Therefore, by pairing the SiCF/MgCo 2 O 4 positive electrode and the SiCF/Fe 3 O 4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g -1 at a scan rate of 5 mV s -1 ) and energy density (maximum energy density of 72.79 Wh kg -1 at a power density of 727.96 W kg -1 ).

Aromatic Polyimide/Graphene Composite Organic Cathodes for Fast and Sustainable Lithium-Ion Batteries

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

Lyu, Hailong; Li, Peipei; Liu, Jiurong

A composite organic cathode material based on aromatic polyimide (PI) and highly conductive graphene was prepared through a facile in situ polymerization method for application in lithium-ion batteries. The in situ polymerization generated intimate contact between PI and electronically conductive graphene, resulting in conductive composites with highly reversible redox reactions and good structure stability. The synergistic effect between PI and graphene enabled not only a high reversible capacity of 232.6 mAh g -1 at a charge–discharge rate of C/10 but also exceptionally high-rate cycling stability, that is, a high capacity of 108.9 mAh g -1 at a very high charge–dischargemore » rate of 50C with a capacity retention of 80 % after 1000 cycles. This improved electrochemical performance resulted from the combination of stable redox reversibility of PI and high electronic conductivity of the graphene additive. In conclusion, the graphene-based composite also exhibited much better performance than composites based on multi-walled carbon nanotubes and the conductive carbon black C45 in terms of specific capacity and long-term cycling stability under the same charge–discharge rates.« less

Symmetric redox supercapacitor based on micro-fabrication with three-dimensional polypyrrole electrodes

NASA Astrophysics Data System (ADS)

Sun, Wei; Zheng, Ruilin; Chen, Xuyuan

To achieve higher energy density and power density, we have designed and fabricated a symmetric redox supercapacitor based on microelectromechanical system (MEMS) technologies. The supercapacitor consists of a three-dimensional (3D) microstructure on silicon substrate micromachined by high-aspect-ratio deep reactive ion etching (DRIE) method, two sputtered Ti current collectors and two electrochemical polymerized polypyrrole (PPy) films as electrodes. Electrochemical tests, including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatical charge/discharge methods have been carried out on the single PPy electrodes and the symmetric supercapacitor in different electrolytes. The specific capacitance (capacitance per unit footprint area) and specific power (power per unit footprint area) of the PPy electrodes and symmetric supercapacitor can be calculated from the electrochemical test data. It is found that NaCl solution is a good electrolyte for the polymerized PPy electrodes. In NaCl electrolyte, single PPy electrodes exhibit 0.128 F cm -2 specific capacitance and 1.28 mW cm -2 specific power at 20 mV s -1 scan rate. The symmetric supercapacitor presents 0.056 F cm -2 specific capacitance and 0.56 mW cm -2 specific power at 20 mV s -1 scan rate.

Aromatic Polyimide/Graphene Composite Organic Cathodes for Fast and Sustainable Lithium-Ion Batteries

DOE PAGES

Lyu, Hailong; Li, Peipei; Liu, Jiurong; ...

2018-01-24

A composite organic cathode material based on aromatic polyimide (PI) and highly conductive graphene was prepared through a facile in situ polymerization method for application in lithium-ion batteries. The in situ polymerization generated intimate contact between PI and electronically conductive graphene, resulting in conductive composites with highly reversible redox reactions and good structure stability. The synergistic effect between PI and graphene enabled not only a high reversible capacity of 232.6 mAh g -1 at a charge–discharge rate of C/10 but also exceptionally high-rate cycling stability, that is, a high capacity of 108.9 mAh g -1 at a very high charge–dischargemore » rate of 50C with a capacity retention of 80 % after 1000 cycles. This improved electrochemical performance resulted from the combination of stable redox reversibility of PI and high electronic conductivity of the graphene additive. In conclusion, the graphene-based composite also exhibited much better performance than composites based on multi-walled carbon nanotubes and the conductive carbon black C45 in terms of specific capacity and long-term cycling stability under the same charge–discharge rates.« less

Production of fungal antibiotics using polymeric solid supports in solid-state and liquid fermentation.

PubMed

Bigelis, Ramunas; He, Haiyin; Yang, Hui Y; Chang, Li-Ping; Greenstein, Michael

2006-10-01

The use of inert absorbent polymeric supports for cellular attachment in solid-state fungal fermentation influenced growth, morphology, and production of bioactive secondary metabolites. Two filamentous fungi exemplified the utility of this approach to facilitate the discovery of new antimicrobial compounds. Cylindrocarpon sp. LL-Cyan426 produced pyrrocidines A and B and Acremonium sp. LL-Cyan416 produced acremonidins A-E when grown on agar bearing moist polyester-cellulose paper and generated distinctly different metabolite profiles than the conventional shaken or stationary liquid fermentations. Differences were also apparent when tenfold concentrated methanol extracts from these fermentations were tested against antibiotic-susceptible and antibiotic-resistant Gram-positive bacteria, and zones of inhibition were compared. Shaken broth cultures of Acremonium sp. or Cylindrocarpon sp. showed complex HPLC patterns, lower levels of target compounds, and high levels of unwanted compounds and medium components, while agar/solid support cultures showed significantly increased yields of pyrrocidines A and B and acremonidins A-E, respectively. This method, mixed-phase fermentation (fermentation with an inert solid support bearing liquid medium), exploited the increase in surface area available for fungal growth on the supports and the tendency of some microorganisms to adhere to solid surfaces, possibly mimicking their natural growth habits. The production of dimeric anthraquinones by Penicillium sp. LL-WF159 was investigated in liquid fermentation using various inert polymeric immobilization supports composed of polypropylene, polypropylene cellulose, polyester-cellulose, or polyurethane. This culture produced rugulosin, skyrin, flavomannin, and a new bisanthracene, WF159-A, after fermentation in the presence and absence of polymeric supports for mycelial attachment. The physical nature of the different support systems influenced culture morphology and relative metabolite yields, as determined by HPLC analysis and measurement of antimicrobial activity. The application of such immobilized-cell fermentation methods under solid and liquid conditions facilitated the discovery of new antibiotic compounds, and offers new approaches to fungal fermentation for natural product discovery.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, M.S.; Saunders, R.

1997-02-18

Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

Block copolymer adhesion promoters via ring-opening metathesis polymerization

DOEpatents

Kent, Michael S.; Saunders, Randall

1997-01-01

Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

Electrochemical measurements and thermodynamic calculations of redox equilibria in pallasite meteorites - Implications for the eucrite parent body

NASA Technical Reports Server (NTRS)

Righter, Kevin; Arculus, Richard J.; Paslick, Cassi; Delano, John W.

1990-01-01

The intrinsic oxygen fugacity (IOF) of olivine separates from the Salta, Springwater, and Eagle Station pallasites was measured between 850 and 1150 C using oxygen-specific solid zirconia electrolytes at 100,000 Pa. Thermodynamic calculations of redox equilibria involving equalibrium pallasite assemblages are in good agreement with the experimental results and provide a lower limit to pallasite redox stability; others involving disequilibrium assemblages, suggest that pallasites experienced localized, late-stage oxidation and reduction effects. Consideration of the redox buffer metal-olivine-orthopyroxene utilizing calculated Eucrite Parent Body (EPB) mantle phase compositions indicates that small redox gradients may have existed in the EPB. Such gradients may have produced strong compositional variation within the EPB. In addition, there is apparently significant redox heterogeneity in the source area of Eagle Station Trio pallasites and Bocaiuva iron meteorites.

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

PubMed

Abdel-Halim, E S

2012-10-01

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

Bimetallic nanosized solids with acid and redox properties for catalytic activation of C–C and C–H bonds† †Electronic supplementary information (ESI) available: General procedures, additional figures and tables, compound characterization and NMR copies. See DOI: 10.1039/c6sc03335k Click here for additional data file.

PubMed Central

Cabrero-Antonino, Jose R.; Tejeda-Serrano, María; Quesada, Manuel; Vidal-Moya, Jose A.

2017-01-01

A new approach is presented to form self-supported bimetallic nanosized solids with acid and redox catalytic properties. They are water-, air- and H2-stable, and are able to activate demanding C–C and C–H reactions. A detailed mechanistic study on the formation of the Ag–Fe bimetallic system shows that a rapid redox-coupled sequence between Ag+, O2 (air) and Fe2+ occurs, giving monodisperse Ag nanoparticles supported by O-bridged diatomic Fe3+ triflimides. The system can be expanded to Ag nanoparticles embedded within a matrix of Cu2+, Bi3+ and Yb3+ triflimide. PMID:28451218

Electrochemical catalyst recovery method

DOEpatents

Silva, L.J.; Bray, L.A.

1995-05-30

A method of recovering catalyst material from latent catalyst material solids includes: (a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; (b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; (c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and (d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications. 3 figs.

Electrochemical catalyst recovery method

DOEpatents

Silva, Laura J.; Bray, Lane A.

1995-01-01

A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

Application of mercapto-silica polymerized high internal phase emulsions for the solid-phase extraction and preconcentration of trace lead(II).

PubMed

Su, Rihui; Ruan, Guihua; Chen, Zhengyi; Du, Fuyou; Li, Jianping

2015-12-01

A new class of solid-phase extraction column prepared with grafted mercapto-silica polymerized high internal phase emulsion particles was used for the preconcentration of trace lead. First, mercapto-silica polymerized high internal phase emulsion particles were synthesized by using high internal phase emulsion polymerization and carefully assembled in a polyethylene syringe column. The influences of various parameters including adsorption pH value, adsorption and desorption solvents, flow rate of the adsorption and desorption procedure were optimized, respectively, and the suitable uploading sample volumes, adsorption capacity, and reusability of solid phase extraction column were also investigated. Under the optimum conditions, Pb(2+) could be preconcentrated quantitatively over a wide pH range (2.0-5.0). In the presence of foreign ions, such as Na(+) , K(+) , Ca(2+) , Zn(2+) , Mg(2+) , Cu(2+) , Fe(2+) , Cd(2+) , Cl(-) and NO3 (-) , Pb(2+) could be recovered successfully. The prepared solid-phase extraction column performed with high stability and desirable durability, which allowed more than 100 replicate extractions without measurable changes of performance. The feasibility of the developed method was further validated by the extraction of Pb(2+) in rice samples. At three spiked levels of 40.0, 200 and 800 μg/kg, the average recoveries for Pb(2+) in rice samples ranged from 87.3 to 105.2%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed Central

2015-01-01

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

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

PubMed

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

2014-05-21

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

Room temperature solid-state synthesis of a conductive polymer for applications in stable I₂-free dye-sensitized solar cells.

PubMed

Kim, Byeonggwan; Koh, Jong Kwan; Kim, Jeonghun; Chi, Won Seok; Kim, Jong Hak; Kim, Eunkyoung

2012-11-01

A solid-state polymerizable monomer, 2,5-dibromo-3,4-propylenedioxythiophene (DBProDOT), was synthesized at 25 °C to produce a conducting polymer, poly(3,4-propylenedioxythiophene) (PProDOT). Crystallographic studies revealed a short interplane distance between DBProDOT molecules, which was responsible for polymerization at low temperature with a lower activation energy and higher exothermic reaction than 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) or its derivatives. Upon solid-state polymerization (SSP) of DBProDOT at 25 °C, PProDOT was obtained in a self-doped state with tribromide ions and an electrical conductivity of 0.05 S cm⁻¹, which is considerably higher than that of chemically-polymerized PProDOT (2×10⁻⁶ S cm⁻¹). Solid-state ¹³C NMR spectroscopy and DFT calculations revealed polarons in PProDOT and a strong perturbation of carbon nuclei in thiophenes as a result of paramagnetic broadening. DBProDOT molecules deeply penetrated and polymerized to fill nanocrystalline TiO₂ pores with PProDOT, which functioned as a hole-transporting material (HTM) for I₂-free solid-state dye-sensitized solar cells (ssDSSCs). With the introduction of an organized mesoporous TiO₂ (OM-TiO₂) layer, the energy conversion efficiency reached 3.5 % at 100 mW cm⁻², which was quite stable up to at least 1500 h. The cell performance and stability was attributed to the high stability of PProDOT, with the high conductivity and improved interfacial contact of the electrode/HTM resulting in reduced interfacial resistance and enhanced electron lifetime. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Temperature Controlled Redox Crystallization Studies

NASA Technical Reports Server (NTRS)

Williams, R. J.

1985-01-01

The crystallization of silicates containing redox sensitive ions (e.g., Fe, Ti, Ce) must be performed under controlled and known redox conditions in order to obtain the maximum scientific benefit from experimental study. Furthermore, many compositions crystallize dense phases which settle during ground-based experiments. This settling influences the texture and chemical evolution of the crystallizing system. The purpose of this investigation is to develop a test system in which controlled redox experiments can be performed in the microgravity environment. The system will use solid ceramic oxygen electrolyte cells for control, measurements, and production of the required redox conditions. A preliminary design for a prototype is developed, the electrolyte and furnace tested, and a tentative protocol for experiment developed. The control parameter is to be established and a laboratory prototype built.

Frontal Polymerization in Microgravity: Bubble Behavior and Convection on the KC-135 Aircraft

NASA Technical Reports Server (NTRS)

Pojman, John A.; Ainsworth, William; Chekanov, Yuri; Masere, Jonathan; Volpert, Vitaly; Dumont, Thierry; Wilke, Hermann

2001-01-01

Frontal polymerization is a mode of converting monomer into polymer via a localized exothermic reaction zone that propagates through the coupling of thermal diffusion and Arrhenius reaction kinetics. Frontal polymerization was discovered in Russia by Chechilo and Enikolopyan in 1972. The macrokinetics and dynamics of frontal polymerization have been examined in detail and applications for materials synthesis considered. Large temperature and concentration gradients that occur in the front lead to large density gradients. A schematic is presented for a liquid monomer, usually a monoacrylate, being converted to a liquid (thermoplastic) polymer. The velocity can be controlled by the initiator concentration but is on the order of a cm/min. If the liquid monomer is multifunctional, then a solid (thermoset) polymer is formed. Convection can occur with all types of monomers if the front propagates up a tube. Bowden et al. studied liquid/solid systems. McCaughey et al. studied liquid polymer systems. Descending fronts in thermoplastic systems are also susceptible to the Rayleigh-Taylor instability.

Tunable Nanocomposite Membranes for Water Remediation and Separations

NASA Astrophysics Data System (ADS)

Sierra, Sebastian Hernandez

Nano-structured material fabrication using functionalized membranes with polyelectrolytes is a promising research field for water pollution, catalytic and mining applications. These responsive polymers react to external stimuli like temperature, pH, radiation, ionic strength or chemical composition. Such nanomaterials provide novel hybrid properties and can also be self-supported in addition to the membranes. Polyelectrolytes (as hydrogels) have pH responsiveness. The hydrogel moieties gain or lose protons based on the pH, displaying swelling properties. These responsive materials can be exploited to synthesize metal nanoparticles in situ using their functional groups, or to immobilize other polyelectrolytes and biomolecules. Due to their properties, these responsive materials prevent the loss of nanomaterials to the environment and improve reactivity due to their larger surface areas, expanding their range of applications. The present work describes different techniques used to create nanocomposites based on poly(vinylidene fluoride) (PVDF) hollow fiber and flat sheet membranes, both thick sponge-like and thin. Due to their hydrophobicity, hollow fiber membranes were hydrophilized by a water-based green process of cross-linking polyvinylpyrrolidone (PVP) onto their surface. Commercial hydrophilic and hydrophilized lab-prepared membranes were subsequently functionalized with a poly(acrylic acid) (PAA) hydrogel through free radical polymerizations. This work advanced membrane functionalization, specifically flat sheet membranes, from lab-scale to full-scale by modifications of the polymerization procedures. The hydrogel functionalized membranes by redox polymerization showed an expected responsive behavior, represented by permeability variation at various pH values (4.0 ≤ pH ≤ 9.0), from 53.9 to 3.4 L/(m2EhEbar) and a change in effective pore size from 222 to 111 nm, being 3800 L/(m 2EhEbar) and 650 nm the former permeability and pore size values of the non-functionalized membrane. Then, throughout a double ion exchange of sodium/iron and a subsequent reduction, bimetallic Fe/Pd nanoparticles were synthesized in-situ. Similarly, it was possible to use the reacted accelerants of the redox polymerization to synthesize Fe0 nanoparticles. These hydrogel-membrane systems with Fe/Pd nanoparticles were studied throughout the reduction of trichloroethylene (TCE). This work has demonstrated an effective improvement in TCE reduction by the variation of the supporting membrane types and the functionalization (polymerization and nanoparticle synthesis) processes. The TCE normalized dechlorination rates (k sa) are 3 times greater and 8 times for hollow fiber and sponge-like flat sheet membranes, respectively, than previous studies. For membrane supported Fe/Pd nanoparticles by redox functionalization, the dechlorination rates are similar to previous works in flat sheet membranes; and for the redox polymerized hydrogel, the dechlorination rates are the highest results with 1.3 times greater than the rates of solution-phase nanoparticles and 10 times the rate values of the membranes. All supports showed nonsignificant nanoparticle loss (up to 1%). Up to 80% of reduction was achieved within 2 hours with chloride production near to stoichiometric values (3:1), demonstrating absence of intermediates. As an extension of the membrane functionalization, it was possible to immobilize Outer membrane protein F precursor (OmpF) from Escherichia coli within the PVDF membrane pore structure, using layer-by-layer (LbL) assembly of polyeletrolytes. This LbL technique allows to reuse the membranes numerous times, having reproducibility and greater selective rejections of uncharged (organic species) over charged solutes (small ions) than similar functionalized membranes without OmpF: 1.7 times and 2.0 times higher for Organic/CaCl2 and Organic/NaCl, respectively. Additionally, the permeability of OmpFmembranes is almost double of the non-OmpF: 2.6 to 1.5 L/(m2˙h˙bar).

Therapeutic and scintigraphic applications of polymeric micelles: combination of chemotherapy and radiotherapy in hepatocellular carcinoma

PubMed Central

Shih, Ying-Hsia; Peng, Cheng-Liang; Chiang, Ping-Fang; Lin, Wuu-Jyh; Luo, Tsai-Yueh; Shieh, Ming-Jium

2015-01-01

This study evaluated a multifunctional micelle simultaneously loaded with doxorubicin (Dox) and labeled with radionuclide rhenium-188 (188Re) as a combined radiotherapy and chemotherapy treatment for hepatocellular carcinoma. We investigated the single photon emission computed tomography, biodistribution, antitumor efficacy, and pathology of 188Re-Dox micelles in a murine orthotopic luciferase-transfected BNL tumor cells hepatocellular carcinoma model. The single photon emission computed tomography and computed tomography images showed high radioactivity in the liver and tumor, which was in agreement with the biodistribution measured by γ-counting. In vivo bioluminescence images showed the smallest size tumor (P<0.05) in mice treated with the combined micelles throughout the experimental period. In addition, the combined 188Re-Dox micelles group had significantly longer survival compared with the control, 188ReO4 alone (P<0.005), and Dox micelles alone (P<0.01) groups. Pathohistological analysis revealed that tumors treated with 188Re-Dox micelles had more necrotic features and decreased cell proliferation. Therefore, 188Re-Dox micelles may enable combined radiotherapy and chemotherapy to maximize the effectiveness of treatment for hepatocellular carcinoma. PMID:26719687

The reactivity of Fe(II) associated with goethite formed during short redox cycles toward Cr(VI) reduction under oxic conditions

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

Tomaszewski, Elizabeth J.; Lee, Seungyeol; Rudolph, Jared

Chromium (Cr) is a toxic metal that causes a myriad of health problems and enters the environment as a result of anthropogenic activities and/or natural processes. The toxicity and solubility of chromium is linked to its oxidation state; Cr(III) is poorly soluble and relatively nontoxic, while Cr(VI) is soluble and a known carcinogen. Solid Fe(II) in iron-bearing minerals, such as pyrite, magnetite, and green rusts, reduce the oxidation state of chromium, reducing its toxicity and mobility. However, these minerals are not the only potential sources of solid-associated Fe(II) available for Cr(VI) reduction. For example, ferric (Fe(III)) (hydr)oxides, such as goethitemore » or hematite, can have Fe(II) in the solid without phase transformation; however, the reactivity of Fe(II) within Fe(III) (hydr)oxides with contaminants, has not been previously investigated. Here, we cyclically react goethite with dissolved Fe(II) followed by dissolved O2, leading to the formation of reactive Fe(II) associated with goethite. In separate reactors, the reactivity of this Fe(II) is probed under oxic conditions, by exposure to chromate (CrO42 -) after either one, two, three or four redox cycles. Cr is not present during redox cycling; rather, it is introduced to a subset of the solid after each oxidation half-cycle. Analysis of X-ray absorption near edge structure (XANES) spectra reveals that the extent of Cr(VI) reduction to Cr(III) depends not only on solid Fe(II) content but also surface area and mean size of ordered crystalline domains, determined by BET surface area analysis and X-ray diffraction (XRD), respectively. Shell-by-shell fitting of the extended X-ray absorption fine structure (EXAFS) spectra demonstrates chromium forms both single and double corner sharing complexes on the surface of goethite, in addition to sorbed Cr(III) species. Finally, transmission electron microscope (TEM) imaging and X-ray energy-dispersive spectroscopy (EDS) illustrate that Cr preferentially localizes on the (100) face of goethite, independent of the number of redox cycles goethite undergoes. This work demonstrates that under oxic conditions, solid Fe(II) associated with goethite resulting from rapid redox cycling is reactive and available for electron transfer to Cr(VI), suggesting Fe(III) (hydr)oxides may act as reservoirs of reactive electron density, even in oxygen saturated environments.« less

Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Li, Hui; ...

2015-01-14

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

Silver doped catalysts for treatment of exhaust

DOEpatents

Park, Paul Worn [Peoria, IL; Boyer, Carrie L [Shiloh, IL

2006-12-26

A method of making an exhaust treatment catalyst includes dispersing a metal-based material in a first solvent to form a first slurry and allowing polymerization of the first slurry to occur. Polymerization of the first slurry may be quenched and the first slurry may be allowed to harden into a solid. This solid may be redistributed in a second solvent to form a second slurry. The second slurry may be loaded with a silver-based material, and a silver-loaded powder may be formed from the second slurry.

Graphene oxide-based composite monolith as new sorbent for the on-line solid phase extraction and high performance liquid chromatography determination of ß-sitosterol in food samples.

PubMed

Cui, Beijiao; Guo, Bin; Wang, Huimin; Zhang, Doudou; Liu, Haiyan; Bai, Ligai; Yan, Hongyuan; Han, Dandan

2018-08-15

A composite monolithic column was prepared by redox initiation method for the on-line purification and enrichment of β-sitosterol, in which graphene oxide (GO) was embedded. The obtained monolithic column was characterized by scanning electron microscopy (SEM) and nitrogen adsorption-desorption isotherm measurement, which indicated that the monolith possessed characteristics of porous structure and high permeability. Under the optimum conditions for extraction and determination, the calibration equation was y = 47.92 × -0.1391; the linear range was 0.008-1.0 mg mL -1 ; the linear regression coefficient was 0.998; the limit of detection (LOD) is 2.4 μg mL -1 ; the limit of quantitation (LOQ) was 8 μg mL -1 ; precisions for intra-day and inter-day assays presented as relative standard deviations were less than 4.3% and 6.8%, respectively. Under the selective conditions, the enrichment factor of the method was 119. The recovery was in the range of 80.40-98.00%. Moreover, the adsorption amount of the monolith was compared with silica gel-C18 adsorbent and the monolith without graphene oxide being embedded. The polymerization monolithic column showed high selectivity and good permeability, and it was successfully used as on-line solid-phase extraction (SPE) column for determination of β-sitosterol in edible oil. Copyright © 2018 Elsevier B.V. All rights reserved.

Chemical oxidative and solid state synthesis of low molecular weight polymers for organic field effect transistors

NASA Astrophysics Data System (ADS)

Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar

2018-03-01

Solution processability of the precursor molecules is a major issue owing to their limited solubility for the synthesis of conjugated polymers. Therefore, we favour the solvent free solid state chemical oxidative polymerization route for the synthesis of diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) type conjugated polymers. D-A type polymer Poly(S-OD-EDOT) which contains DPP coupled with EDOT donor units is synthesized via solid state polymerization method. The polymer is employed as an active layer for organic field-effect transistors to measure charge transport properties. The Polymer shows good hole mobility 3.1 × 10-2 cm2 V-1 s-1, with a on/off ratio of 1.1 × 103.

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...

Investigation of excited-state relaxation processes of organic dyes by time-resolved spectroscopy

NASA Astrophysics Data System (ADS)

Przhonska, O.; Slominsky, Yu.; Kachkovsky, A.; Stahl, U.; Senoner, M.; Dähne, S.

1996-04-01

The results of the measurements of the fluorescence decay kinetics of the new series of polymethine dyes in liquid and solid polymeric media are reported. The effects of polymeric media on absorption-relaxation-emission processes are studied at wide excitation, emission and temperature regions.

Chemoselective phototransformation of C-H bonds on a polymer surface through a photoinduced cerium recycling redox reaction.

PubMed

Huang, Zhenhua; Wu, Zhengfang; Yang, Peng; Yang, Wantai

2014-09-01

It is generally accepted that Ce(4+) is unable to directly oxidize unreactive alkyl C-H bonds without the assistance of adjacent polar groups. Herein, we demonstrate in our newly developed confined photochemical reaction system that this recognized issue may be challenged. As we found, when a thin layer of a CeCl(3)/HCl aqueous solution was applied to a polymeric substrate and the substrate subjected to UV irradiation, Ce(3+) was first photooxidized to form Ce(4+) in the presence of H(+), and the in situ formed Ce(4+) then performs an oxidation reaction on the C-H bonds of the polymer surface to form surface-carbon radicals for radical graft polymerization reactions and functional-group transformations, while reducing to Ce(3+) and releasing H(+) in the process. This photoinduced cerium recycling redox (PCRR) reaction behaved as a biomimetic system in an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C-H bonds on polymer surfaces into small-molecule groups and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer-surface modification. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes.

PubMed

Godet-Bar, T; Leprêtre, J-C; Le Bacq, O; Sanchez, J-Y; Deronzier, A; Pasturel, A

2015-10-14

Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries.

(234)U/(238)U signatures associated with uranium ore bodies: part 3 Koongarra.

PubMed

Lowson, Richard T

2013-04-01

The Koongarra ore body is an early Proterozoic U ore body in the Alligator Rivers U province, Northern Territory, Australia. It has surface expression with a redox front located ∼30 m below the surface. The (234)U/(238)U activity ratios (AR) for the ground water and the amorphous phase of the solid have been analysed for the ore zone and dispersion halo as a function of depth. The results display a (234)U/(238)U AR signature with depth which may be common to all U ore bodies. The (234)U/(238)U AR is depressed below secular equilibrium in the weathered material above the redox front; rises significantly above secular equilibrium in the vicinity of the redox front; and is followed by a gradual decrease with depth below the redox front. The amplitude of the profile is a function of local conditions. A model is proposed for the signature in which oxidising waters preferentially leach the (234)U sites at the redox front due to preconditioning of the (234)U sites by α recoil during the decay of (23)(8)U to (23)(4)U. Mass balance requires the solid material left behind the redox front to have a (234)U/(238)U AR reduced below 1. Local second order effects may be superimposed on the signature. The signature may have application to calibrating scenarios for nuclear waste repositories, assisting in understanding historical climates, economic evaluation of U ore bodies and U exploration. Copyright © 2012 Elsevier Ltd. All rights reserved.

Synthesis and redox activity of "clicked" triazolylbiferrocenyl polymers, network encapsulation of gold and silver nanoparticles and anion sensing.

PubMed

Rapakousiou, Amalia; Deraedt, Christophe; Irigoyen, Joseba; Wang, Yanlan; Pinaud, Noël; Salmon, Lionel; Ruiz, Jaime; Moya, Sergio; Astruc, Didier

2015-03-02

The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.

Drug delivery properties of macroporous polystyrene solid foams.

PubMed

Canal, Cristina; Aparicio, Rosa Maria; Vilchez, Alejandro; Esquena, Jordi; García-Celma, Maria José

2012-01-01

Polymeric porous foams have been evaluated as possible new pharmaceutical dosage forms. These materials were obtained by polymerization in the continuous phase of highly concentrated emulsions prepared by the phase inversion temperature method. Their porosity, specific surface and surface topography were characterized, and the incorporation and release of active principles was studied using ketoprofen as model lipophilic molecule. Solid foams with very high pore volume, mainly inside macropores, were obtained by this method. The pore morphology of the materials was characterized, and very rough topography was observed, which contributed to their nearly superhydrophobic properties. These solid foams could be used as delivery systems for active principles with pharmaceutical interest, and in the present work ketoprofen was used as a model lipophilic molecule. Drug incorporation and release was studied from solid foam disks, using different concentrations of the loading solutions, achieving a delayed release with short lag-time.

Graphene nanocomposites for electrochemical cell electrodes

DOEpatents

Zhamu, Aruna; Jang, Bor Z.; Shi, Jinjun

2015-11-19

A composite composition for electrochemical cell electrode applications, the composition comprising multiple solid particles, wherein (a) a solid particle is composed of graphene platelets dispersed in or bonded by a first matrix or binder material, wherein the graphene platelets are not obtained from graphitization of the first binder or matrix material; (b) the graphene platelets have a length or width in the range of 10 nm to 10 .mu.m; (c) the multiple solid particles are bonded by a second binder material; and (d) the first or second binder material is selected from a polymer, polymeric carbon, amorphous carbon, metal, glass, ceramic, oxide, organic material, or a combination thereof. For a lithium ion battery anode application, the first binder or matrix material is preferably amorphous carbon or polymeric carbon. Such a composite composition provides a high anode capacity and good cycling response. For a supercapacitor electrode application, the solid particles preferably have meso-scale pores therein to accommodate electrolyte.

Investigation of multi-state charge-storage properties of redox-active organic molecules in silicon-molecular hybrid devices for DRAM and Flash applications

NASA Astrophysics Data System (ADS)

Gowda, Srivardhan Shivappa

Molecular electronics has recently spawned a considerable amount of interest with several molecules possessing charge-conduction and charge-storage properties proposed for use in electronic devices. Hybrid silicon-molecular technology has the promise of augmenting the current silicon technology and provide for a transitional path to future molecule-only technology. The focus of this dissertation work has been on developing a class of hybrid silicon-molecular electronic devices for DRAM and Flash memory applications utilizing redox-active molecules. This work exploits the ability of molecules to store charges with single-electron precision at room temperature. The hybrid devices are fabricated by forming self-assembled monolayers of redox-active molecules on Si and oxide (SiO2 and HfO2) surfaces via formation of covalent linkages. The molecules possess discrete quantum states from which electrons can tunnel to the Si substrate at discrete applied voltages (oxidation process, cell write), leaving behind a positively charged layer of molecules. The reduction (erase) process, which is the process of electrons tunneling back from Si to the molecules, neutralizes the positively charged molecular monolayer. Hybrid silicon-molecular capacitor test structures were electrically characterized with an electrolyte gate using cyclic voltammetry (CyV) and impedance spectroscopy (CV) techniques. The redox voltages, kinetics (write/erase speeds) and charge-retention characteristics were found to be strongly dependent on the Si doping type and densities, and ambient light. It was also determined that the redox energy states in the molecules communicate with the valence band of the Si substrate. This allows tuning of write and read states by modulating minority carriers in n- and p-Si substrates. Ultra-thin dielectric tunnel barriers (SiO2, HfO2) were placed between the molecules and the Si substrate to augment charge-retention for Flash memory applications. The redox response was studied as a function of tunnel oxide thickness, dielectric permittivity and energy barrier, and modified Butler-Volmer expressions were postulated to describe the redox kinetics. The speed vs. retention performance of the devices was improved via asymmetric layered tunnel barriers. The properties of molecules can be tailored by molecular design and synthetic chemistry. In this work, it was demonstrated that an alternate route to tune/enhance the properties of the hybrid device is to engineer the substrate (silicon) component. The molecules were attached to diode surfaces to tune redox voltages and improve charge-retention characteristics. N+ pockets embedded in P-Si well were utilized to obtain multiple states from a two-state molecule. The structure was also employed as a characterization tool in investigating the intrinsic properties of the molecules such as lateral conductivity within the monolayer. Redox molecules were also incorporated on an ultra thin gate-oxide of Si MOSFETs with the intent of studying the interaction of redox states with Si MOSFETs. The discrete molecular states were manifested in the drain current and threshold voltage characteristics of the device. This work demonstrates the multi-state modulation of Si-MOSFETs' drain current via redox-active molecular monolayers. Polymeric films of redox-active molecules were incorporated to improve the charge-density (ON/OFF ratio) and these structures may be employed for multi-state, low-voltage Flash memory applications. The most critical aspect of this research effort is to build a reliable and high density solid state memory technology. To this end, efforts were directed towards replacement of the electrolytic gate, which forms an extremely thin insulating double layer (˜10 nm) at the electrolyte-molecule interface, with a combination of an ultra-thin high-K dielectric layer and a metal gate. Several interesting observations were made in the research approaches towards integration and provided valuable insights into the electrolyte-redox systems. In summary, this work provides fundamental insights into the interaction of redox-energy states with silicon substrate and realistic approaches for exploiting the unique properties of the molecules that may enable solutions for nanoscale high density, low-voltage, long retention and multiple bit memory applications.

Determination of the mechanical properties of solid and cellular polymeric dosage forms by diametral compression.

PubMed

Blaesi, Aron H; Saka, Nannaji

2016-07-25

At present, the immediate-release solid dosage forms, such as the oral tablets and capsules, are granular solids. They release drug rapidly and have adequate mechanical properties, but their manufacture is fraught with difficulties inherent in processing particulate matter. Such difficulties, however, could be overcome by liquid-based processing. Therefore, we have recently introduced polymeric cellular (i.e., highly porous) dosage forms prepared from a melt process. Experiments have shown that upon immersion in a dissolution medium, the cellular dosage forms with polyethylene glycol (PEG) as excipient and with predominantly open-cell topology disintegrate by exfoliation, thus enabling rapid drug release. If the volume fraction of voids of the open-cell structures is too large, however, their mechanical strength is adversely affected. At present, the common method for determining the tensile strength of brittle, solid dosage forms (such as select granular forms) is the diametral compression test. In this study, the theory of diametral compression is first refined to demonstrate that the relevant mechanical properties of ductile and cellular solids (i.e., the elastic modulus and the yield strength) can also be extracted from this test. Diametral compression experiments are then conducted on PEG-based solid and cellular dosage forms. It is found that the elastic modulus and yield strength of the open-cell structures are about an order of magnitude smaller than those of the non-porous solids, but still are substantially greater than the stiffness and strength requirements for handling the dosage forms manually. This work thus demonstrates that melt-processed polymeric cellular dosage forms that release drug rapidly can be designed and manufactured to have adequate mechanical properties. Copyright © 2016. Published by Elsevier B.V.

A system using solid ceramic oxygen electrolyte cells to measure oxygen fugacities in gas-mixing systems

NASA Technical Reports Server (NTRS)

Williams, R. J.; Mullins, O.

1976-01-01

Details are given for the construction and operation of a 101.3 kN/sq m (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the high input impedance electronics necessary for measurements, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change relative to temperature and redox state. The calibration and maintenance of the system are discussed.

JSC systems using solid ceramic oxygen electrolyte cells to measure oxygen fugacites in gas-mixing systems

NASA Technical Reports Server (NTRS)

Williams, R. J.; Mullins, O.

1981-01-01

Details are given for the construction and operation of a 101.3 KN/sq meter (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change of temperature. A thermogravimetric analysis system employing these techniques of redox control and measurement is also described. The calibration and maintenance of the system are discussed.

Hybrid anodes for redox flow batteries

DOEpatents

Wang, Wei; Xiao, Jie; Wei, Xiaoliang; Liu, Jun; Sprenkle, Vincent L.

2015-12-15

RFBs having solid hybrid electrodes can address at least the problems of active material consumption, electrode passivation, and metal electrode dendrite growth that can be characteristic of traditional batteries, especially those operating at high current densities. The RFBs each have a first half cell containing a first redox couple dissolved in a solution or contained in a suspension. The solution or suspension can flow from a reservoir to the first half cell. A second half cell contains the solid hybrid electrode, which has a first electrode connected to a second electrode, thereby resulting in an equipotential between the first and second electrodes. The first and second half cells are separated by a separator or membrane.

Reversible chemical delithiation/lithiation of LiFePO4: towards a redox flow lithium-ion battery.

PubMed

Huang, Qizhao; Li, Hong; Grätzel, Michael; Wang, Qing

2013-02-14

Reversible chemical delithiation/lithiation of LiFePO(4) was successfully demonstrated using ferrocene derivatives, based on which a novel energy storage system--the redox flow lithium-ion battery (RFLB), was devised by integrating the operation flexibility of a redox flow battery and high energy density of a lithium-ion battery. Distinct from the recent semi-solid lithium rechargeable flow battery, the energy storage materials of RFLB stored in separate energy tanks remain stationary upon operation, giving us a fresh perspective on building large-scale energy storage systems with higher energy density and improved safety.

Lithium/organosulfur redox cell having protective solid electrolyte barrier formed on anode and method of making same

DOEpatents

De Jonghe, Lutgard C.; Visco, Steven J.; Liu, Meilin; Mailhe, Catherine C.

1990-01-01

A lithium/organosulfur redox cell is disclosed which comprises a solid lium anode, a liquid organosulfur cathode, and a barrier layer formed adjacent a surface of the solid lithium anode facing the liquid organosulfur cathode consisting of a reaction product of the lithium anode with the organosulfur cathode. The organosulfur cathode comprises a material having the formula (R(S).sub.y).sub.N where y=1 to 6, n=2 to 20 and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the linear chain may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

Polymerization of amino acids under high-pressure conditions: Implication to chemical evolution on the early Earth

NASA Astrophysics Data System (ADS)

Kakegawa, T.; Ohara, S.; Ishiguro, T.; Abiko, H.; Nakazawa, H.

2008-12-01

Prebiotic polymerization of amino acids is the most fundamental reaction to promote the chemical evolution for origin of life. Polymerization of amino acids is the dehydration reaction. This questions as to if submarine hydrothermal conditions, thus hydrated enironments, were appropreate for peptide formations. Our previous experiments implied that non-aqueous and high-pressure environments (more than 20 MPa) would be suitable for polymerization of amino acids (Ohara et al., 2006). This leads to the hypothesis that the first peptides may have formed in the Hadean oceanic crustal environments, where dehydration proceeded with availability of appropriate temperatures and pressures. In the present study, experiments simulating the crustal conditions were performed with various pressures (1-175 MPa) and temperatures (100- 200 C degree) using autoclaves. Purified powders (100 mg) of alanine, glycine, valine and aspartic acid were used in the experiments without mixing water in order to examine the solid-solid reactions. The products were analyzed using HPLC and LC-MS. Results indicate that: (1) longer time is required to form peptide compared to those of previous aqueous experiments; (2) pressure has a role to limit the production of melanoidine and cyclic amino acids, which are inhibitors for elongation of peptides; (3) glycine was polymerized up to 11-mer, which was not formed in any previous experiments without catalyses; (4) valine was polymerized up to 3-mer; and (5) aspartic acid was polymerized to 4-mer, accompanied with production of other amino acids. It is noteworthy that high-pressure environments favor all examined polymerization reactions. Such situations would have happened inside of deep oceanic crusts of the early Earth.

Enzymatic polymerization of natural anacardic acid and antibiofouling effects of polyanacardic acid coatings.

PubMed

Chelikani, Rahul; Kim, Yong Hwan; Yoon, Do-Young; Kim, Dong-Shik

2009-05-01

Anacardic acid, separated from cashew nut shell liquid, is well known for its strong antibiotic and antioxidant activities. Recent findings indicate that phenolic compounds from plant sources have an effect on Gram-negative bacteria biofilm formation. In this work, a polyphenolic coating was prepared from anacardic acid using enzymatic synthesis and tested for its effects on biofilm formation of both Gram-negative and Gram-positive bacteria. Natural anacardic acid was enzymatically polymerized using soybean peroxidase. Hydrogen peroxide and phenothiazine-10-propionic acid were used as an oxidizing agent and redox mediator, respectively. Nuclear magnetic resonance and Fourier transform infrared (FTIR) analyses showed the formation of oxyphenylene and phenylene units through the phenol rings. No linkage through the alkyl chain was observed, which proved a high chemo-selectivity of the enzyme. Aqueous solvents turned out to play an important role in the polymer production yield and molecular weight. With 2-propanol, the highest production yield (61%) of polymer (molecular weight = 3,900) was observed, and with methanol, higher-molecular-weight polymers (5,000) were produced with lower production yields (43%). The resulting polyanacardic acid was cross-linked on a solid surface to form a permanent natural polymer coating. The FTIR analysis indicates that the cross-linking between the polymers took place through the unsaturated alkyl side chains. The polyanacardic acid coating was then tested for its antibiofouling effect against Gram-negative and Gram-positive bacteria and compared with the antibiofouling effects of polycardanol coatings reported in the literature. The polyanacardic acid coating showed more reduction in biofilm formation on its surface than polycardanol coatings in the case of Gram-positive bacteria, while in the case of Gram-negative bacteria, it showed a similar reduction in biofilm formation as polycardanol.

Polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids for flexible, all-solid-state supercapacitors.

PubMed

Chen, Yuyun; Han, Min; Tang, Yujia; Bao, Jianchun; Li, Shunli; Lan, Yaqian; Dai, Zhihui

2015-08-11

Novel polypyrrole-polyoxometalate/reduced graphene oxide ternary nanohybrids (TNHs) are synthesized via a one-pot redox relay strategy. The TNHs exhibit high areal specific capacitance (2.61 mF cm(-2)), and the fabricated solid device also exhibits good rate capability, excellent flexibility and mechanical stability.

The self-assembly of redox active peptides: Synthesis and electrochemical capacitive behavior.

PubMed

Piccoli, Julia P; Santos, Adriano; Santos-Filho, Norival A; Lorenzón, Esteban N; Cilli, Eduardo M; Bueno, Paulo R

2016-05-01

The present work reports on the synthesis of a redox-tagged peptide with self-assembling capability aiming applications in electrochemically active capacitive surfaces (associated with the presence of the redox centers) generally useful in electroanalytical applications. Peptide containing ferrocene (fc) molecular (redox) group (Ac-Cys-Ile-Ile-Lys(fc)-Ile-Ile-COOH) was thus synthesized by solid phase peptide synthesis (SPPS). To obtain the electrochemically active capacitive interface, the side chain of the cysteine was covalently bound to the gold electrode (sulfur group) and the side chain of Lys was used to attach the ferrocene in the peptide chain. After obtaining the purified redox-tagged peptide, the self-assembly and redox capability was characterized by cyclic voltammetry (CV) and electrochemical impedance-based capacitance spectroscopy techniques. The obtained results confirmed that the redox-tagged peptide was successfully attached by forming an electroactive self-assembled monolayer onto gold electrode. The design of redox active self-assembly ferrocene-tagged peptide is predictably useful in the development of biosensor devices precisely to detect, in a label-free platform, those biomarkers of clinical relevance. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 357-367, 2016. © 2016 Wiley Periodicals, Inc.

Solid-Lubricant, Polymer - Polymeric and Functionalized Fiber- and Powder Reinforced Composites of Ultra-High Molecular Weight Polyethylene

NASA Astrophysics Data System (ADS)

Panin, S. V.; Alexenko, V. O.; Buslovich, D. G.; Anh, Nguyen Duc; Qitao, Huang

2018-01-01

Mechanical and tribotechnical characteristics of solid-lubricant and polymer-polymeric composites of UHMWPE were studied for the sake of design extrudable, wear-resistant, self-lubricant polymer mixtures for Additive Manufacturing (AM). Tribotechnical properties of UHMWPE blends with the optimized content of solid lubricant fillers (polytetrafluoroethylene, calcium stearate, molybdenum disulphide, colloidal graphite, boron nitride) were studied under dry sliding friction at different velocities (V = 0.3 and 0.5 m/s) and loads (P = 60 and 140 N). Also, in order to increase strength and wear-resistance of UHMWPE composites they were reinforced with wollastonite microfibers and aluminum metahydroxide AlO (OH) microparticles preliminary treated (functionalized) in polyorganosiloxane. The comparison on measured mechanical and tribotechnical properties are given with interpretation of the mechanisms of observed phenomenon.

A Review on Surface Stress-Based Miniaturized Piezoresistive SU-8 Polymeric Cantilever Sensors

NASA Astrophysics Data System (ADS)

Mathew, Ribu; Ravi Sankar, A.

2018-06-01

In the last decade, microelectromechanical systems (MEMS) SU-8 polymeric cantilevers with piezoresistive readout combined with the advances in molecular recognition techniques have found versatile applications, especially in the field of chemical and biological sensing. Compared to conventional solid-state semiconductor-based piezoresistive cantilever sensors, SU-8 polymeric cantilevers have advantages in terms of better sensitivity along with reduced material and fabrication cost. In recent times, numerous researchers have investigated their potential as a sensing platform due to high performance-to-cost ratio of SU-8 polymer-based cantilever sensors. In this article, we critically review the design, fabrication, and performance aspects of surface stress-based piezoresistive SU-8 polymeric cantilever sensors. The evolution of surface stress-based piezoresistive cantilever sensors from solid-state semiconductor materials to polymers, especially SU-8 polymer, is discussed in detail. Theoretical principles of surface stress generation and their application in cantilever sensing technology are also devised. Variants of SU-8 polymeric cantilevers with different composition of materials in cantilever stacks are explained. Furthermore, the interdependence of the material selection, geometrical design parameters, and fabrication process of piezoresistive SU-8 polymeric cantilever sensors and their cumulative impact on the sensor response are also explained in detail. In addition to the design-, fabrication-, and performance-related factors, this article also describes various challenges in engineering SU-8 polymeric cantilevers as a universal sensing platform such as temperature and moisture vulnerability. This review article would serve as a guideline for researchers to understand specifics and functionality of surface stress-based piezoresistive SU-8 cantilever sensors.[Figure not available: see fulltext.

STIR: Redox-Switchable Olefin Polymerization Catalysis: Electronically Tunable Ligands for Controlled Polymer Synthesis

DTIC Science & Technology

2013-03-28

positions leading us to utilize a two-step procedure in which the amines were treated with methylchloroformate before being fully reduced with lithium ...was carried out using lithium aluminum hydride before undergoing a similar two-step methylation as described above to yield bisferrocenyl ligand 16...of Ni-based complex 30. CV’s were ran in DCM with tetrabutylammonium hexafluorophosphate electrolyte and referenced to a ferrocene standard. In

Nanocellular foam with solid flame retardant

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

Chen, Liang; Kelly-Rowley, Anne M.; Bunker, Shana P.

Prepare nanofoam by (a) providing an aqueous solution of a flame retardant dissolved in an aqueous solvent, wherein the flame retardant is a solid at 23.degree. C. and 101 kiloPascals pressure when in neat form; (b) providing a fluid polymer composition selected from a solution of polymer dissolved in a water-miscible solvent or a latex of polymer particles in a continuous aqueous phase; (c) mixing the aqueous solution of flame retardant with the fluid polymer composition to form a mixture; (d) removing water and, if present, solvent from the mixture to produce a polymeric composition having less than 74 weight-percentmore » flame retardant based on total polymeric composition weight; (e) compound the polymeric composition with a matrix polymer to form a matrix polymer composition; and (f) foam the matrix polymer composition into nanofoam having a porosity of at least 60 percent.« less

Hydrocarbon polymeric binder for advanced solid propellant

NASA Technical Reports Server (NTRS)

Potts, J. E. (Editor); Ashcraft, A. C., Jr.; Wise, E. W.

1971-01-01

Various experimental factors were examined to determine the source of difficulty in an isoprene polymerization in the 5-gallon reactor which gave a non-uniform product of low functionality. It was concluded that process improvements relating to initiator and monomer purity were desirable, but that the main difficulty was in the initiator feed system. A new pumping system was installed and an analog simulation of the reactor, feed system and initiator decomposition kinetics was devised which permits the selection of initial initiator concentrations and feed rates to use to give a nearly uniform initiator concentration throughout a polymerization run. An isoprene polymerization was run in which the process improvements were implemented.

Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s: Synthesis, Structure, and Properties.

PubMed

Feng, Xueling; Zhang, Kaihuan; Chen, Peng; Sui, Xiaofeng; Hempenius, Mark A; Liedberg, Bo; Vancso, G Julius

2016-12-01

Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side groups are copolymerized with NIPAM in aqueous solutions under ultraviolet light (λ = 365 nm) in the presence of a photoinitiator. The PFS-PILs serve as a macro-cross-linker and also provide redox responsiveness. The swelling ratio, morphology, and lower critical solution temperature (LCST) of the hydrogels are studied as a function of the PNIPAM/PFS ratio. The value of the LCST is dependent on the choice of the counterion of the PIL and the PNIPAM/PFS ratio. The hydrogel is employed as a reducing environment for the in situ fabrication of gold nanoparticles (AuNPs), forming AuNP-hydrogel composites. The localized surface plasmon resonance peak of the as-synthesized Au nanoparticles inside the hydrogel could be tuned by altering the temperature. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Creation of an optically tunable, solid tissue phantom for use in cancer detection

NASA Astrophysics Data System (ADS)

Tucker, Matthew B.; Wallace, Catherine; Mantena, Sreekar; Cornwell, Neil; Ross, Weston; Odion, Ren; Vo-Dinh, Tuan; Codd, Patrick

2018-02-01

An optically tunable, solid tissue phantom was developed in order to aid in the verification and validation of non-destructive cancer detection technologies based on fluorescence spectroscopy. The solid tissue phantom contained agarose, hemoglobin, Intralipid, NADH, and FAD. The redox ratio of the solid phantoms were shown to be tunable; thus, indicating that these phantoms could be used to tailor specific optical conditions that mimic cancerous and healthy tissues. Therefore, this solid tissue phantom can serve as a suitable test bed to evaluate fluorescence spectroscopy based cancer detection devices.

Polyethylenimine architecture-dependent metabolic imprints and perturbation of cellular redox homeostasis.

PubMed

Hall, Arnaldur; Parhamifar, Ladan; Lange, Marina Krarup; Meyle, Kathrine Damm; Sanderhoff, May; Andersen, Helene; Roursgaard, Martin; Larsen, Anna Karina; Jensen, Per Bo; Christensen, Claus; Bartek, Jiri; Moghimi, Seyed Moein

2015-03-01

Polyethylenimines (PEIs) are among the most efficient polycationic non-viral transfectants. PEI architecture and size not only modulate transfection efficiency, but also cytotoxicity. However, the underlying mechanisms of PEI-induced multifaceted cell damage and death are largely unknown. Here, we demonstrate that the central mechanisms of PEI architecture- and size-dependent perturbations of integrated cellular metabolomics involve destabilization of plasma membrane and mitochondrial membranes with consequences on mitochondrial oxidative phosphorylation (OXPHOS), glycolytic flux and redox homeostasis that ultimately modulate cell death. In comparison to linear PEI, the branched architectures induced greater plasma membrane destabilization and were more detrimental to glycolytic activity and OXPHOS capacity as well as being a more potent inhibitor of the cytochrome c oxidase. Accordingly, the branched architectures caused a greater lactate dehydrogenase (LDH) and ATP depletion, activated AMP kinase (AMPK) and disturbed redox homeostasis through diminished availability of nicotinamide adenine dinucleotide phosphate (NADPH), reduced antioxidant capacity of glutathione (GSH) and increased burden of reactive oxygen species (ROS). The differences in metabolic and redox imprints were further reflected in the transfection performance of the polycations, but co-treatment with the GSH precursor N-acetyl-cysteine (NAC) counteracted redox dysregulation and increased the number of viable transfected cells. Integrated biomembrane integrity and metabolomic analysis provides a rapid approach for mechanistic understanding of multifactorial polycation-mediated cytotoxicity, and could form the basis for combinatorial throughput platforms for improved design and selection of safer polymeric vectors. Copyright © 2014 Elsevier B.V. All rights reserved.

MALDI-TOF mass spectrometry: avoidance of artifacts and analysis of caffeine-precipitated SII thearubigins from 15 commercial black teas.

PubMed

Drynan, J Warren; Clifford, Michael N; Obuchowicz, Jacek; Kuhnert, Nikolai

2012-05-09

Thearubigins are the quantitatively major phenolic compounds in black tea, accounting for some 60-70% of the solids in a typical black tea infusion. MALDI-TOF mass spectra for caffeine-precipitated SII thearubigins (SII CTRs) from 15 different commercial teas support previous conclusions that SII CTRs are polyhydroxylated oligomers (rather than polymers) of catechins and catechin gallates in redox equilibrium with their quinone counterparts. Some 4500 peaks were revealed in a mass range from m/z 500 to 2100. Polyphenols are redox-susceptible and readily generate artifacts during MALDI-TOF analysis when the matrix is also redox-susceptible. Of the nine matrices evaluated, 3',4',5'-trihydroxyacetophenone (F) provided the best compromise between signal intensity and redox artifact formation.

Preparation of Sic/AIN Solid Solutions Using Organometallic Precursors

DTIC Science & Technology

1989-02-15

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

Supramolecular intermediates in the synthesis of polymeric carbon nitride from melamine cyanurate

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

Dante, Roberto C., E-mail: rcdante@yahoo.com; Sánchez-Arévalo, Francisco M.; Chamorro-Posada, Pedro

The adduct of melamine and cyanuric acid (MCA) was used in past research to produce polymeric carbon nitride and precursors. The reaction yield was considerably incremented by the addition of sulfuric acid. The polymeric carbon nitride formation occurs around 450 °C at temperatures above the sublimation of the adduct components, which occurs around 400 °C. In this report the effect of sulfuric acid on MCA was investigated. It was found that the MCA rosette supramolecular channel structures behave as a solid solvent able to host small molecules, such as sulfuric acid, inside these channels and interact with them. Therefore, themore » sulfuric acid effect was found to be close to that of a solute that causes a temperature increment of the “solvent sublimation” enough to allowing the formation of polymeric carbon nitride to occur. Sulfate ions are presumably hosted in the rosette channels of MCA as shown by simulations. - Graphical abstract: The blend of melamine cyanurate and sulfuric acid behaves like a solution so that melamine cyanurate decomposition is shifted to temperatures high enough to react and form polymeric carbon nitride. - Highlights: • The adduct of melamine and cyanuric acid behaves as a solid solvent. • The blend of sulfuric acid and melamine cyanurate behaves like a solution. • Melamine cyanurate decomposition is shifted to higher temperatures by sulfuric acid. • The formation of polymeric carbon nitride occurs for these higher temperatures.« less

Analysis of beer volatiles by polymeric imidazolium-solid phase microextraction coatings: Synthesis and characterization of polymeric imidazolium ionic liquids.

PubMed

González-Álvarez, Jaime; Blanco-Gomis, Domingo; Arias-Abrodo, Pilar; Pello-Palma, Jairo; Ríos-Lombardía, Nicolás; Busto, Eduardo; Gotor-Fernández, Vicente; Gutiérrez-Álvarez, María Dolores

2013-08-30

Two polymeric ionic liquids, 3-(but-3″-en-1″-yl)-1-[2'-hydroxycyclohexyl]-1H-imidazol-3-ium bis(trifluoromethanesulfonyl)imide (IL-1) and 1-(2'-hydroxycyclohexyl)-3-(4″-vinylbenzyl)-1H-imidazol-3-ium bis(trifluoromethylsulfonyl)imide (IL-2), have been synthesized by a free radical polymerization reaction and used as coatings for solid-phase microextraction (SPME). These new fibers exhibit good film stability, high thermal stability (270-290°C) and long lifetimes, and are used for the extraction of volatile compounds in lemon beer using gas chromatography separation and flame ionization detection. The scanning electron micrographs of the fiber surface revealed a polymeric ionic liquid (PIL) film, which is distributed homogeneously on the fiber. The developed PIL fiber showed good linearity between 50 and 2000μg/L with regression coefficients in the range of 0.996-0.999. The relative standard deviations (RSD) obtained in the peak area were found to vary between 1% and 12%, which assured that adequate repeatability was achieved. The spiked recoveries for three beer samples ranged from 78.4% to 123.6%. Experimental design has been employed in the optimization of extraction factors and robustness assessment. The polymeric IL-1 butenyl fiber showed a greater efficiency compared to the PDMS-DVB (65μm) and CAR-PDMS (75μm) for the extraction of all of the analytes studied. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Investigation of Expandable Polymeric Microspheres for Packaging Applications

DTIC Science & Technology

2012-06-06

FILMS COST REDUCTION OLEFIN POLYMERS COSTS PACKAGING MICROSPHERES WASTE DISPOSAL WEIGHT...MANAGEMENT THERMAL INSULATION DENSITY SOLID WASTES ENVIRONMENTAL IMPACT THERMOPLASTIC POLYMERS POLYMERS ...research. The purpose was to provide information on the incorporation of hollow, expandable  polymeric microspheres  into  thermoplastic   polymers   to

Charging a Li-O₂ battery using a redox mediator.

PubMed

Chen, Yuhui; Freunberger, Stefan A; Peng, Zhangquan; Fontaine, Olivier; Bruce, Peter G

2013-06-01

The non-aqueous Li-air (O2) battery is receiving intense interest because its theoretical specific energy exceeds that of Li-ion batteries. Recharging the Li-O2 battery depends on oxidizing solid lithium peroxide (Li2O2), which is formed on discharge within the porous cathode. However, transporting charge between Li2O2 particles and the solid electrode surface is at best very difficult and leads to voltage polarization on charging, even at modest rates. This is a significant problem facing the non-aqueous Li-O2 battery. Here we show that incorporation of a redox mediator, tetrathiafulvalene (TTF), enables recharging at rates that are impossible for the cell in the absence of the mediator. On charging, TTF is oxidized to TTF(+) at the cathode surface; TTF(+) in turn oxidizes the solid Li2O2, which results in the regeneration of TTF. The mediator acts as an electron-hole transfer agent that permits efficient oxidation of solid Li2O2. The cell with the mediator demonstrated 100 charge/discharge cycles.

A Thermally Re-mendable Cross-Linked Polymeric Material

NASA Astrophysics Data System (ADS)

Chen, Xiangxu; Dam, Matheus A.; Ono, Kanji; Mal, Ajit; Shen, Hongbin; Nutt, Steven R.; Sheran, Kevin; Wudl, Fred

2002-03-01

We have developed a transparent organic polymeric material that can repeatedly mend or ``re-mend'' itself under mild conditions. The material is a tough solid at room temperature and below with mechanical properties equaling those of commercial epoxy resins. At temperatures above 120°C, approximately 30% (as determined by solid-state nuclear magnetic resonance spectroscopy) of ``intermonomer'' linkages disconnect but then reconnect upon cooling, This process is fully reversible and can be used to restore a fractured part of the polymer multiple times, and it does not require additional ingredients such as a catalyst, additional monomer, or special surface treatment of the fractured interface.

Establishment of redox conditions during planetary collisions as an origin of chondrites

NASA Technical Reports Server (NTRS)

Tsuchiyama, A.; Kitamura, M.

1994-01-01

Collisions between a 'cometlike' body (mixtures of chondritic materials and ice) and a slightly differentiated body were proposed for shock origin of ordinary chondrites. In this model, chondrules were formed with shock melting, and matrices were formed both by fracturing of materials and by recondensation of evaporated materials. This model can explain different redox conditions of chondrite formations by ice evaporation. Although this model was originally proposed for ordinary chondrites, we assume here that the model can be extended to chondrite formation in general. In this paper, redox conditions during chondrite formation by collisions will be discussed in the light of phase diagrams for solid-vapor equilibria.

Neuromorphic transistor achieved by redox reaction of WO3 thin film

NASA Astrophysics Data System (ADS)

Tsuchiya, Takashi; Jayabalan, Manikandan; Kawamura, Kinya; Takayanagi, Makoto; Higuchi, Tohru; Jayavel, Ramasamy; Terabe, Kazuya

2018-04-01

An all-solid-state neuromorphic transistor composed of a WO3 thin film and a proton-conducting electrolyte was fabricated for application to next-generation information and communication technology including artificial neural networks. The drain current exhibited a 4-order-of-magnitude increment by redox reaction of the WO3 thin film owing to proton migration. Learning and forgetting characteristics were well tuned by the gate control of WO3 redox reactions owing to the separation of the current reading path and pulse application path in the transistor structure. This technique should lead to the development of versatile and low-power-consumption neuromorphic devices.

Redox-active porous coordination polymer based on trinuclear pivalate: Temperature-dependent crystal rearrangement and redox-behavior

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

Lytvynenko, Anton S.; Kiskin, Mikhail A., E-mail: mkiskin@igic.ras.ru; Dorofeeva, Victoria N.

2015-03-15

Linking of trinuclear pivalate Fe{sub 2}NiO(Piv){sub 6} (Piv=O{sub 2}CC(CH{sub 3}){sub 3}) by 2,6-bis(4-pyridyl)-4-(1-naphthyl)pyridine (L) resulted in formation of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)·Solv, which was characterized in two forms: DMSO solvate Fe{sub 2}NiO(Piv){sub 6}(L)(DMSO)·2.5DMSO (1) or water solvate Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) (2). X-ray structure of 1 was determined. Crystal lattice of 1 at 160 K contained open channels, filled by captured solvent, while temperature growth to 296 K led to the crystal lattice rearrangement and formation of closed voids. Redox-behavior of 2 was studied by cyclic voltammetry for a solid compound, deposited on glassy-carbon electrode. Redox-activity of Lmore » preserved upon incorporation in the coordination polymer. The presence of pores in desolvated sample Fe{sub 2}NiO(Piv){sub 6}(L) was confirmed by the measurements of N{sub 2} and H{sub 2} adsorption at 77 K. Potential barriers of the different molecules diffusion through pores were estimated by the means of molecular mechanics. - Graphical abstract: Redox-behavior of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) was studied by cyclic voltammetry in thin film, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. Potential barriers of different molecules diffusion through pores were estimated by the means of molecular mechanics. - Highlights: • Porous 1D coordination polymer was synthesized. • Temperature growth led to pores closing due to crystal lattice rearrangement. • Redox-activity of ligand preserved upon incorporation into coordination polymer. • Redox-properties of solid coordination polymer were studied in thin film. • Diffusion barriers were evaluated by molecular mechanics.« less

Anti-inflammatory polymersomes of redox-responsive polyprodrug amphiphiles with inflammation-triggered indomethacin release characteristics.

PubMed

Tan, Jiajia; Deng, Zhengyu; Liu, Guhuan; Hu, Jinming; Liu, Shiyong

2018-03-21

Inflammation serves as a natural defense mechanism to protect living organisms from infectious diseases. Nonsteroidal anti-inflammatory drugs (NSAIDs) can help relieve inflammatory reactions and are clinically used to treat pain, fever, and inflammation, whereas long-term use of NSAIDs may lead to severe side effects including gastrointestinal damage and cardiovascular toxicity. Therefore, it is of increasing importance to configure new dosing strategies and alleviate the side effects of NSAIDs. Towards this goal, glutathione (GSH)-responsive disulfide bonds and hydrogen peroxide (H 2 O 2 )-reactive phenylboronic ester linkages were utilized as triggering moieties in this work to design redox-responsive prodrug monomers and polyprodrug amphiphiles based on indomethacin (IND) drug. Note that IND is a widely prescribed NSAID in the clinic. Starting from three types of redox-reactive IND prodrug monomers, redox-responsive polyprodrug amphiphiles were synthesized through reversible addition-fragmentation chain transfer (RAFT) polymerizations of prodrug monomers using poly(ethylene oxide) (PEO)-based macroRAFT agent. The resultant polyprodrug amphiphiles with high IND loading contents (>33 wt%) could self-assemble into polymersomes with PEO shielding coronas and redox-responsive bilayer membranes composed of IND prodrugs. Upon incubation with GSH or H 2 O 2 , controlled release of intact IND in the active form from polyprodrug polymersomes was actuated by GSH-mediated disulfide cleavage reaction and H 2 O 2 -mediated oxidation of phenylboronic ester moieties, respectively, followed by self-immolative degradation events. Furthermore, in vitro studies at the cellular level revealed that redox-responsive polymersomes could efficiently relieve inflammatory responses induced by lipopolysaccharide (LPS) in RAW264.7 macrophage cells. Copyright © 2018. Published by Elsevier Ltd.

Amine enriched solid sorbents for carbon dioxide capture

DOEpatents

Gray, McMahan L.; Soong, Yee; Champagne, Kenneth J.

2003-04-15

A new method for making low-cost CO.sub.2 sorbents that can be used in large-scale gas-solid processes. The new method entails treating a solid substrate with acid or base and simultaneous or subsequent treatment with a substituted amine salt. The method eliminates the need for organic solvents and polymeric materials for the preparation of CO.sub.2 capture systems.

Thermal Coefficient of Redox Potential of Alkali Metals

NASA Astrophysics Data System (ADS)

Fukuzumi, Yuya; Hinuma, Yoyo; Moritomo, Yutaka

2018-05-01

The thermal coefficient (α) of redox potential (V) is a significant physical quantity that converts the thermal energy into electric energy. In this short note, we carefully determined α of alkali metals (A = Li and Na) against electrolyte solution. The obtained α is much larger than that expected from the specific heat (CpA) of solid A and depends on electrolyte solution. These observations indicate that the solvent has significant effect on α.

Heterogeneous chemical reactions: Preparation of monodisperse latexes

NASA Technical Reports Server (NTRS)

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

1977-01-01

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

A Coordination Network with Ligand-Centered Redox Activity Based on facial-[CrIII (2-mercaptophenolato)3 ]3- Metalloligands.

PubMed

Wakizaka, Masanori; Matsumoto, Takeshi; Kobayashi, Atsushi; Kato, Masako; Chang, Ho-Chol

2017-07-21

The design of redox-active metal-organic frameworks and coordination networks (CNs), which exhibit metal- and/or ligand-centered redox activity, has recently received increased attention. In this study, the redox-active metalloligand (RML) [Me 4 N] 3 fac-[Cr III (mp) 3 ] (1) (mp=2-mercaptophenolato) was synthesized and characterized by single-crystal X-ray diffraction analysis, and its reversible ligand-centered one-electron oxidation was examined by cyclic voltammetry and spectroelectrochemical measurements. Since complex 1 contains O/S coordination sites in three directions, complexation with K + ions led to the formation of the two-dimensional honeycomb sheet-structured [K 3 fac-{Cr III (mp) 3 }(H 2 O) 6 ] n (2⋅6 H 2 O), which is the first example of a redox-active CN constructed from a RML with o-disubstituted benzene ligands. Herein, we unambiguously demonstrate the ligand-centered redox activity of the RML within the CN 2⋅6 H 2 O in the solid state. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic matter and modeling redox reactions during river bank filtration in an alluvial aquifer of the Lot River, France.

PubMed

Kedziorek, Monika A M; Geoffriau, Stephane; Bourg, Alain C M

2008-04-15

A 3 year study of the infiltration of Lot River water into a well field located in an adjacent gravel and clay alluvial aquifer was conducted to assess the importance of organic matter regarding the redox processes which influence groundwater quality in a positive (denitrification) or negative (Mn dissolution) manner. Chloride was used to quantify the mixing of river water with groundwater. According to modeling with PHREEQC, the biodegradation of the infiltrated dissolved organic carbon (DOCi) is not sufficient to explain the observed consequences of the redox reactions (dissolved O2 depletion, denitrification, Mn dissolution). Another electron donor source must therefore be involved: we propose solid organic carbon (SOC) as a likely candidate, if made available for degradation by prior hydrolysis. Its contribution to redox reactions could be significant (30-80% of the total organic carbon consumed by redox reactions during river bank filtration). We show here also that even though the first few meters of infiltration are highly reactive, significant redox reactions can take place further in the aquifer, possibly affecting groundwater quality away from the river bank.

3D-Hydrogel Based Polymeric Nanoreactors for Silver Nano-Antimicrobial Composites Generation.

PubMed

Soto-Quintero, Albanelly; Romo-Uribe, Ángel; Bermúdez-Morales, Víctor H; Quijada-Garrido, Isabel; Guarrotxena, Nekane

2017-08-01

This study underscores the development of Ag hydrogel nanocomposites, as smart substrates for antibacterial uses, via innovative in situ reactive and reduction pathways. To this end, two different synthetic strategies were used. Firstly thiol-acrylate (PSA) based hydrogels were attained via thiol-ene and radical polymerization of polyethylene glycol (PEG) and polycaprolactone (PCL). As a second approach, polyurethane (PU) based hydrogels were achieved by condensation polymerization from diisocyanates and PCL and PEG diols. In fact, these syntheses rendered active three-dimensional (3D) hydrogel matrices which were used as nanoreactors for in situ reduction of AgNO₃ to silver nanoparticles. A redox chemistry of stannous catalyst in PU hydrogel yielded spherical AgNPs formation, even at 4 °C in the absence of external reductant; and an appropriate thiol-functionalized polymeric network promoted spherical AgNPs well dispersed through PSA hydrogel network, after heating up the swollen hydrogel at 103 °C in the presence of citrate-reductant. Optical and swelling behaviors of both series of hydrogel nanocomposites were investigated as key factors involved in their antimicrobial efficacy over time. Lastly, in vitro antibacterial activity of Ag loaded hydrogels exposed to Pseudomona aeruginosa and Escherichia coli strains indicated a noticeable sustained inhibitory effect, especially for Ag-PU hydrogel nanocomposites with bacterial inhibition growth capabilities up to 120 h cultivation.

Role of Co-Vapors in Vapor Deposition Polymerization

PubMed Central

Lee, Ji Eun; Lee, Younghee; Ahn, Ki-Jin; Huh, Jinyoung; Shim, Hyeon Woo; Sampath, Gayathri; Im, Won Bin; Huh, Yang–Il; Yoon, Hyeonseok

2015-01-01

Polypyrrole (PPy)/cellulose (PPCL) composite papers were fabricated by vapor phase polymerization. Importantly, the vapor-phase deposition of PPy onto cellulose was assisted by employing different co-vapors namely methanol, ethanol, benzene, water, toluene and hexane, in addition to pyrrole. The resulting PPCL papers possessed high mechanical flexibility, large surface-to-volume ratio, and good redox properties. Their main properties were highly influenced by the nature of the co-vaporized solvent. The morphology and oxidation level of deposited PPy were tuned by employing co-vapors during the polymerization, which in turn led to change in the electrochemical properties of the PPCL papers. When methanol and ethanol were used as co-vapors, the conductivities of PPCL papers were found to have improved five times, which was likely due to the enhanced orientation of PPy chain by the polar co-vapors with high dipole moment. The specific capacitance of PPCL papers obtained using benzene, toluene, water and hexane co-vapors was higher than those of the others, which is attributed to the enlarged effective surface area of the electrode material. The results indicate that the judicious choice and combination of co-vapors in vapor-deposition polymerization (VDP) offers the possibility of tuning the morphological, electrical, and electrochemical properties of deposited conducting polymers. PMID:25673422

Redox agents and N-ethylmaleimide affect protein polymerization during laboratory scale dry pasta production and cooking.

PubMed

Bruneel, Charlotte; Buggenhout, Joke; Lagrain, Bert; Brijs, Kristof; Delcour, Jan A

2016-04-01

Durum wheat (Triticum durum Desf.) semolina gluten proteins consist of monomeric gliadin and polymeric glutenin and determine the quality of pasta products made therefrom. During pasta drying, glutenin starts polymerizing already below 60 °C (65% relative humidity (RH)), whereas gliadin only is incorporated in the protein network at temperatures exceeding 68 °C (68% RH) through thiol (SH)/disulfide (SS) exchange reactions. Removal of free SH groups in glutenin by adding 2.3 μmol KBrO3 or KIO3 per g dry matter semolina protein (g protein) or 13.8 μmol N-ethylmaleimide/g protein reduces gliadin-glutenin cross-linking during pasta drying and/or cooking and yields cooked pasta of high quality. Introducing free SH groups by adding 13.8 μmol glutathione/g protein increases gliadin-glutenin cross-linking during pasta processing, resulting in cooked pasta of lower quality. We hypothesize that too much gliadin incorporation in the glutenin network during pasta processing tightens the protein network and results in lower cooking quality. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed

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

2007-05-08

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

Faradic redox active material of Cu7S4 nanowires with a high conductance for flexible solid state supercapacitors

NASA Astrophysics Data System (ADS)

Javed, Muhammad Sufyan; Dai, Shuge; Wang, Mingjun; Xi, Yi; Lang, Qiang; Guo, Donglin; Hu, Chenguo

2015-08-01

The exploration of high Faradic redox active materials with the advantages of low cost and low toxicity has been attracting great attention for producing high energy storage supercapacitors. Here, the high Faradic redox active material of Cu7S4-NWs coated on a carbon fiber fabric (CFF) is directly used as a binder-free electrode for a high performance flexible solid state supercapacitor. The Cu7S4-NW-CFF supercapacitor exhibits excellent electrochemical performance such as a high specific capacitance of 400 F g-1 at the scan rate of 10 mV s-1 and a high energy density of 35 Wh kg-1 at a power density of 200 W kg-1, with the advantages of a light weight, high flexibility and long term cycling stability by retaining 95% after 5000 charge-discharge cycles at a constant current of 10 mA. The high Faradic redox activity and high conductance behavior of the Cu7S4-NWs result in a high pseudocapacitive performance with a relatively high specific energy and specific power. Such a new type of pseudocapacitive material of Cu7S4-NWs with its low cost is very promising for actual application in supercapacitors.The exploration of high Faradic redox active materials with the advantages of low cost and low toxicity has been attracting great attention for producing high energy storage supercapacitors. Here, the high Faradic redox active material of Cu7S4-NWs coated on a carbon fiber fabric (CFF) is directly used as a binder-free electrode for a high performance flexible solid state supercapacitor. The Cu7S4-NW-CFF supercapacitor exhibits excellent electrochemical performance such as a high specific capacitance of 400 F g-1 at the scan rate of 10 mV s-1 and a high energy density of 35 Wh kg-1 at a power density of 200 W kg-1, with the advantages of a light weight, high flexibility and long term cycling stability by retaining 95% after 5000 charge-discharge cycles at a constant current of 10 mA. The high Faradic redox activity and high conductance behavior of the Cu7S4-NWs result in a high pseudocapacitive performance with a relatively high specific energy and specific power. Such a new type of pseudocapacitive material of Cu7S4-NWs with its low cost is very promising for actual application in supercapacitors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03363b

Melting phase relations in the Fe-S and Fe-S-O systems at core conditions in small terrestrial bodies

NASA Astrophysics Data System (ADS)

Pommier, Anne; Laurenz, Vera; Davies, Christopher J.; Frost, Daniel J.

2018-05-01

We report an experimental investigation of phase equilibria in the Fe-S and Fe-S-O systems. Experiments were performed at high temperatures (1400-1850 °C) and high pressures (14 and 20 GPa) using a multi-anvil apparatus. The results of this study are used to understand the effect of sulfur and oxygen on core dynamics in small terrestrial bodies. We observe that the formation of solid FeO grains occurs at the Fe-S liquid - Fe solid interface at high temperature ( > 1400 °C at 20 GPa). Oxygen fugacities calculated for each O-bearing sample show that redox conditions vary from ΔIW = -0.65 to 0. Considering the relative density of each phase and existing evolutionary models of terrestrial cores, we apply our experimental results to the cores of Mars and Ganymede. We suggest that the presence of FeO in small terrestrial bodies tends to contribute to outer-core compositional stratification. Depending on the redox and thermal history of the planet, FeO may also help form a transitional redox zone at the core-mantle boundary.

Method of fabrication of microarray of gel-immobilized compounds on a chip by copolymerization

DOEpatents

Mirzabekov, Andrei; Timofeev, Edouard; Vasiliskov, Vadim

2003-12-02

A method for making polymerized molecules is provided whereby a solution containing monomer is contacted to a solid substrate so as to form discrete accumulations of the monomer on the substrate; and the accumulations are contacted with a polymerizing agent, wherein the agent is dispersed in a vehicle which prevents cross contamination of the accumulations.

Monitoring the solid-state electrochemistry of Cu(2,7-AQDC) (AQDC = anthraquinone dicarboxylate) in a lithium battery: coexistence of metal and ligand redox activities in a metal-organic framework.

PubMed

Zhang, Zhongyue; Yoshikawa, Hirofumi; Awaga, Kunio

2014-11-19

By adopting a facile synthetic strategy, we obtained a microporous redox-active metal-organic framework (MOF), namely, Cu(2,7-AQDC) (2,7-H2AQDC = 2,7-anthraquinonedicarboxylic acid) (1), and utilized it as a cathode active material in lithium batteries. With a voltage window of 4.0-1.7 V, both metal clusters and anthraquinone groups in the ligands exhibited reversible redox activity. The valence change of copper cations was clearly evidenced by in situ XANES analysis. By controlling the voltage window of operation, extremely high recyclability of batteries was achieved, suggesting the framework was robust. This MOF is the first example of a porous material showing independent redox activity on both metal cluster nodes and ligand sites.

Seasonal cycling of sulfur and iron in porewaters of a Delaware salt marsh

NASA Technical Reports Server (NTRS)

Luther, George W., III; Church, Thomas M.

1987-01-01

An extensive pore water data set has been gathered in the Great Marsh, Delaware over various seasons, salinities, and tides. The data all point to a complimentary redox cycle for sulfur and iron which operates seasonally and tidally. Surface oxidizing conditions prevail in summer, with more reducing conditions at depth during the winter. During the spring tides which flood the marsh, pyrite oxidation occurs releasing excess dissolved iron (II) and sulfate to the porewaters, and precipitating authigenic solid iron phases. The redox conditions in the porewaters of the upper zone during the summer is poised between mildly oxidizing and mildly reducing conditions as shown by pE calculations. This redox environment and intermediate iron-sulfur redox species may be important for the stimulation of plant growth (photosynthesis) and sustenance of a viable microbial community (heterotrophy and chemoautropy).

Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids

NASA Astrophysics Data System (ADS)

Romero, F. Denis; Pitcher, M. J.; Hiley, C. I.; Whitehead, G. F. S.; Kar, S.; Ganin, A. Y.; Antypov, D.; Collins, C.; Dyer, M. S.; Klupp, G.; Colman, R. H.; Prassides, K.; Rosseinsky, M. J.

2017-07-01

Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid-solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure.

Integrated Interface Strategy toward Room Temperature Solid-State Lithium Batteries.

PubMed

Ju, Jiangwei; Wang, Yantao; Chen, Bingbing; Ma, Jun; Dong, Shanmu; Chai, Jingchao; Qu, Hongtao; Cui, Longfei; Wu, Xiuxiu; Cui, Guanglei

2018-04-25

Solid-state lithium batteries have drawn wide attention to address the safety issues of power batteries. However, the development of solid-state lithium batteries is substantially limited by the poor electrochemical performances originating from the rigid interface between solid electrodes and solid-state electrolytes. In this work, a composite of poly(vinyl carbonate) and Li 10 SnP 2 S 12 solid-state electrolyte is fabricated successfully via in situ polymerization to improve the rigid interface issues. The composite electrolyte presents a considerable room temperature conductivity of 0.2 mS cm -1 , an electrochemical window exceeding 4.5 V, and a Li + transport number of 0.6. It is demonstrated that solid-state lithium metal battery of LiFe 0.2 Mn 0.8 PO 4 (LFMP)/composite electrolyte/Li can deliver a high capacity of 130 mA h g -1 with considerable capacity retention of 88% and Coulombic efficiency of exceeding 99% after 140 cycles at the rate of 0.5 C at room temperature. The superior electrochemical performance can be ascribed to the good compatibility of the composite electrolyte with Li metal and the integrated compatible interface between solid electrodes and the composite electrolyte engineered by in situ polymerization, which leads to a significant interfacial impedance decrease from 1292 to 213 Ω cm 2 in solid-state Li-Li symmetrical cells. This work provides vital reference for improving the interface compatibility for room temperature solid-state lithium batteries.

Redox-sensitive self-assembled nanoparticles based on alpha-tocopherol succinate-modified heparin for intracellular delivery of paclitaxel.

PubMed

Yang, Xiaoye; Cai, Xiaoqing; Yu, Aihua; Xi, Yanwei; Zhai, Guangxi

2017-06-15

To remedy the problems riddled in cancer chemotherapy, such as poor solubility, low selectivity, and insufficient intra-cellular release of drugs, novel heparin-based redox-sensitive polymeric nanoparticles were developed. The amphiphilic polymer, heparin-alpha-tocopherol succinate (Hep-cys-TOS) was synthesized by grafting hydrophobic TOS to heparin using cystamine as the redox-sensitive linker, which could self-assemble into nanoparticles in phosphate buffer saline (PBS) with low critical aggregation concentration (CAC) values ranging from 0.026 to 0.093mg/mL. Paclitaxel (PTX)-loaded Hep-cys-TOS nanoparticles were prepared via a dialysis method, exhibiting a high drug-loading efficiency of 18.99%. Physicochemical properties of the optimized formulation were characterized by dynamic light scattering (DLS), transmission electron microscope (TEM) and differential scanning calorimetry (DSC). Subsequently, the redox-sensitivity of Hep-cys-TOS nanoparticles was confirmed by the changes in size distribution, morphology and appearance after dithiothreitol (DTT) treatment. Besides, the in vitro release of PTX from Hep-cys-TOS nanoparticles also exhibited a redox-triggered profile. Also, the uptake behavior and pathways of coumarin 6-loaded Hep-cys-TOS nanoparticles were investigated, suggesting the nanoparticles could be taken into MCF-7 cells in energy-dependent, caveolae-mediated and cholesterol-dependent endocytosis manners. Later, MTT assays of different PTX-free and PTX-loaded formulations revealed the desirable safety of PTX-free nanoparticles and the enhanced anti-cancer activity of PTX-loaded Hep-cys-TOS nanoparticles (IC 50 =0.79μg/mL). Apoptosis study indicated the redox-sensitive formulation could induce more apoptosis of MCF-7 cells than insensitive one (55.2% vs. 41.7%), showing the importance of intracellular burst release of PTX. Subsequently, the hemolytic toxicity confirmed the safety of the nanoparticles for intravenous administration. The results indicated the developed redox-sensitive nanoparticles were promising as intracellular drug delivery vehicles for cancer treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

Polymeric micelles as a new drug carrier system and their required considerations for clinical trials.

PubMed

Yokoyama, Masayuki

2010-02-01

A polymeric micelle is a macromolecular assembly composed of an inner core and an outer shell, and most typically is formed from block copolymers. In the last two decades, polymeric micelles have been actively studied as a new type of drug carrier system, in particular for drug targeting of anticancer drugs to solid tumors. In this review, polymeric micelle drug carrier systems are discussed with a focus on toxicities of the polymeric micelle carrier systems and on pharmacological activities of the block copolymers. In the first section, the importance of the above-mentioned evaluation of these properties is explained, as this importance does not seem to be well recognized compared with the importance of targeting and enhanced pharmacological activity of drugs, particularly in the basic studies. Then, designs, types and classifications of the polymeric micelle system are briefly summarized and explained, followed by a detailed discussion regarding several examples of polymeric micelle carrier systems. Readers will gain a strategy of drug delivery with polymeric carriers as well as recent progress of the polymeric micelle carrier systems in their basic studies and clinical trials. The purpose of this review is to achieve tight connections between the basic studies and clinical trials.

Polymeric micelles for multi-drug delivery in cancer.

PubMed

Cho, Hyunah; Lai, Tsz Chung; Tomoda, Keishiro; Kwon, Glen S

2015-02-01

Drug combinations are common in cancer treatment and are rapidly evolving, moving beyond chemotherapy combinations to combinations of signal transduction inhibitors. For the delivery of drug combinations, i.e., multi-drug delivery, major considerations are synergy, dose regimen (concurrent versus sequential), pharmacokinetics, toxicity, and safety. In this contribution, we review recent research on polymeric micelles for multi-drug delivery in cancer. In concurrent drug delivery, polymeric micelles deliver multi-poorly water-soluble anticancer agents, satisfying strict requirements in solubility, stability, and safety. In sequential drug delivery, polymeric micelles participate in pretreatment strategies that "prime" solid tumors and enhance the penetration of secondarily administered anticancer agent or nanocarrier. The improved delivery of multiple poorly water-soluble anticancer agents by polymeric micelles via concurrent or sequential regimens offers novel and interesting strategies for drug combinations in cancer treatment.

An Ultrastable Heterobimetallic Uranium(IV)/Vanadium(III) Solid Compound Protected by a Redox-Active Phosphite Ligand: Crystal Structure, Oxidative Dissolution, and First-Principles Simulation.

PubMed

Gui, Daxiang; Dai, Xing; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Chen, Lanhua; Zhang, Chao; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2018-02-05

The first heterobimetallic uranium(IV)/vanadium(III) phosphite compound, Na 2 UV 2 (HPO 3 ) 6 (denoted as UVP), was synthesized via an in situ redox-active hydrothermal reaction. It exhibits superior hydrolytic and antioxidant stability compared to the majority of structures containing low-valent uranium or vanadium, further elucidated by first-principles simulations, and therefore shows potential applications in nuclear waste management.

Redox Mediators for Li-O2 Batteries: Status and Perspectives.

PubMed

Park, Jin-Bum; Lee, Seon Hwa; Jung, Hun-Gi; Aurbach, Doron; Sun, Yang-Kook

2018-01-01

Li-O 2 batteries have received much attention due to their extremely large theoretical energy density. However, the high overpotentials required for charging Li-O 2 batteries lower their energy efficiency and degrade the electrolytes and carbon electrodes. This problem is one of the main obstacles in developing practical Li-O 2 batteries. To solve this problem, it is important to facilitate the oxidation of Li 2 O 2 upon charging by using effective electrocatalysis. Using solid catalysts is not too effective for oxidizing the electronically isolating Li-peroxide layers. In turn, for soluble catalysts, red-ox mediators (RMs) are homogeneously dissolved in the electrolyte solutions and can effectively oxidize all of the Li 2 O 2 precipitated during discharge. RMs can decompose solid Li 2 O 2 species no matter their size, morphology, or thickness and thus dramatically increase energy efficiency. However, some negative side effects, such as the shuttle reactions of RMs and deterioration of the Li-metal occur. Therefore, it is necessary to study the activity and stability of RMs in Li-O 2 batteries in detail. Herein, recent studies related to redox mediators are reviewed and the mechanisms of redox reactions are illustrated. The development opportunities of RMs for this important battery technology are discussed and future directions are suggested. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Berger, Cornelius M.; Mahmoud, Abdelfattah; Hermann, Raphaël P.

Rechargeable oxide batteries (ROB) comprise a regenerative solid oxide cell (rSOC) and a storage medium for oxygen ions. A sealed ROB avoids pumping loss, heat loss, and gas purity expenses in comparison with conventional rSOC. However, the iron oxide base storage medium degrades during charging–discharging cycles. In comparison, CaFe 3O 5 has improved cyclability and a high reversible oxygen storage capacity of 22.3 mol%. In this paper, we analyzed the redox mechanism of this compound. After a solid-state synthesis of CaFe 3O 5, we verified the phase composition and studied the redox reaction by means of X-ray diffraction, Mössbauer spectrometry,more » and scanning electron microscopy. Finally, results show a great potential to operate the battery with this storage material during multiple charging–discharging cycles.« less

Polymeric Amorphous Solid Dispersions: A Review of Amorphization, Crystallization, Stabilization, Solid-State Characterization, and Aqueous Solubilization of Biopharmaceutical Classification System Class II Drugs.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2016-09-01

Poor water solubility of many drugs has emerged as one of the major challenges in the pharmaceutical world. Polymer-based amorphous solid dispersions have been considered as the major advancement in overcoming limited aqueous solubility and oral absorption issues. The principle drawback of this approach is that they can lack necessary stability and revert to the crystalline form on storage. Significant upfront development is, therefore, required to generate stable amorphous formulations. A thorough understanding of the processes occurring at a molecular level is imperative for the rational design of amorphous solid dispersion products. This review attempts to address the critical molecular and thermodynamic aspects governing the physicochemical properties of such systems. A brief introduction to Biopharmaceutical Classification System, solid dispersions, glass transition, and solubility advantage of amorphous drugs is provided. The objective of this review is to weigh the current understanding of solid dispersion chemistry and to critically review the theoretical, technical, and molecular aspects of solid dispersions (amorphization and crystallization) and potential advantage of polymers (stabilization and solubilization) as inert, hydrophilic, pharmaceutical carrier matrices. In addition, different preformulation tools for the rational selection of polymers, state-of-the-art techniques for preparation and characterization of polymeric amorphous solid dispersions, and drug supersaturation in gastric media are also discussed. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Conductivity measurements on CdCl2 doped PVA solid polymeric electrolyte for battery application

NASA Astrophysics Data System (ADS)

Baraker, Basavarajeshwari M.; Lobo, Blaise

2018-04-01

Ionic conductivity of pure polyvinyl alcohol (PVA) and 6.3 wt% of CdCl2 doped PVA solid polymeric electrolyte have been studied using DC and AC electrical measurements. From DC electrical results, the determination transference number confirmed that ions are the dominant charge carriers in CdCl2 doped PVA. Interestingly, the ion transference number (ti) for 6.3 wt% CdCl2 doped sample is significantly more (0.993), when compared to that of pure PVA (for which, ti is 0.988). Temperature dependent dielectric studies showed interesting results at different frequencies: 120 Hz, 500 Hz, 1 kHz, 5 kHz, 10 kHz and 100 kHz.

Ion conducting organic/inorganic hybrid polymers

NASA Technical Reports Server (NTRS)

Meador, Maryann B. (Inventor); Kinder, James D. (Inventor)

2010-01-01

This invention relates to a series of organic/inorganic hybrid polymers that are easy to fabricate into dimensionally stable films with good ion-conductivity over a wide range of temperatures for use in a variety of applications. The polymers are prepared by the reaction of amines, preferably diamines and mixtures thereof with monoamines with epoxy-functionalized alkoxysilanes. The products of the reaction are polymerized by hydrolysis of the alkoxysilane groups to produce an organic-containing silica network. Suitable functionality introduced into the amine and alkoxysilane groups produce solid polymeric membranes which conduct ions for use in fuel cells, high-performance solid state batteries, chemical sensors, electrochemical capacitors, electro-chromic windows or displays, analog memory devices and the like.

Synthesis of new solid polymer electrolyte and actuator based on PEDOT/NBR/ionic liquid

NASA Astrophysics Data System (ADS)

Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

2006-03-01

The conducting polymer actuator was presented. The solid polymer electrolyte based on nitrile rubber (NBR) activated with different ionic liquids was prepared. The three different grades of NBR films were synthesized by emulsion polymerization with different amount of acrylonitrile, 23, 35, and 40 mol. %, respectively. The effect of acrylonitrile content on the ionic conductivity and dielectric constant of solid polymer electrolytes was characterized. A conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique, and room temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X [where X= BF 4 -, PF 6 -, (CF 3SO II) IIN -], were absorbed into the composite film. The effects of the anion size of the ionic liquids on the displacement of the actuator were examined. The displacement increased with increasing the anion-size of the ionic liquids.

Mechanical instabilities in periodic porous elasto-plastic solids.

NASA Astrophysics Data System (ADS)

Singamaneni, Srikanth; Bertoldi, Katia; Chang, Sehoon; Jang, Ji-Hyun; Young, Seth; Thomas, Edwin; Boyce, Mary; Tsukruk, Vladimir

2009-03-01

We describe the transformation of the periodic microporous structures fabricated by interference lithography followed by their freezing below glass transition. Periodic porous microstructures subjected to internal compressive stresses can undergo sudden structural transformation at a critical strain. The pattern transformation of collapsed pores is caused by the stresses originated during the polymerization of acrylic acid (rubbery component) inside of cylindrical pores and the subsequent solvent evaporation in the organized microporous structure. The results of a non-linear numerical investigation confirm the critical role of the bifurcation of the periodic solid under compressive stresses. In striking contrast to the earlier observations of elastic instabilities in porous elastomeric solids, the elastic-plastic nature of the crosslinked periodic microstructure studied here provides for the ability to lock in the transformed pattern with complete relaxation of the internal stresses. By confining the polymerization of acrylic acid to localized porous areas complex microscopic periodic structures are obtained.

Polymeric CO: A new class of High Energy Density Material

NASA Astrophysics Data System (ADS)

Lipp, Magnus

2005-03-01

Covalently bonded extended phases of molecular solids made of first- and second-row elements at high pressures are a new class of material with advanced optical, mechanical and energetic properties. The existence of such extended solids has recently been demonstrated using diamond anvil cells in several systems, including N2, CO2, and CO. However, the microscopic quantities produced at the formidable high-pressure/temperature conditions have limited the characterization of their predicted novel properties including high-energy content. Here we present the first experimental evidence that these extended low-Z solids are indeed high energy density materials via milligram-scale high-pressure synthesis, recovery and characterization of polymeric CO (p-CO). This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

Discovering Volatile Chemicals from Window Weatherstripping through Solid-Phase Microextraction/Gas Chromatography-Mass Spectrometry

ERIC Educational Resources Information Center

Rosu, Cornelia; Cueto, Rafael; Veillion, Lucas; David, Connie; Laine, Roger A.; Russo, Paul S.

2017-01-01

Volatile compounds from polymeric materials such as weatherstripping were identified by solid-phase microextraction (SPME), a solvent-free analytical method, coupled to gas chromatography-mass spectrometry (GC-MS). These compounds, originating from additives and fillers used in weatherstripping processing, were mostly polycyclic aromatic…

A Discovery-Oriented Approach to Solid-Phase Peptide Synthesis

ERIC Educational Resources Information Center

Bockman, Matthew R.; Miedema, Christopher J.; Brennan, Brian B.

2012-01-01

In this discovery-oriented laboratory experiment, students use solid-phase synthesis techniques to construct a dipeptide containing an unknown amino acid. Following synthesis and cleavage from the polymeric support, electrospray ionization-mass spectrometry is employed to identify the unknown amino acid that was used in the peptide coupling. This…

Combustion Mechanisms of Solids

DTIC Science & Technology

1986-08-01

PYROLYSIS OF POLYMERIC SOLID PROPELLANT BINDERS Approved Edward W. Price, Chairman Gary A. randro Jech e I.dJagoda Robert K. SVigman Date Approved by...committee, Drs. I. A. Jagoda, F. L. Cook, G. A. Flandro , R. K. Sigman, I am indebted for their many hours of discussion and their suggestions. Special

Applications of Polymers as Pharmaceutical Excipients in Solid Oral Dosage Forms.

PubMed

Debotton, Nir; Dahan, Arik

2017-01-01

Over the last few decades, polymers have been extensively used as pharmaceutical excipients in drug delivery systems. Pharmaceutical polymers evolved from being simply used as gelatin shells comprising capsule to offering great formulation advantages including enabling controlled/slow release and specific targeting of drugs to the site(s) of action (the "magic bullets" concept), hence hold a significant clinical promise. Oral administration of solid dosage forms (e.g., tablets and capsules) is the most common and convenient route of drug administration. When formulating challenging molecules into solid oral dosage forms, polymeric pharmaceutical excipients permit masking undesired physicochemical properties of drugs and consequently, altering their pharmacokinetic profiles to improve the therapeutic effect. As a result, the number of synthetic and natural polymers available commercially as pharmaceutical excipients has increased dramatically, offering potential solutions to various difficulties. For instance, the different polymers may allow increased solubility, swellability, viscosity, biodegradability, advanced coatings, pH dependency, mucodhesion, and inhibition of crystallization. The aim of this article is to provide a wide angle prospect of the different uses of pharmaceutical polymers in solid oral dosage forms. The various types of polymeric excipients are presented, and their distinctive role in oral drug delivery is emphasized. The comprehensive know-how provided in this article may allow scientists to use these polymeric excipients rationally, to fully exploit their different features and potential influence on drug delivery, with the overall aim of making better drug products. © 2016 Wiley Periodicals, Inc.

Fiscal Year 1996 Annual Report and Five-Year (1996-2000) Strategic Investment Plan

DTIC Science & Technology

1996-03-01

dissolved and solid-associated organic carbon compounds associated with sorption and biodegradative processes. The participation of faculty and graduate...created by adsorbed monolayers of closely packed perfluorinated compounds . Since adsorbed monolayers are not practical as hull coatings, we propose to...the perfluorinated compounds into a polymeric backbone to create comb type polymers with perfluoroalkyl sidechains. These types of polymeric

Hydrocarbon polymeric binder for advanced solid propellant

NASA Technical Reports Server (NTRS)

Potts, J. E. (Editor); Ashcraft, A. C., Jr.; Wise, E. W.

1971-01-01

The results of curing vinyl alcohol terpolymers of ethylene, propylene and vinyl acetate are reported for an average functionality of 1.24 when reacted with an equivalent amount of diisocynate, and saturated polyisoprene derivative is described having terminal methyl ester functionality. The development is reported of two hydroxy-telechelic polyisoprenes prepared by DEAB initiated free radical polymerization followed by LiAlH4 reduction of the end groups.

Flexible and conductive waste tire-derived carbon/polymer composite paper as pseudocapacitive electrode

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

Naskar, Amit K.; Paranthaman, Mariappan Parans; Boota, Muhammad

A method of making a supercapacitor from waste tires, includes the steps of providing rubber pieces and contacting the rubber pieces with a sulfonation bath to produce sulfonated rubber; pyrolyzing the sulfonated rubber to produce a tire-derived carbon composite comprising carbon black embedded in rubber-derived carbon matrix comprising graphitized interface portions; activating the tire-derived carbon composite by contacting the tire-derived carbon composite with a specific surface area-increasing composition to increase the specific surface area of the carbon composite to provide an activated tire-derived carbon composite; and, mixing the activated tire-derived carbon composite with a monomer and polymerizing the monomer tomore » produce a redox-active polymer coated, activated tire-derived carbon composite. The redox-active polymer coated, activated tire-derived carbon composite can be formed into a film. An electrode and a supercapacitor are also disclosed.« less

Bacteria-instructed synthesis of polymers for self-selective microbial binding and labelling

NASA Astrophysics Data System (ADS)

Magennis, E. Peter; Fernandez-Trillo, Francisco; Sui, Cheng; Spain, Sebastian G.; Bradshaw, David J.; Churchley, David; Mantovani, Giuseppe; Winzer, Klaus; Alexander, Cameron

2014-07-01

The detection and inactivation of pathogenic strains of bacteria continues to be an important therapeutic goal. Hence, there is a need for materials that can bind selectively to specific microorganisms for diagnostic or anti-infective applications, but that can be formed from simple and inexpensive building blocks. Here, we exploit bacterial redox systems to induce a copper-mediated radical polymerization of synthetic monomers at cell surfaces, generating polymers in situ that bind strongly to the microorganisms that produced them. This ‘bacteria-instructed synthesis’ can be carried out with a variety of microbial strains, and we show that the polymers produced are self-selective binding agents for the ‘instructing’ cell types. We further expand on the bacterial redox chemistries to ‘click’ fluorescent reporters onto polymers directly at the surfaces of a range of clinical isolate strains, allowing rapid, facile and simultaneous binding and visualization of pathogens.

Composite separators and redox flow batteries based on porous separators

DOEpatents

Li, Bin; Wei, Xiaoliang; Luo, Qingtao; Nie, Zimin; Wang, Wei; Sprenkle, Vincent L.

2016-01-12

Composite separators having a porous structure and including acid-stable, hydrophilic, inorganic particles enmeshed in a substantially fully fluorinated polyolefin matrix can be utilized in a number of applications. The inorganic particles can provide hydrophilic characteristics. The pores of the separator result in good selectivity and electrical conductivity. The fluorinated polymeric backbone can result in high chemical stability. Accordingly, one application of the composite separators is in redox flow batteries as low cost membranes. In such applications, the composite separator can also enable additional property-enhancing features compared to ion-exchange membranes. For example, simple capacity control can be achieved through hydraulic pressure by balancing the volumes of electrolyte on each side of the separator. While a porous separator can also allow for volume and pressure regulation, in RFBs that utilize corrosive and/or oxidizing compounds, the composite separators described herein are preferable for their robustness in the presence of such compounds.

Lasing properties of polymerized chiral nematic Bragg onion microlasers.

PubMed

Humar, Matjaž; Araoka, Fumito; Takezoe, Hideo; Muševič, Igor

2016-08-22

Dye doped photocurable cholesteric liquid crystal was used to produce solid Bragg onion omnidirectional lasers. The lasers were produced by dispersing and polymerizing chiral nematic LC with parallel surface anchoring of LC molecules at the interface, extracted and transferred into another medium. Lasing characteristics were studied in carrier medium with different refractive index. The lasing in spherical cholesteric liquid crystal was attributed to two mechanisms, photonic bandedge lasing and lasing of whispering-gallery modes. The latter can be suppressed by using a higher index carrier fluid to prevent total internal reflection on the interface of the spheres. Pulse-to-pulse stability and threshold characteristics were also studied and compared to non-polymerized lasers. The polymerization process greatly increases the lasing stability.

Atypical effects of incorporated surfactants on stability and dissolution properties of amorphous polymeric dispersions.

PubMed

Al-Obaidi, Hisham; Lawrence, M Jayne; Buckton, Graham

2016-11-01

To understand the impact of ionic and non-ionic surfactants on the dissolution and stability properties of amorphous polymeric dispersions using griseofulvin (GF) as a model for poorly soluble drugs. Solid dispersions of the poorly water-soluble drug, griseofulvin (GF) and the polymers, poly(vinylpyrrolidone) (PVP) and poly(2-hydroxypropyl methacrylate) (PHPMA), have been prepared by spray drying and bead milling and the effect of the ionic and non-ionic surfactants, namely sodium dodecyl sulphate (SDS) and Tween-80, on the physico-chemical properties of the solid dispersions studied. The X-ray powder diffraction data and hot-stage microscopy showed a fast re-crystallisation of GF. While dynamic vapour sorption (DVS) measurements indicated an increased water uptake, slow dissolution rates were observed for the solid dispersions incorporating surfactants. The order by which surfactants free dispersions were prepared seemed critical as indicated by DVS and thermal analysis. Dispersions prepared by milling with SDS showed significantly better stability than spray-dried dispersions (drug remained amorphous for more than 6 months) as well as improved dissolution profile. We suggest that surfactants can hinder the dissolution by promoting aggregation of polymeric chains, however that effect depends mainly on how the particles were prepared. © 2016 Royal Pharmaceutical Society.

Functional Materials from Polymeric Ionic Liquids

NASA Astrophysics Data System (ADS)

Segalman, Rachel; Sanoja, Gabriel; Michenfelder-Schauser, Nicole; Mitragotri, Samir; Seshadri, Ram

Ionic liquids (IL's) have been suggested for applications as diverse as solubilizing cellulose, antimicrobial treatments, and electrolytes in batteries due to their molten salt properties. A polymeric cation (such as imidazolium) is an excellent host for any associated anion. As a result, polymerized ionic liquids are not just solid counterparts to IL's, but are shown to be vectors for the inclusion of a wide variety of functionalities ranging from multi-valent ions to magnetic anions. Moreover, PIL block copolymers allow orthogonal control over mechanical and morphological properties, ultimately leading to a conceptual framework for processable, tunable, multifunctional materials.

Heat resistant substrates and battery separators made therefrom

NASA Technical Reports Server (NTRS)

Langer, Alois (Inventor); Scala, Luciano C. (Inventor); Ruffing, Charles R. (Inventor)

1976-01-01

A flexible substrate having a caustic resistant support and at least one membrane comprising a solid polymeric matrix containing a network of interconnected pores and interdispersed inorganic filler particles with a ratio of filler: polymer in the polymeric matrix of between about 1:1 to 5:1, is made by coating at least one side of the support with a filler:coating formulation mixture of inorganic filler particles and a caustic resistant, water insoluble polymer dissolved in an organic solvent, and removing the solvent from the mixture to provide a porous network within the polymeric matrix.

Determining Li+-Coupled Redox Targeting Reaction Kinetics of Battery Materials with Scanning Electrochemical Microscopy.

PubMed

Yan, Ruiting; Ghilane, Jalal; Phuah, Kia Chai; Pham Truong, Thuan Nguyen; Adams, Stefan; Randriamahazaka, Hyacinthe; Wang, Qing

2018-02-01

The redox targeting reaction of Li + -storage materials with redox mediators is the key process in redox flow lithium batteries, a promising technology for next-generation large-scale energy storage. The kinetics of the Li + -coupled heterogeneous charge transfer between the energy storage material and redox mediator dictates the performance of the device, while as a new type of charge transfer process it has been rarely studied. Here, scanning electrochemical microscopy (SECM) was employed for the first time to determine the interfacial charge transfer kinetics of LiFePO 4 /FePO 4 upon delithiation and lithiation by a pair of redox shuttle molecules FcBr 2 + and Fc. The effective rate constant k eff was determined to be around 3.70-6.57 × 10 -3 cm/s for the two-way pseudo-first-order reactions, which feature a linear dependence on the composition of LiFePO 4 , validating the kinetic process of interfacial charge transfer rather than bulk solid diffusion. In addition, in conjunction with chronoamperometry measurement, the SECM study disproves the conventional "shrinking-core" model for the delithiation of LiFePO 4 and presents an intriguing way of probing the phase boundary propagations induced by interfacial redox reactions. This study demonstrates a reliable method for the kinetics of redox targeting reactions, and the results provide useful guidance for the optimization of redox targeting systems for large-scale energy storage.

Liquid-Solid Self-Lubricated Coatings

NASA Astrophysics Data System (ADS)

Armada, S.; Schmid, R.; Equey, S.; Fagoaga, I.; Espallargas, N.

2013-02-01

Self-lubricated coatings have been a major topic of interest in thermal spray in the last decades. Self-lubricated coatings obtained by thermal spray are exclusively based on solid lubricants (PTFE, h-BN, graphite, MoS2, etc.) embedded in the matrix. Production of thermal spray coatings containing liquid lubricants has not yet been achieved because of the complexity of keeping a liquid in a solid matrix during the spraying process. In the present article, the first liquid-solid self-lubricating thermal spray coatings are presented. The coatings are produced by inserting lubricant-filled capsules inside a polymeric matrix. The goal of the coating is to release lubricant to the system when needed. The first produced coatings consisted solely of capsules for confirming the feasibility of the process. For obtaining such a coating, the liquid-filled capsules were injected in the thermal spray flame without any other feedstock material. Once the concept and the idea were proven, a polymer was co-sprayed together with the capsules to obtain a coating containing the lubricant-filled capsules distributed in the solid polymeric matrix. The coatings and the self-lubricated properties have been investigated by means of optical microscopy, Scanning Electron Microscopy, and tribological tests.

Extended Solids of Carbon Monoxide formed from Re2(CO)12

NASA Astrophysics Data System (ADS)

Ciezak-Jenkins, Jennifer

Extended solids are formed from simple molecular gases under extreme P/T and are of considerable interest as high-energy-density materials. It has been postulated that a transformation from a single-bonded polymeric-like material back to the more stable triply-bonded diatomic phase would be a highly exothermic process yielding large amounts of energy. The extended polymeric solid of CO was first reported and recovered from high pressure conditions in 2005. Although the material was found to have potentially interesting energetic properties, it showed a number of stability issues, degrading into CO2 and graphitic carbon over 3 to 5 days. As such, our lab has been focused on the identification of methods to increase the metastability of the recovered solid. Metal carbonyls offer one such route for stabilization. In this talk, our progress in the study of the synthesis, characterization, and recovery of extended solids of CO starting from Re2(CO)12\\ to pressures near 50 GPa will be presented. I will discuss the analysis and the implications of these results. New opportunities and challenges that have arisen in the course of our studies that will be pursued in the future will also be presented. Ref

Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array.

PubMed

Dong, Wei; Zeng, Xian-Xiang; Zhang, Xu-Dong; Li, Jin-Yi; Shi, Ji-Lei; Xiao, Yao; Shi, Yang; Wen, Rui; Yin, Ya-Xia; Wang, Tai-Shan; Wang, Chun-Ru; Guo, Yu-Guo

2018-05-02

The poor contact between the solid-state electrolyte and cathode materials leads to high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a micro-channel current collector array and nano-sized cathode particles. In-situ formed GPSE encapsulates cathode nanoparticles in the micro-channel with ductile inclusions to lower interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses Li dendrites growth. Li metal batteries based on GPSE and Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high-rate response of up to 5 C (the capacity ratio of 5 C / 1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. Other Li-containing cathodes as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at 5 C and 2 C rate, respectively. Such an ingenious design may provide new insights into other solid metal batteries through interfacial engineering manipulation at micro and nano level.

pH/redox dual-sensitive dextran nanogels for enhanced intracellular drug delivery.

PubMed

Curcio, Manuela; Diaz-Gomez, Luis; Cirillo, Giuseppe; Concheiro, Angel; Iemma, Francesca; Alvarez-Lorenzo, Carmen

2017-08-01

pH/redox dual-responsive nanogels (DEX-SS) were prepared by precipitation polymerization of methacrylated dextran (DEXMA), 2-aminoethylmethacrylate (AEMA) and N,N'-bis(acryloyl)cystamine (BAC), and then loaded with methotrexate (MTX). Nanogels were spherical and exhibited homogeneous size distribution (460nm, PDI<0.30) as observed using dynamic light scattering (DLS) and scanning electron microscopy (SEM). DEX-SS were sensitive to the variations of pH and redox environment. Nanogels incubated in buffer pH 5.0 containing 10mM glutathione (GSH) synergistically increased the mean diameter and the PDI to 750nm and 0.42, respectively. In vitro release experiments were performed at pH 7.4 and 5.0 with and without GSH. The cumulative release of MTX in pH 5.0 medium with 10mMGSH was 5-fold higher than that recorded at pH 7.4 without GSH. Fibroblasts and tumor cells were used to tests the effects of blank DEX-SS and MTX@DEX-SS nanogels on cell viability. Remarkable influence of pH on nanogels internalization into HeLa cells was evidenced by means of confocal microscopy and flow cytometry. Copyright © 2017 Elsevier B.V. All rights reserved.

Releasing metal catalysts via phase transition: (NiO)0.05-(SrTi0.8Nb0.2O3)0.95 as a redox stable anode material for solid oxide fuel cells.

PubMed

Xiao, Guoliang; Wang, Siwei; Lin, Ye; Zhang, Yanxiang; An, Ke; Chen, Fanglin

2014-11-26

Donor-doped perovskite-type SrTiO3 experiences stoichiometric changes at high temperatures in different Po2 involving the formation of Sr or Ti-rich impurities. NiO is incorporated into the stoichiometric strontium titanate, SrTi0.8Nb0.2O3-δ (STN), to form an A-site deficient perovskite material, (NiO)0.05-(SrTi0.8Nb0.2O3)0.95 (Ni-STN), for balancing the phase transition. Metallic Ni nanoparticles can be released upon reduction instead of forming undesired secondary phases. This material design introduces a simple catalytic modification method with good compositional control of the ceramic backbones, by which transport property and durability of solid oxide fuel cell anodes are largely determined. Using Ni-STN as anodes for solid oxide fuel cells, enhanced catalytic activity and remarkable stability in redox cycling have been achieved. Electrolyte-supported cells with the cell configuration of Ni-STN-SDC anode, La0.8Sr0.2Ga0.87Mg0.13O3 (LSGM) electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode produce peak power densities of 612, 794, and 922 mW cm(-2) at 800, 850, and 900 °C, respectively, using H2 as the fuel and air as the oxidant. Minor degradation in fuel cell performance resulted from redox cycling can be recovered upon operating the fuel cells in H2. Such property makes Ni-STN a promising regenerative anode candidate for solid oxide fuel cells.

Fluoride-selective optical sensor based on the dipyrrolyl-tetrathiafulvalene chromophore.

PubMed

Rivadehi, Shadi; Reid, Ellen F; Hogan, Conor F; Bhosale, Sheshanath V; Langford, Steven J

2012-01-28

A chemosensor bearing dipyrrolyl motifs as recognition sites and a tetrathiafulvalene redox tag has been evaluated as an optical and redox sensor for a series of anions (F(-), Cl(-), Br(-), HSO(4)(-), CH(3)COO(-), and H(2)PO(4)(-)) in DCM solution. The receptor shows specific optical signaling for fluoride but little electrochemical effect in solution. The solid-state performance of the sensor leads to measurable changes in water. Design implications towards better systems based on these results and other examples are discussed.

Recent progress of atomic layer deposition on polymeric materials.

PubMed

Guo, Hong Chen; Ye, Enyi; Li, Zibiao; Han, Ming-Yong; Loh, Xian Jun

2017-01-01

As a very promising surface coating technology, atomic layer deposition (ALD) can be used to modify the surfaces of polymeric materials for improving their functions and expanding their application areas. Polymeric materials vary in surface functional groups (number and type), surface morphology and internal structure, and thus ALD deposition conditions that typically work on a normal solid surface, usually do not work on a polymeric material surface. To date, a large variety of research has been carried out to investigate ALD deposition on various polymeric materials. This paper aims to provide an in-depth review of ALD deposition on polymeric materials and its applications. Through this review, we will provide a better understanding of surface chemistry and reaction mechanism for controlled surface modification of polymeric materials by ALD. The integrated knowledge can aid in devising an improved way in the reaction between reactant precursors and polymer functional groups/polymer backbones, which will in turn open new opportunities in processing ALD materials for better inorganic/organic film integration and potential applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Iterative absolute electroanalytical approach to characterization of bulk redox conducting systems.

PubMed

Lewera, Adam; Miecznikowski, Krzysztof; Chojak, Malgorzata; Makowski, Oktawian; Golimowski, Jerzy; Kulesza, Pawel J

2004-05-15

A novel electroanalytical approach is proposed here, and it is demonstrated with the direct and simultaneous determination of two unknowns: the concentration of redox sites and the apparent diffusion coefficient for charge propagation in a single crystal of dodecatungstophosphoric acid. This Keggin-type polyoxometalate serves as a model bulk redox conducting inorganic material for solid-state voltammetry. The system has been investigated using an ultramicrodisk working electrode in the absence of external liquid supporting electrolyte. The analytical method requires numerical solution of the combination of two equations in which the first one describes current (or charge) in a well-defined (either spherical or linear) diffusional regime and the second general equation describes chronoamperometric (or normal pulse voltammetric current) under mixed (linear-spherical) conditions. The iterative approach is based on successive approximations through calculation and minimizing the least-squares error function. The method is fairly universal, and in principle, it can be extended to the investigation of other bulk systems including sol-gel processed materials, redox melts, and solutions on condition that they are electroactive and well behaved, they contain redox centers at sufficiently high level, and a number of electrons for the redox reaction considered is known.

Molecular Orbital Principles of Oxygen-Redox Battery Electrodes.

PubMed

Okubo, Masashi; Yamada, Atsuo

2017-10-25

Lithium-ion batteries are key energy-storage devices for a sustainable society. The most widely used positive electrode materials are LiMO 2 (M: transition metal), in which a redox reaction of M occurs in association with Li + (de)intercalation. Recent developments of Li-excess transition-metal oxides, which deliver a large capacity of more than 200 mAh/g using an extra redox reaction of oxygen, introduce new possibilities for designing higher energy density lithium-ion batteries. For better engineering using this fascinating new chemistry, it is necessary to achieve a full understanding of the reaction mechanism by gaining knowledge on the chemical state of oxygen. In this review, a summary of the recent advances in oxygen-redox battery electrodes is provided, followed by a systematic demonstration of the overall electronic structures based on molecular orbitals with a focus on the local coordination environment around oxygen. We show that a π-type molecular orbital plays an important role in stabilizing the oxidized oxygen that emerges upon the charging process. Molecular orbital principles are convenient for an atomic-level understanding of how reversible oxygen-redox reactions occur in bulk, providing a solid foundation toward improved oxygen-redox positive electrode materials for high energy-density batteries.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

1989-01-01

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, T.A.; Okamoto, Yoshiyuki; Lee, H.S.

1989-11-21

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

Hydrocarbon polymeric binder for advanced solid propellant

NASA Technical Reports Server (NTRS)

Potts, J. E. (Editor)

1972-01-01

A series of DEAB initiated isoprene polymerizations were run in the 5-gallon stirred autoclave reactor. Polymerization run parameters such as initiator concentration and feed rate were correlated with the molecular weight to provide a basis for molecular weight control in future runs. Synthetic methods were developed for the preparation of n-1,3-alkadienes. By these methods, 1,3-nonadiene was polymerized using DEAB initiator to give an ester-telechelic polynonadiene. This was subsequently hydrogenated with copper chromite catalyst to give a hydroxyl terminated saturated liquid hydrocarbon prepolymer having greatly improved viscosity characteristics and a Tg 18 degrees lower than that of the hydrogenated polyisoprenes. The hydroxyl-telechelic saturated polymers prepared by the hydrogenolysis of ester-telechelic polyisoprene were reached with diisocyanates under conditions favoring linear chain extension gel permeation chromatography was used to monitor this condensation polymerization. Fractions having molecular weights above one million were produced.

2DCOS and PCMW2D analysis of FT-IR/ATR spectra measured at variable temperatures on-line to a polyurethane polymerization

NASA Astrophysics Data System (ADS)

Schuchardt, Patrick; Unger, Miriam; Siesler, Heinz W.

2018-01-01

In the present communication the potential of 2DCOS analysis and the spin-off technique perturbation-correlation moving window 2D (PCMW2D) analysis is illustrated with reference to spectroscopic changes observed in a data set recorded by in-line fiber-coupled FT-IR spectroscopy in the attenuated total reflection (ATR) mode during a polyurethane solution polymerization at different temperatures. In view of the chemical functionalities involved, hydrogen bonding plays an important role in this polymerization reaction. Based on the 2DCOS and PCMW2D analysis, the sequence of hydrogen bonding changes accompanying the progress of polymerization and precipitation of solid polymer can be determined. Complementary to the kinetic data derived from the original variable-temperature spectra in a previous publication the results provide a more detailed picture of the investigated solution polymerization.

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

PubMed

Feng, Juanjuan; Sun, Min; Xu, Lili; Li, Jubai; Liu, Xia; Jiang, Shengxiang

2011-10-28

Polymeric 1-vinyl-3-octylimidazolium hexafluorophosphate was synthesized in situ on stainless steel wire by surface radical chain-transfer polymerization and used as sensitive coatings in solid-phase microextraction. The outer surface of the stainless steel wire was firstly coated with microstructured silver layer via silver mirror reaction and then functionalized with self-assembled monolayers of 1,8-octanedithiol, which acted as chain transfer agent in the polymerization. Coupled to gas chromatography, extraction performance of the fiber was studied with both headspace and direct-immersion modes using benzene, toluene, ethylbenzene and xylenes (BTEX), phenols and polycyclic aromatic hydrocarbon (PAHs) as model analytes. In combination with the microstructured silver layer, the PIL-coated fiber exhibited high extraction efficiency. Linear ranges for BTEX with headspace mode were in the range of 0.2-1000 μg L(-1) for benzene, and 0.1-1000 μg L(-1) for toluene, ethylbenzene and xylenes. Limits of detection (LODs) were from 0.02 to 0.05 μg L(-1). Wide linear ranges of direct-immersion mode for the extraction of several phenols and PAHs were also obtained with correlation coefficients (R) from 0.9943 to 0.9997. The proposed fiber showed good durability with long lifetime. RSDs of 56 times extraction were still in an acceptable range, from 8.85 to 22.8%. Copyright © 2011 Elsevier B.V. All rights reserved.

Rapid Three-Dimensional Printing in Water Using Semiconductor-Metal Hybrid Nanoparticles as Photoinitiators.

PubMed

Pawar, Amol Ashok; Halivni, Shira; Waiskopf, Nir; Ben-Shahar, Yuval; Soreni-Harari, Michal; Bergbreiter, Sarah; Banin, Uri; Magdassi, Shlomo

2017-07-12

Additive manufacturing processes enable fabrication of complex and functional three-dimensional (3D) objects ranging from engine parts to artificial organs. Photopolymerization, which is the most versatile technology enabling such processes through 3D printing, utilizes photoinitiators that break into radicals upon light absorption. We report on a new family of photoinitiators for 3D printing based on hybrid semiconductor-metal nanoparticles. Unlike conventional photoinitiators that are consumed upon irradiation, these particles form radicals through a photocatalytic process. Light absorption by the semiconductor nanorod is followed by charge separation and electron transfer to the metal tip, enabling redox reactions to form radicals in aerobic conditions. In particular, we demonstrate their use in 3D printing in water, where they simultaneously form hydroxyl radicals for the polymerization and consume dissolved oxygen that is a known inhibitor. We also demonstrate their potential for two-photon polymerization due to their giant two-photon absorption cross section.

Lithium metal protection enabled by in-situ olefin polymerization for high-performance secondary lithium sulfur batteries

NASA Astrophysics Data System (ADS)

An, Yongling; Zhang, Zhen; Fei, Huifang; Xu, Xiaoyan; Xiong, Shenglin; Feng, Jinkui; Ci, Lijie

2017-09-01

Lithium metal is considered to be the optimal choice of next-generation anode materials due to its ultrahigh theoretical capacity and the lowest redox potential. However, the growth of dendritic and mossy lithium for rechargeable Li metal batteries lead to the possible short circuiting and subsequently serious safety issues during charge/discharge cycles. For the further practical applications of Li anode, here we report a facile method for fabricating robust interfacial layer via in-situ olefin polymerization. The resulting polymer layer effectively suppresses the formation of Li dendrites and enables the long-term operation of Li metal batteries. Using Li-S cells as a test system, we also demonstrate an improved capacity retention with the protection of tetramethylethylene-polymer. Our results indicate that this method could be a promising strategy to tackle the intrinsic problems of lithium metal anodes and promote the development of Li metal batteries.

Synthesis of perm-selective membranes by grafting acrylic acid into air-irradiated Teflon-FEP films

NASA Astrophysics Data System (ADS)

Bozzi, Annick; Chapiro, Adolphe

Grafting acrylic acid into air-irradiated Teflon-FEP films was investigated. Pre-irradiation doses ranged from 0.5 to 10 kGy. Grafting occurred at 45 or 60°C. Homopolymerization inhibitors, ferrous ions or methylene blue, were added to the system. It was found that after completion of the reaction, within 40-100 min, membranes were obtained with very low electric resistivities. The influence of added inhibitors, pre-irradiation dose and grafting temperature was studied. From the results it is concluded that the initiating centers in air-irradiated Teflon-FEP are, on the one hand, peroxides of structure POOP', in which P is a polymeric radical and Pprime; a small fragment, and on the other trapped PO .2 radicals. The latter only react after losing their oxygen. In the presence of polymerization inhibitors, initiation involves a redox process which reduces the overall activation energy.

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

PubMed

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

2016-08-04

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

Nanophosphor composite scintillators comprising a polymer matrix

DOEpatents

Muenchausen, Ross Edward; Mckigney, Edward Allen; Gilbertson, Robert David

2010-11-16

An improved nanophosphor composite comprises surface modified nanophosphor particles in a solid matrix. The nanophosphor particle surface is modified with an organic ligand, or by covalently bonding a polymeric or polymeric precursor material. The surface modified nanophosphor particle is essentially charge neutral, thereby preventing agglomeration of the nanophosphor particles during formation of the composite material. The improved nanophosphor composite may be used in any conventional scintillator application, including in a radiation detector.

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

PubMed

Rosenthal-Kim, Emily Q; Puskas, Judit E

2015-04-13

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

Synthesis of polypyrrole within the cell wall of yeast by redox-cycling of [Fe(CN)6](3-)/[Fe(CN)6](4-).

PubMed

Ramanavicius, Arunas; Andriukonis, Eivydas; Stirke, Arunas; Mikoliunaite, Lina; Balevicius, Zigmas; Ramanaviciene, Almira

2016-02-01

Yeast cells are often used as a model system in various experiments. Moreover, due to their high metabolic activity, yeast cells have a potential to be applied as elements in the design of biofuel cells and biosensors. However a wider application of yeast cells in electrochemical systems is limited due to high electric resistance of their cell wall. In order to reduce this problem we have polymerized conducting polymer polypyrrole (Ppy) directly in the cell wall and/or within periplasmic membrane. In this research the formation of Ppy was induced by [Fe(CN)6](3-)ions, which were generated from K4[Fe(CN)6], which was initially added to polymerization solution. The redox process was catalyzed by oxido-reductases, which are present in the plasma membrane of yeast cells. The formation of Ppy was confirmed by spectrophotometry and atomic force microscopy. It was confirmed that the conducting polymer polypyrrole was formed within periplasmic space and/or within the cell wall of yeast cells, which were incubated in solution containing pyrrole, glucose and [Fe(CN)6](4-). After 24h drying at room temperature we have observed that Ppy-modified yeast cell walls retained their initial spherical form. In contrast to Ppy-modified cells, the walls of unmodified yeast have wrinkled after 24h drying. The viability of yeast cells in the presence of different pyrrole concentrations has been evaluated. Copyright © 2015 Elsevier Inc. All rights reserved.

A simple method to separate red wine nonpolymeric and polymeric phenols by solid-phase extraction.

PubMed

Pinelo, Manuel; Laurie, V Felipe; Waterhouse, Andrew L

2006-04-19

Simple polyphenols and tannins differ in the way that they contribute to the organoleptic profile of wine and their effects on human health. Very few straightforward techniques to separate red wine nonpolymeric phenols from the polymeric fraction are available in the literature. In general, they are complex, time-consuming, and generate large amounts of waste. In this procedure, the separation of these compounds was achieved using C18 cartridges, three solvents with different elution strengths, and pH adjustments of the experimental matrices. Two full factorial 2(3) experimental designs were performed to find the optimal critical variables and their values, allowing for the maximization of tannin recovery and separation efficiency (SE). Nonpolymeric phenols such as phenolic acids, monomers, and oligomers of flavonol and flavan-3-ols and anthocyanins were removed from the column by means of an aqueous solvent followed by ethyl acetate. The polymeric fraction was then eluted with a combination of methanol/acetone/water. The best results were attained with 1 mL of wine sample, a 10% methanol/water solution (first eluant), ethyl acetate (second eluant), and 66% acetone/water as the polymeric phenols-eluting solution (third eluant), obtaining a SE of ca. 90%. Trials with this method on fruit juices also showed high separation efficiency. Hence, this solid-phase extraction method has been shown to be a simple and efficient alternative for the separation of nonpolymeric phenolic fractions and the polymeric ones, and this method could have important applications to sample purification prior to biological testing due to the nonspecific binding of polymeric phenolics to nearly all enzymes and receptor sites.

Calcium-Iron Oxide as Energy Storage Medium in Rechargeable Oxide Batteries

DOE PAGES

Berger, Cornelius M.; Mahmoud, Abdelfattah; Hermann, Raphaël P.; ...

2016-08-08

Rechargeable oxide batteries (ROB) comprise a regenerative solid oxide cell (rSOC) and a storage medium for oxygen ions. A sealed ROB avoids pumping loss, heat loss, and gas purity expenses in comparison with conventional rSOC. However, the iron oxide base storage medium degrades during charging–discharging cycles. In comparison, CaFe 3O 5 has improved cyclability and a high reversible oxygen storage capacity of 22.3 mol%. In this paper, we analyzed the redox mechanism of this compound. After a solid-state synthesis of CaFe 3O 5, we verified the phase composition and studied the redox reaction by means of X-ray diffraction, Mössbauer spectrometry,more » and scanning electron microscopy. Finally, results show a great potential to operate the battery with this storage material during multiple charging–discharging cycles.« less

3D-Hydrogel Based Polymeric Nanoreactors for Silver Nano-Antimicrobial Composites Generation

PubMed Central

Soto-Quintero, Albanelly; Romo-Uribe, Ángel; Bermúdez-Morales, Víctor H.; Quijada-Garrido, Isabel

2017-01-01

This study underscores the development of Ag hydrogel nanocomposites, as smart substrates for antibacterial uses, via innovative in situ reactive and reduction pathways. To this end, two different synthetic strategies were used. Firstly thiol-acrylate (PSA) based hydrogels were attained via thiol-ene and radical polymerization of polyethylene glycol (PEG) and polycaprolactone (PCL). As a second approach, polyurethane (PU) based hydrogels were achieved by condensation polymerization from diisocyanates and PCL and PEG diols. In fact, these syntheses rendered active three-dimensional (3D) hydrogel matrices which were used as nanoreactors for in situ reduction of AgNO3 to silver nanoparticles. A redox chemistry of stannous catalyst in PU hydrogel yielded spherical AgNPs formation, even at 4 °C in the absence of external reductant; and an appropriate thiol-functionalized polymeric network promoted spherical AgNPs well dispersed through PSA hydrogel network, after heating up the swollen hydrogel at 103 °C in the presence of citrate-reductant. Optical and swelling behaviors of both series of hydrogel nanocomposites were investigated as key factors involved in their antimicrobial efficacy over time. Lastly, in vitro antibacterial activity of Ag loaded hydrogels exposed to Pseudomona aeruginosa and Escherichia coli strains indicated a noticeable sustained inhibitory effect, especially for Ag–PU hydrogel nanocomposites with bacterial inhibition growth capabilities up to 120 h cultivation. PMID:28763050

Reduction-Responsive Polymeric Micelles and Vesicles for Triggered Intracellular Drug Release

PubMed Central

Sun, Huanli; Cheng, Ru; Deng, Chao

2014-01-01

Abstract Significance: The therapeutic effects of current micellar and vesicular drug formulations are restricted by slow and inefficient drug release at the pathological site. The development of smart polymeric nanocarriers that release drugs upon arriving at the target site has received a tremendous amount of attention for cancer therapy. Recent Advances: Taking advantage of a high reducing potential in the tumor tissues and in particular inside the tumor cells, various reduction-sensitive polymeric micelles and vesicles have been designed and explored for triggered anticancer drug release. These reduction-responsive nanosystems have demonstrated several unique features, such as good stability under physiological conditions, fast response to intracellular reducing environment, triggering drug release right in the cytosol and cell nucleus, and significantly improved antitumor activity, compared to traditional reduction-insensitive counterparts. Critical Issues: Although reduction-sensitive micelles and polymersomes have accomplished rapid intracellular drug release and enhanced in vitro antitumor effect, their fate inside the cells including the mechanism, site, and rate of reduction reaction remains unclear. Moreover, the systemic fate and performance of reduction-sensitive polymeric drug formulations have to be investigated. Future Directions: Biophysical studies should be carried out to gain insight into the degradation and drug release behaviors of reduction-responsive nanocarriers inside the tumor cells. Furthermore, novel ligand-decorated reduction-sensitive nanoparticulate drug formulations should be designed and explored for targeted cancer therapy in vivo. Antioxid. Redox Signal. 21, 755–767. PMID:24279980

Engineering Folate-Targeting Diselenide-containing Triblock Copolymer as a Redox-Responsive Shell-sheddable Micelle for Antitumor Therapy In Vivo.

PubMed

Behroozi, Farnaz; Abdkhodaie, Mohammad-Jafar; Sadeghi Abandansari, Hamid; Satarian, Leila; Molazem, Mohammad; Al-Jamal, Khuloud T; Baharvand, Hossein

2018-06-18

The oxidation-reduction (redox)-responsive micelle system is based on a diselenide-containing triblock copolymer, poly(ε-caprolactone)-bis(diselenide-methoxy poly(ethylene glycol)/poly(ethylene glycol)-folate) [PCL-(SeSe-mPEG/PEG-FA) 2 ]. This has helped in the development of tumor-targeted delivery for hydrophobic anticancer drugs. The diselenide bond, as a redox-sensitive linkage, was designed in such a manner that it is located at the hydrophilic-hydrophobic hinge to allow complete collapse of the micelle and thus efficient drug release in redox environments. The amphiphilic block copolymers self-assembled into micelles at concentrations higher than the critical micelle concentration (CMC) in an aqueous environment. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) analyses showed that the micelles were spherical with an average diameter of 120 nm. The insoluble anticancer drug paclitaxel (PTX) was loaded into micelles, and its triggered release behavior under different redox conditions was verified. Folate-targeting micelles showed an enhanced uptake in 4T1 breast cancer cells and in vitro cytotoxicity by flow cytometry and (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) (MTS) assay, respectively. Delayed tumor growth was confirmed in the subcutaneously implanted 4T1 breast cancer in mice after intraperitoneal injection. The proposed redox-responsive copolymer offers a new type of biomaterial for drug delivery into cancer cells in vivo. On-demand drug actuation is highly desired. Redox-responsive polymeric DDSs have been shown to be able to respond and release their cargo in a selective manner when encountering a significant change in the potential difference, such as that present between cancerous and healthy tissues. This study offers an added advantage to the field of redox-responsive polymers by reporting a new type of shell-sheddable micelle based on an amphiphilic triblock co-polymer, containing diselenide as a redox-sensitive linkage. The linkage was smartly located at the hydrophilic-hydrophilic bridge in the co-polymer offering complete collapse of the micelle when exposed to the right trigger. The system was able to delay tumor growth and reduce toxicity in a breast cancer tumor model following intraperitoneal injection in mice. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

Advanced Synthesis of Conductive Polyaniline Using Laccase as Biocatalyst.

PubMed

de Salas, Felipe; Pardo, Isabel; Salavagione, Horacio J; Aza, Pablo; Amougi, Eleni; Vind, Jesper; Martínez, Angel T; Camarero, Susana

2016-01-01

Polyaniline is a conductive polymer with distinctive optical and electrical properties. Its enzymatic synthesis is an environmentally friendly alternative to the use of harsh oxidants and extremely acidic conditions. 7D5L, a high-redox potential laccase developed in our lab, is the biocatalyst of choice for the synthesis of green polyaniline (emeraldine salt) due to its superior ability to oxidize aniline and kinetic stability at the required polymerization conditions (pH 3 and presence of anionic surfactants) as compared with other fungal laccases. Doses as low as 7.6 nM of 7D5L catalyze the polymerization of 15 mM aniline (in 24 h, room temperature, 7% yield) in the presence of different anionic surfactants used as doping templates to provide linear and water-soluble polymers. Aniline polymerization was monitored by the increase of the polaron absorption band at 800 nm (typical for emeraldine salt). Best polymerization results were obtained with 5 mM sodium dodecylbenzenesulfonate (SDBS) as template. At fixed conditions (15 mM aniline and 5mM SDBS), polymerization rates obtained with 7D5L were 2.5-fold the rates obtained with commercial Trametes villosa laccase. Moreover, polyaniline yield was notably boosted to 75% by rising 7D5L amount to 0.15 μM, obtaining 1g of green polyaniline in 1L-reaction volume. The green polymer obtained with the selected system (7D5L/SDBS) holds excellent electrochemical and electro-conductive properties displayed in water-dispersible nanofibers, which is advantageous for the nanomaterial to be readily cast into uniform films for different applications.

Advanced Synthesis of Conductive Polyaniline Using Laccase as Biocatalyst

PubMed Central

de Salas, Felipe; Pardo, Isabel; Salavagione, Horacio J.; Aza, Pablo; Amougi, Eleni; Vind, Jesper; Martínez, Angel T.; Camarero, Susana

2016-01-01

Polyaniline is a conductive polymer with distinctive optical and electrical properties. Its enzymatic synthesis is an environmentally friendly alternative to the use of harsh oxidants and extremely acidic conditions. 7D5L, a high-redox potential laccase developed in our lab, is the biocatalyst of choice for the synthesis of green polyaniline (emeraldine salt) due to its superior ability to oxidize aniline and kinetic stability at the required polymerization conditions (pH 3 and presence of anionic surfactants) as compared with other fungal laccases. Doses as low as 7.6 nM of 7D5L catalyze the polymerization of 15 mM aniline (in 24 h, room temperature, 7% yield) in the presence of different anionic surfactants used as doping templates to provide linear and water-soluble polymers. Aniline polymerization was monitored by the increase of the polaron absorption band at 800 nm (typical for emeraldine salt). Best polymerization results were obtained with 5 mM sodium dodecylbenzenesulfonate (SDBS) as template. At fixed conditions (15 mM aniline and 5mM SDBS), polymerization rates obtained with 7D5L were 2.5-fold the rates obtained with commercial Trametes villosa laccase. Moreover, polyaniline yield was notably boosted to 75% by rising 7D5L amount to 0.15 μM, obtaining 1g of green polyaniline in 1L-reaction volume. The green polymer obtained with the selected system (7D5L/SDBS) holds excellent electrochemical and electro-conductive properties displayed in water-dispersible nanofibers, which is advantageous for the nanomaterial to be readily cast into uniform films for different applications. PMID:27741301

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

Wang, Wenwen; Wang, Weiyu; Li, Hui

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

Redox processes and water quality of selected principal aquifer systems

USGS Publications Warehouse

McMahon, P.B.; Chapelle, F.H.

2008-01-01

Reduction/oxidation (redox) conditions in 15 principal aquifer (PA) systems of the United States, and their impact on several water quality issues, were assessed from a large data base collected by the National Water-Quality Assessment Program of the USGS. The logic of these assessments was based on the observed ecological succession of electron acceptors such as dissolved oxygen, nitrate, and sulfate and threshold concentrations of these substrates needed to support active microbial metabolism. Similarly, the utilization of solid-phase electron acceptors such as Mn(IV) and Fe(III) is indicated by the production of dissolved manganese and iron. An internally consistent set of threshold concentration criteria was developed and applied to a large data set of 1692 water samples from the PAs to assess ambient redox conditions. The indicated redox conditions then were related to the occurrence of selected natural (arsenic) and anthropogenic (nitrate and volatile organic compounds) contaminants in ground water. For the natural and anthropogenic contaminants assessed in this study, considering redox conditions as defined by this framework of redox indicator species and threshold concentrations explained many water quality trends observed at a regional scale. An important finding of this study was that samples indicating mixed redox processes provide information on redox heterogeneity that is useful for assessing common water quality issues. Given the interpretive power of the redox framework and given that it is relatively inexpensive and easy to measure the chemical parameters included in the framework, those parameters should be included in routine water quality monitoring programs whenever possible.

Solvent free chemical oxidative polymerization as a universal method for the synthesis of ultra high molecular weight conjugated polymers based on 3,4-propylenedioxythiophenes.

PubMed

Kumar, Anshu; Singh, Rekha; Gopinathan, Sreelekha P; Kumar, Anil

2012-05-18

In this communication, we report on a solvent free chemical oxidative polymerization route for the monomers based on 3,4-propylenedioxythiophenes wherein the process is applicable to both solid as well as liquid monomers and results in the bulk synthesis of ultra high molecular weight polymers. This journal is © The Royal Society of Chemistry 2012

Synthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)

NASA Technical Reports Server (NTRS)

Paley, M. S.; Frazier, D. O.; Abeledeyem, H.; Mcmanus, S. P.; Zutaut, S. E.

1992-01-01

In the present work two diacetylene derivatives of pyrrole which are predicted by semiempirical AM1 calculations to have very different properties, are synthesized; the polymerizability of these diacetylenes in the solid state is determined, and the results are compared to the computer predictions. Diacetylene 1 is novel in that the monomer is a liquid at room temperature; this may allow for the possibility of polymerization in the liquid state as well as the solid state. Thin poly(diacetylene) films are obtained from compound 1 by growing films of the monomer using vapor deposition and polymerizing with UV light; these films are then characterized. Interestingly, while the poly(diacetylene) from 1 does not possess good nonlinear optical properties, the monomer exhibits very good third-order effects (phase conjugation) in solution. Dilute acetone solutions of the monomer 1 give intensity-dependent refractive indices on the order of 10 exp -6 esu; these are 10 exp 6 times better than for CS2.

Polymeric ionic liquid bucky gels as sorbent coatings for solid-phase microextraction.

PubMed

Zhang, Cheng; Anderson, Jared L

2014-05-30

Novel cross-linked polymeric ionic liquid (PIL) bucky gels were formed by free-radical polymerization of polymerizable ionic liquids gelled with multi-walled carbon nanotubes (MWCNT) and used as sorbent coatings for solid-phase microextraction (SPME). The combination of PIL with MWCNTs significantly enhanced the π-π interaction between the sorbent coatings and the aromatic analytes. Compared to the neat PIL-based sorbent coating, the PIL bucky gel sorbent coatings demonstrated higher extraction efficiency for the extraction of polycyclic aromatic hydrocarbons (PAHs). A partitioning extraction mechanism was observed for the PIL/MWCNT-based sorbent coatings indicating that the addition of MWCNTs did not seem to affect the extraction mechanism of the sorbent coating. The analyte-to-coating partition coefficients (logKfs) were estimated and the limits of detection (LOD) for selected PIL bucky gel sorbent coating were determined to be in the range of 1-2.5 ng L(-1). Recovery studies were also performed for PAHs in river and tap water to validate the applicability of the developed method. Copyright © 2014 Elsevier B.V. All rights reserved.

Two-Dimensional Fullerene Assembly from an Exfoliated van der Waals Template.

PubMed

Lee, Kihong; Choi, Bonnie; Plante, Ilan Jen-La; Paley, Maria V; Zhong, Xinjue; Crowther, Andrew C; Owen, Jonathan S; Zhu, Xiaoyang; Roy, Xavier

2018-05-22

Two-dimensional (2D) materials are commonly prepared by exfoliating bulk layered van der Waals crystals. The creation of synthetic 2D materials from bottom-up methods is an important challenge as their structural flexibility will enable chemists to tune the materials properties. A 2D material was assembled using C 60 as a polymerizable monomer. The C 60 building blocks are first assembled into a layered solid using a molecular cluster as structure director. The resulting hierarchical crystal is used as a template to polymerize its C 60 monolayers, which can be exfoliated down to 2D crystalline nanosheets. Derived from the parent template, the 2D structure is composed of a layer of inorganic cluster, sandwiched between two monolayers of polymerized C 60 . The nanosheets can be transferred onto solid substrates and depolymerized by heating. Electronic absorption spectroscopy reveals an optical gap of 0.25 eV, narrower than that of the bulk parent crystalline solid. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-phase synthesis of molecularly imprinted nanoparticles.

PubMed

Canfarotta, Francesco; Poma, Alessandro; Guerreiro, Antonio; Piletsky, Sergey

2016-03-01

Molecularly imprinted polymers (MIPs) are synthetic materials, generally based on acrylic or methacrylic monomers, that are polymerized in the presence of a specific target molecule called the 'template' and capable of rebinding selectively to this target molecule. They have the potential to be low-cost and robust alternatives to biomolecules such as antibodies and receptors. When prepared by traditional synthetic methods (i.e., with free template in solution), their usefulness has been limited by high binding site heterogeneity, the presence of residual template and the fact that the production methods are complex and difficult to standardize. To overcome some of these limitations, we developed a method for the synthesis of MIP nanoparticles (nanoMIPs) using an innovative solid-phase approach, which relies on the covalent immobilization of the template molecules onto the surface of a solid support (glass beads). The obtained nanoMIPs are virtually free of template and demonstrate high affinity for the target molecule (e.g., melamine and trypsin in our published work). Because of an affinity separation step performed on the solid phase after polymerization, poor binders and unproductive polymer are removed, so the final product has more uniform binding characteristics. The overall protocol, starting from the immobilization of the template onto the solid phase and including the purification and characterization of the nanoparticles, takes up to 1 week.

Thiol surface functionalization via continuous phase plasma polymerization of allyl mercaptan, with subsequent maleimide-linked conjugation of collagen.

PubMed

Stynes, Gil D; Gengenbach, Thomas R; Kiroff, George K; Morrison, Wayne A; Kirkland, Mark A

2017-07-01

Thiol groups can undergo a large variety of chemical reactions and are used in solution phase to conjugate many bioactive molecules. Previous research on solid substrates with continuous phase glow discharge polymerization of thiol-containing monomers may have been compromised by oxidation. Thiol surface functionalization via glow discharge polymerization has been reported as requiring pulsing. Herein, continuous phase glow discharge polymerization of allyl mercaptan (2-propene-1-thiol) was used to generate significant densities of thiol groups on a mixed macrodiol polyurethane and tantalum. Three general classes of chemistry are used to conjugate proteins to thiol groups, with maleimide linkers being used most commonly. Here the pH specificity of maleimide reactions was used effectively to conjugate surface-bound thiol groups to amine groups in collagen. XPS demonstrated surface-bound thiol groups without evidence of oxidation, along with the subsequent presence of maleimide and collagen. Glow discharge reactor parameters were optimized by testing the resistance of bound collagen to degradation by 8 M urea. The nature of the chemical bonding of collagen to surface thiol groups was effectively assessed by colorimetric assay (ELISA) of residual collagen after incubation in 8 M urea over 8 days and after incubation with keratinocytes over 15 days. The facile creation of useable solid-supported thiol groups via continuous phase glow discharge polymerization of allyl mercaptan opens a route for attaching a vast array of bioactive molecules. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1940-1948, 2017. © 2017 Wiley Periodicals, Inc.

Solid polymeric electrolytes for lithium batteries

DOEpatents

Angell, Charles A.; Xu, Wu; Sun, Xiaoguang

2006-03-14

Novel conductive polyanionic polymers and methods for their preparion are provided. The polyanionic polymers comprise repeating units of weakly-coordinating anionic groups chemically linked to polymer chains. The polymer chains in turn comprise repeating spacer groups. Spacer groups can be chosen to be of length and structure to impart desired electrochemical and physical properties to the polymers. Preferred embodiments are prepared from precursor polymers comprising the Lewis acid borate tri-coordinated to a selected ligand and repeating spacer groups to form repeating polymer chain units. These precursor polymers are reacted with a chosen Lewis base to form a polyanionic polymer comprising weakly coordinating anionic groups spaced at chosen intervals along the polymer chain. The polyanionic polymers exhibit high conductivity and physical properties which make them suitable as solid polymeric electrolytes in lithium batteries, especially secondary lithium batteries.

Potentiometric sensors with carbon black supporting platinum nanoparticles.

PubMed

Paczosa-Bator, Beata; Cabaj, Leszek; Piech, Robert; Skupień, Krzysztof

2013-11-05

For the first time, a single-piece, all-solid-state ion-selective electrode was fabricated with carbon black supporting platinum nanoparticles (PtNPs-CB) and a polymeric membrane. The PtNPs-CB, as an intermediate layer, was drop-casted directly on the solid substrate, and then an ionophore-doped solvent polymeric membrane was added in order to form a sensor. The performance of the newly developed electrodes was evaluated on the basis of potassium and nitrate ions. The stability of the electrical potential for the electrodes was examined by performing current-reversal chronopotentiometry, and the influence of the interfacial water film was assessed by the potentiometric aqueous-layer test. Fabricated potassium- and nitrate-selective electrodes displayed a Nernstian slope and several outstanding properties such as high long-term potential stability, potential repeatability, and reproducibility.

Conductivity enhancement of surface-polymerized polyaniline films via control of processing conditions

NASA Astrophysics Data System (ADS)

Park, Chung Hyoi; Jang, Sung Kyu; Kim, Felix Sunjoo

2018-01-01

We investigate a fast and facile approach for the simultaneous synthesis and coating of conducting polyaniline (PANI) onto a substrate and the effects of processing conditions on the electrical properties of the fabricated films. Simultaneous polymerizing and depositing on the substrate forms a thin film with the average thickness of 300 nm and sheet resistance of 304 Ω/sq. Deposition conditions such as polymerization time (3-240 min), temperature (-10 to 40 °C), concentrations of monomer and oxidant (0.1-0.9 M), and type of washing solvents (acetone, water, and/or HCl solution) affect the film thickness, doping state, absorption characteristics, and solid-state nanoscale morphology, therefore affecting the electrical conductivity. Among the conditions, the surface-polymerized PANI film deposited at room temperature with acetone washing showed the highest conductivity of 22.2 S/cm.

Variations of structures and solid-state conductivity of isomeric silver(I) coordination polymers having linear and V-shaped thiophene-centered ditriazole ligands

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

Hu, Bin; School of Environmental and Chemical Engineering, Nanchang Hangkong University, Nanchang, 330063; Geng, Jiao

2014-07-01

A pair of new linear and V-shaped acceptor–donor–acceptor (A−D−A) thiophene-centered ditriazole structural isomers, i.e., 2,5-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 1}) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 2}), has been synthesized and characterized. They are used as μ{sub 2}-bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L{sup 1})(NO{sub 3})]{sub n} (1) and [Ag(L{sup 2})(NO{sub 3})]{sub n} (2), which are also structural isomers at the supramolecular level. X-ray single-crystal diffraction analyses for 1 and 2 reveal that they exhibit the same one-dimensional (1D) coordination polymers but different structural architectures because of the distinguishable shape and configuration of isomeric ligands (L{sup 1} and L{sup 2})more » and the alterations of the coordination numbers. More interestingly, compared with the free ligands, 1D silver(I) polymeric isomers 1 and 2 show significant enhancement of solid-state conductivity to different extents (1.42×10{sup 4} and 2.17×10{sup 3} times), where 6.96 times' enhancement of solid-state conductivity from 1 to 2 has been observed. The formation of Ag–N coordinative bonds and the configurational discrepancy of L{sup 1} and L{sup 2} are believed to play important roles in facilitating the electron transport between molecules, which can also be supported by Density Function Theory calculations of their band gaps. - Graphical abstract: A pair of linear and V-shaped isomeric thiophene-centered ditriazole ligands (L{sup 1}) and L{sup 2} are used to prepare a pair of silver(I) polymeric isomers (1 and 2), where significant enhancement of solid-state conductivity to different extents are observed originating from the distinguishable shape and configuration of isomeric ligands. - Highlights: • A pair of linear and V-shaped thiophene-centered ditriazole structural isomers is prepared. • They are used as µ{sub 2}-bridging ligands to prepare a pair of silver(I) polymeric isomers. • Significant enhancement of solid-state conductivity is observed for each polymeric isomer.« less

Reducing or stopping the uncontrolled flow of fluid such as oil from a well

DOEpatents

Hermes, Robert E

2014-02-18

The uncontrolled flow of fluid from an oil or gas well may be reduced or stopped by injecting a composition including 2-cyanoacrylate ester monomer into the fluid stream. Injection of the monomer results in a rapid, perhaps instantaneous, polymerization of the monomer within the flow stream of the fluid. This polymerization results in formation of a solid plug that reduces or stops the flow of additional fluid from the well.

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

PubMed

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

2018-01-01

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

[Preparation and structural analysis of diatomite-supported SPFS flocculant].

PubMed

Zheng, Huai-li; Fang, Hui-li; Jiang, Shao-jie; Yang, Chun; Ma, Jiang-ya; Zhang, Zhao-qing

2011-07-01

In the presetn study, polymerized ferric sulphate (PFS) flocculant was prepared and tested. In the preparation of PFS flocculant, industrial by-product ferrous sulfate heptahydrate (FeSO4.7H2O) was reused as the main material. By composition with diatomite and drying up at certain temperature in vacuum drying oven, solid PFS flocculant was produced. Structural characteristics of the new flocculant product were examined through infrared spectroscopy and scanning electron microscopy (SEM), which showed that by compositing with diatomite, new group bridging emerged in the structure of PFS, which made the bond of groups stronger. In addition, part of the metalic contents in diatomite was polymerized with PFS, the product of which was polymerized ferric complex. Furthermore, the absorbing and agglomerating capacity of the diatomite carrier was significant. Considering the factors listed above, the new solid polymerized ferric sulphate (SPFS) flocculant was characterized with a larger molecule structure and enhanced absorbing, bridging and rolling sweep capacities. Through orthogonal experiment, optimum conditions of synthesis were as follows: the ratio of FeSO4.7H2O/diatomite in weight was 43/1, the reaction time is 1 h and the reaction temperature is 55 degrees C. By wastewater treatment experiment, it was found that the synthetic products showed good flocculation performance in the treatment of domestic sewage, the removal of COD was 80.00% and the removal of turbidity was 99.98%.

Novel (meth)acrylate monomers for ultrarapid polymerization and enhanced polymer properties

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

Beckel, E. R.; Berchtold, K. A.; Nie, J.

2002-01-01

Ultraviolet light is known to be one of the most efficient methods to initiatc polymeric reactions in the presence of a photonitiator. Photopolymerizations are advantageous because the chemistry of the materials can be tailored to design liquid monomers for ultrarapid polymerization into a solid polymer material. One way to achieve rapid photopolymerizations is to utilize multifunctional (meth)acrylate monomers. which form highly crosslinked polymers; however, these monomers typically do not achieve complete functional group conversion. Recently, Decker et al. developed novel monovinyl acrylate monomers that display polyriicrization kinetics that rival those of multifunctional acrylate monomers. These novel acrylate monomers incorporate secondarymore » functionalities and end groups such as carbonates, carbamates, cyclic carbonates and oxazolidone which promote the increased polymerization kinetics of these monomers. In addition to thc polynierization kinetics, these novel monovinyl monomers form crosslinked polymers, which are characterized by having high strength and high flexibility. Unfortunately, the exact mechanism or mechanisms responsible for the polymerization kinetics and crosslinking are not well understood.« less

Mechanochemical Ring-Opening Polymerization of Lactide: Liquid-Assisted Grinding for the Green Synthesis of Poly(lactic acid) with High Molecular Weight.

PubMed

Ohn, Nuri; Shin, Jihoon; Kim, Sung Sik; Kim, Jeung Gon

2017-09-22

Mechanochemical polymerization of lactide is carried out by using ball milling. Mechanical energy from collisions between the balls and the vessel efficiently promotes an organic-base-mediated metal- and solvent-free solid-state polymerization. Investigation of the parameters of the ball-milling synthesis revealed that the degree of lactide ring-opening polymerization could be modulated by the ball-milling time, vibration frequency, mass of the ball media, and liquid-assisted grinding. Liquid-assisted grinding was found to be an especially important factor for achieving a high degree of mechanochemical polymerization. Although polymer-chain scission from the strong collision energy prevented mechanical-force-driven high-molecular-weight polymer synthesis, the addition of only a small amount of liquid enabled sufficient energy dissipation and poly(lactic acid) was thereby obtained with a molecular weight of over 1×10 5  g mol -1 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reductive de-polymerization of kraft lignin for chemicals and fuels using formic acid as an in-situ hydrogen source.

PubMed

Huang, Shanhua; Mahmood, Nubla; Tymchyshyn, Matthew; Yuan, Zhongshun; Xu, Chunbao Charles

2014-11-01

In this study, formic acid (FA) was employed as an in-situ hydrogen donor for the reductive de-polymerization of kraft lignin (KL). Under the optimum operating conditions, i.e., 300 °C, 1 h, 18.6 wt.% substrate concentration, 50/50 (v/v) water-ethanol medium with FA at a FA-to-lignin mass ratio of 0.7, KL (Mw∼10,000 g/mol) was effectively de-polymerized, producing de-polymerized lignin (DL, Mw 1270 g/mol) at a yield of ∼90 wt.% and <1 wt.% yield of solid residue (SR). The MW of the DL products decreased with increasing reaction temperature, time and FA-to-lignin mass ratio. The sulfur contents of all DL products were remarkably lower than that in the original KL. It was also demonstrated that FA is a more reactive hydrogen source than external hydrogen for reductive de-polymerization of KL. Copyright © 2014 Elsevier Ltd. All rights reserved.

An Ambient Temperature Molten Sodium-Vanadium Battery with Aqueous Flowing Catholyte.

PubMed

Liu, Caihong; Shamie, Jack S; Shaw, Leon L; Sprenkle, Vincent L

2016-01-20

In this study, we have investigated the key factors dictating the cyclic performance of a new type of hybrid sodium-based flow batteries (HNFBs) that can operate at room temperature with high cell voltages (>3 V), multiple electron transfer redox reactions per active ion, and decoupled design of power and energy. HNFBs are composed of a molten Na-Cs alloy anode, flowing aqueous catholyte, and a Na-β″-Al2O3 solid electrolyte as the separator. The surface functionalization of graphite felt electrodes for the flowing aqueous catholyte has been studied for its effectiveness in enhancing V(2+)/V(3+), V(3+)/V(4+), and V(4+)/V(5+) redox couples. The V(4+)/V(5+) redox reaction has been further investigated at different cell operation temperatures for its cyclic stability and how the properties of the solid electrolyte membrane play a role in cycling. These fundamental understandings provide guidelines for improving the cyclic performance and stability of HNFBs with aqueous catholytes. We show that the HNFB with aqueous V-ion catholyte can reach high storage capacity (∼70% of the theoretical capacity) with good Coulombic efficiency (90% ± 1% in 2-30 cycles) and cyclic performance (>99% capacity retention for 30 cycles). It demonstrates, for the first time, the potential of high capacity HNFBs with aqueous catholytes, good capacity retention and long cycling life. This is also the first demonstration that Na-β″-Al2O3 solid electrolyte can be used with aqueous electrolyte at near room temperature for more than 30 cycles.

Automatic reactor for solid-phase synthesis of molecularly imprinted polymeric nanoparticles (MIP NPs) in water.

PubMed

Poma, Alessandro; Guerreiro, Antonio; Caygill, Sarah; Moczko, Ewa; Piletsky, Sergey

We report the development of an automated chemical reactor for solid-phase synthesis of MIP NPs in water. Operational parameters are under computer control, requiring minimal operator intervention. In this study, "ready for use" MIP NPs with sub-nanomolar affinity are prepared against pepsin A, trypsin and α-amylase in only 4 hours.

Automatic reactor for solid-phase synthesis of molecularly imprinted polymeric nanoparticles (MIP NPs) in water

PubMed Central

Poma, Alessandro; Guerreiro, Antonio; Caygill, Sarah; Moczko, Ewa; Piletsky, Sergey

2015-01-01

We report the development of an automated chemical reactor for solid-phase synthesis of MIP NPs in water. Operational parameters are under computer control, requiring minimal operator intervention. In this study, “ready for use” MIP NPs with sub-nanomolar affinity are prepared against pepsin A, trypsin and α-amylase in only 4 hours. PMID:26722622

Homogeneous synthesis of cellulose acrylate-g-poly (n-alkyl acrylate) solid-solid phase change materials via free radical polymerization.

PubMed

Qian, Yong-Qiang; Han, Na; Bo, Yi-Wen; Tan, Lin-Li; Zhang, Long-Fei; Zhang, Xing-Xiang

2018-08-01

A novel solid-solid phase change materials, namely, cellulose acrylate-g-poly (n-alkyl acrylate) (CA-g-PAn) (n = 14, 16 and 18) were successfully synthesized by free radical polymerization in N, N-dimethylacetamide (DMAc). The successful grafting was confirmed by fourier transform infrared spectra (FT-IR) and nuclear magnetic resonance (NMR). The properties of the CA-g-PAn copolymers were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The phase change temperatures and the melting enthalpies of CA-g-PAn copolymers are in the range of 10.1-53.2 °C and 15-95 J/g, respectively. It can be adjusted by the contents of poly (n-alkyl acrylate) and the length of alkyl side-chain. The thermal resistant temperatures of CA-g-PA14, 16 and 18 copolymers are 308 °C, 292 °C and 273 °C, respectively. It show that all of grafting materials exhibit good thermal stability and shape stability. Therefore, it is expected to be applied in the cellulose-based thermos-regulating field. Copyright © 2018 Elsevier Ltd. All rights reserved.

Investigating buried polymer interfaces using sum frequency generation vibrational spectroscopy

PubMed Central

Chen, Zhan

2010-01-01

This paper reviews recent progress in the studies of buried polymer interfaces using sum frequency generation (SFG) vibrational spectroscopy. Both buried solid/liquid and solid/solid interfaces involving polymeric materials are discussed. SFG studies of polymer/water interfaces show that different polymers exhibit varied surface restructuring behavior in water, indicating the importance of probing polymer/water interfaces in situ. SFG has also been applied to the investigation of interfaces between polymers and other liquids. It has been found that molecular interactions at such polymer/liquid interfaces dictate interfacial polymer structures. The molecular structures of silane molecules, which are widely used as adhesion promoters, have been investigated using SFG at buried polymer/silane and polymer/polymer interfaces, providing molecular-level understanding of polymer adhesion promotion. The molecular structures of polymer/solid interfaces have been examined using SFG with several different experimental geometries. These results have provided molecular-level information about polymer friction, adhesion, interfacial chemical reactions, interfacial electronic properties, and the structure of layer-by-layer deposited polymers. Such research has demonstrated that SFG is a powerful tool to probe buried interfaces involving polymeric materials, which are difficult to study by conventional surface sensitive analytical techniques. PMID:21113334

Novel composite membrane coated with a poly(diallyldimethylammonium chloride)/urushi semi-interpenetrating polymer network for non-aqueous redox flow battery application

NASA Astrophysics Data System (ADS)

Cho, Eunhae; Won, Jongok

2016-12-01

Novel composite membranes of a semi-interpenetrating network (semi-IPN) coated on the surfaces of a porous Celgard 2400 support are prepared and investigate for application in a non-aqueous redox flow battery (RFB). A natural polymer, urushi, is used for the matrix because of its high mechanical robustness, and poly(diallyldimethylammonium chloride) (PDDA) provides anionic exchange sites. The PDDA/urushi (P/U) semi-IPN film is prepared by the photo polymerization of urushiol in the presence of PDDA. The thin layer composed of the P/U semi-IPN on the porous support provides selectivity while maintaining the ion conductivity. The coulombic and energy efficiencies increase with increasing amounts of PDDA in the P/U semi-IPN layer, and the values reach 69.5% and 42.5%, respectively, for the one containing 40 wt% of PDDA. These values are substantially higher than those of the Neosepta AHA membrane and the Celgard membrane, indicating that the selective layer reduces the crossover of the redox active species through the membrane. This result implies that the formation of composite membranes using semi-IPN selective layers on the dimensionally stable porous membrane enable the successful use of a non-aqueous RFB for future energy storage systems.

Ag/Au/Polypyrrole Core-shell Nanowire Network for Transparent, Stretchable and Flexible Supercapacitor in Wearable Energy Devices

NASA Astrophysics Data System (ADS)

Moon, Hyunjin; Lee, Habeom; Kwon, Jinhyeong; Suh, Young Duk; Kim, Dong Kwan; Ha, Inho; Yeo, Junyeob; Hong, Sukjoon; Ko, Seung Hwan

2017-02-01

Transparent and stretchable energy storage devices have attracted significant interest due to their potential to be applied to biocompatible and wearable electronics. Supercapacitors that use the reversible faradaic redox reaction of conducting polymer have a higher specific capacitance as compared with electrical double-layer capacitors. Typically, the conducting polymer electrode is fabricated through direct electropolymerization on the current collector. However, no research have been conducted on metal nanowires as current collectors for the direct electropolymerization, even though the metal nanowire network structure has proven to be superior as a transparent, flexible, and stretchable electrode platform because the conducting polymer’s redox potential for polymerization is higher than that of widely studied metal nanowires such as silver and copper. In this study, we demonstrated a highly transparent and stretchable supercapacitor by developing Ag/Au/Polypyrrole core-shell nanowire networks as electrode by coating the surface of Ag NWs with a thin layer of gold, which provide higher redox potential than the electropolymerizable monomer. The Ag/Au/Polypyrrole core-shell nanowire networks demonstrated superior mechanical stability under various mechanical bending and stretching. In addition, proposed supercapacitors showed fine optical transmittance together with fivefold improved areal capacitance compared to pristine Ag/Au core-shell nanowire mesh-based supercapacitors.

Ag/Au/Polypyrrole Core-shell Nanowire Network for Transparent, Stretchable and Flexible Supercapacitor in Wearable Energy Devices

PubMed Central

Moon, Hyunjin; Lee, Habeom; Kwon, Jinhyeong; Suh, Young Duk; Kim, Dong Kwan; Ha, Inho; Yeo, Junyeob; Hong, Sukjoon; Ko, Seung Hwan

2017-01-01

Transparent and stretchable energy storage devices have attracted significant interest due to their potential to be applied to biocompatible and wearable electronics. Supercapacitors that use the reversible faradaic redox reaction of conducting polymer have a higher specific capacitance as compared with electrical double-layer capacitors. Typically, the conducting polymer electrode is fabricated through direct electropolymerization on the current collector. However, no research have been conducted on metal nanowires as current collectors for the direct electropolymerization, even though the metal nanowire network structure has proven to be superior as a transparent, flexible, and stretchable electrode platform because the conducting polymer’s redox potential for polymerization is higher than that of widely studied metal nanowires such as silver and copper. In this study, we demonstrated a highly transparent and stretchable supercapacitor by developing Ag/Au/Polypyrrole core-shell nanowire networks as electrode by coating the surface of Ag NWs with a thin layer of gold, which provide higher redox potential than the electropolymerizable monomer. The Ag/Au/Polypyrrole core-shell nanowire networks demonstrated superior mechanical stability under various mechanical bending and stretching. In addition, proposed supercapacitors showed fine optical transmittance together with fivefold improved areal capacitance compared to pristine Ag/Au core-shell nanowire mesh-based supercapacitors. PMID:28155913

Acridine Orange Conjugated Polymersomes for Simultaneous Nuclear Delivery of Gemcitabine and Doxorubicin to Pancreatic Cancer Cells.

PubMed

Anajafi, Tayebeh; Scott, Michael D; You, Seungyong; Yang, Xiaoyu; Choi, Yongki; Qian, Steven Y; Mallik, Sanku

2016-03-16

Considering the systemic toxicity of chemotherapeutic agents, there is an urgent need to develop new targeted drug delivery systems. Herein, we have developed a new nuclear targeted, redox sensitive, drug delivery vehicle to simultaneously deliver the anticancer drugs gemcitabine and doxorubicin to the nuclei of pancreatic cancer cells. We prepared polymeric bilayer vesicles (polymersomes), and actively encapsulated the drug combination by the pH gradient method. A redox-sensitive polymer (PEG-S-S-PLA) was incorporated to sensitize the formulation to reducing agent concentration. Acridine orange (AO) was conjugated to the surface of the polymersomes imparting nuclear localizing property. The polymersomes' toxicity and efficacy were compared with those of a free drug combination using monolayer and three-dimensional spheroid cultures of pancreatic cancer cells. We observed that the redox sensitive, nuclear-targeted polymersomes released more than 60% of their encapsulated contents in response to 50 mM glutathione. The nanoparticles are nontoxic; however, the drug encapsulated vesicles have significant toxicity. The prepared formulation can increase the drug's therapeutic index by delivering the drugs directly to the cells' nuclei, one of the key organelles in the cells. This study is likely to initiate research in targeted nuclear delivery using other drug formulations in other types of cancers.

The cohesive law of particle/binder interfaces in solid propellants

NASA Astrophysics Data System (ADS)

Tan, H.

2011-10-01

Solid propellants are treated as composites with high volume fraction of particles embedded in the polymeric binder. A micromechanics model is developed to establish the link between the microscopic behavior of particle/binder interfaces and the macroscopic constitutive information. This model is then used to determine the tension/shearing coupled interface cohesive law of a redesigned solid rocket motor propellant, based on the experimental data of the stress-strain and dilatation-strain curves for the material under slow rate uniaxial tension.

Synthesis of acrylic polymer beads for solid-supported proline-derived organocatalysts.

PubMed

Kristensen, Tor E; Vestli, Kristian; Fredriksen, Kim A; Hansen, Finn K; Hansen, Tore

2009-07-16

A completely non-chromatographic and highly large-scale adaptable synthesis of acrylic polymer beads containing proline and prolineamides has been developed. Novel monomeric proline (meth)acrylates are prepared from hydroxyproline in only one step. Free-radical copolymerization then gives solid-supported proline organocatalysts directly in as little as two steps overall, without using any prefabricated solid supports, by using either droplet or dispersion polymerization. These affordable acrylic beads have highly favorable and adjustable swelling characteristics and are excellent reusable catalysts for organocatalytic reactions.

Rheology of Hyperbranched Poly(triglyceride)-Based Thermoplastic Elastomers via RAFT polymerization

NASA Astrophysics Data System (ADS)

Yan, Mengguo; Cochran, Eric

2014-03-01

In this contribution we discuss how melt- and solid-state properties are influenced by the degree of branching and molecular weight in a family of hyperbranched thermoplastics derived from soybean oil. Acrylated epoxidized triglycerides from soybean oils have been polymerized to hyperbranched thermoplastic elastomers using reversible addition-fragmentation chain transfer (RAFT) polymerization. With the proper choice of chain transfer agent, both homopolymer and block copolymer can be synthesized. By changing the number of acrylic groups per triglycerides, the chain architectures can range from nearly linear to highly branched. We show how the fundamental viscoelastic properties (e.g. entanglement molecular weight, plateau modulus, etc.) are influenced by chain architecture and molecular weight.

Tetrahedrally Coordinated Fe3+ in Silicate Glasses: A Mossbauer, Iron K-edge XANES and Raman Spectroscopies Study

NASA Astrophysics Data System (ADS)

Cochain, B.; Neuville, D. R.; McCammon, C.; Henderson, G. S.; de Ligny, D.; Pinet, O.; Richet, P.

2009-05-01

In natural or industrial glasses, iron is the most abundant transition metal. A good knowledge of its redox equilibrium is important to better understand the chemical and structural evolution of magmas (crystallization, viscosity), and also to optimize vitrification processes and properties of iron-bearing glasses. To study the role of iron in silicate glasses and melts, we have used in a consistent manner the Mössbauer, iron K-edge XANES and Raman spectroscopies to investigate several series of silicate glasses as a function of redox state. The samples were selected to cover a wide composition range and to investigate the interactions of iron with two network forming cations, namely, Al3+ and B3+. The glasses investigated were synthesized at high temperature under various conditions of oxygen fugacity to achieve different redox ratios for each composition. Therefore, the iron redox state was varied from the most oxidized to the most reduced. Iron redox ratios were first determined by wet chemical analysis and in some cases by room temperature Mossbauer spectroscopy. This experimental method was also used to determine the local structure of iron of some of the investigated glasses. These results where compared to iron K-edge XANES/EXAFS spectroscopy results, which lead to the iron redox state and indicate that Fe2+ is in octahedral coordination whereas Fe3+ is in tetrahedral coordination. In addition, Raman spectroscopy gave us information on the network polymerization of glasses. Clearly changes in Raman spectra are visible with the evolution of iron redox ratio. For a given composition, we observed systematically, in the 800-1200 cm-1 envelope, which is sensitive to the environment of tetrahedrally coordinated cations, the growth of a band with the iron content and the oxidation state of the sample. The peak area of this band, which we attribute to vibrational modes involving tetrahedrally coordinated Fe3+, increases with the oxidation of the sample. This evolution leads us to establish a calibration procedure for a given composition. Calibration curves can be followed to investigate in situ kinetics of redox reactions. We present here results on the role of iron and its interactions with the silicate network for several compositions as pyroxene based glasses and iron bearing alkali alumino-borosilicate glasses.

Electrochemical storage cell containing a substituted anisole or di-anisole redox shuttle additive for overcharge protection and suitable for use in liquid organic and solid polymer electrolytes

DOEpatents

Kerr, John B.; Tian, Minmin

2000-01-01

A electrochemical cell is described comprising an anode, a cathode, a solid polymer electrolyte, and a redox shuttle additive to protect the cell against overcharging and a redox shuttle additive to protect the cell against overcharging selected from the group consisting of: (a) a substituted anisole having the general formula (in an uncharged state): ##STR1## where R.sub.1 is selected from the group consisting of H, OCH.sub.3, OCH.sub.2 CH.sub.3, and OCH.sub.2 phenyl, and R.sub.2 is selected from the group consisting of OCH.sub.3, OCH.sub.2 CH.sub.3, OCH.sub.2 phenyl, and O.sup.- Li.sup.+ ; and (b) a di-anisole compound having the general formula (in an uncharged state): ##STR2## where R is selected from the group consisting of -OCH.sub.3 and -CH.sub.3, m is either 1 or 0, n is either 1 or 0, and X is selected from the group consisting of -OCH.sub.3 (methoxy) or its lithium salt --O.sup.- Li.sup.+. The lithium salt of the di-anisole is the preferred form of the redox shuttle additive because the shuttle anion will then initially have a single negative charge, it loses two electrons when it is oxidized at the cathode, and then moves toward the anode as a single positively charged species where it is then reduced to a single negatively charged species by gaining back two electrons.

In Vivo Monitoring of pH, Redox Status, and Glutathione Using L-Band EPR for Assessment of Therapeutic Effectiveness in Solid Tumors

PubMed Central

Bobko, Andrey A.; Eubank, Timothy D.; Voorhees, Jeffrey L.; Efimova, Olga V.; Kirilyuk, Igor A.; Petryakov, Sergey; Trofimiov, Dmitrii G.; Marsh, Clay B.; Zweier, Jay L.; Grigor’ev, Igor A.; Samouilov, Alexandre; Khramtsov, Valery V.

2011-01-01

Approach for in vivo real-time assessment of tumor tissue extracellular pH (pHe), redox, and intracellular glutathione based on L-band EPR spectroscopy using dual function pH and redox nitroxide probe and disulfide nitroxide biradical, is described. These parameters were monitored in PyMT mice bearing breast cancer tumors during treatment with granulocyte macrophage colony-stimulating factor. It was observed that tumor pHe is about 0.4 pH units lower than that in normal mammary gland tissue. Treatment with granulocyte macrophage colony-stimulating factor decreased the value of pHe by 0.3 units compared with PBS control treatment. Tumor tissue reducing capacity and intracellular glutathione were elevated compared with normal mammary gland tissue. Granulocyte macrophage colony-stimulating factor treatment resulted in a decrease of the tumor tissue reducing capacity and intracellular glutathione content. In addition to spectroscopic studies, pHe mapping was performed using recently proposed variable frequency proton–electron double-resonance imaging. The pH mapping superimposed with MRI image supports probe localization in mammary gland/tumor tissue, shows high heterogeneity of tumor tissue pHe and a difference of about 0.4 pH units between average pHe values in tumor and normal mammary gland. In summary, the developed multifunctional approach allows for in vivo, noninvasive pHe, extracellular redox, and intracellular glutathione content monitoring during investigation of various therapeutic strategies for solid tumors. Magn Reson Med 000:000–000, 2011. PMID:22113626

High performance solid-state electric double layer capacitor from redox mediated gel polymer electrolyte and renewable tamarind fruit shell derived porous carbon.

PubMed

Senthilkumar, S T; Selvan, R Kalai; Melo, J S; Sanjeeviraja, C

2013-11-13

The activated carbon was derived from tamarind fruit shell and utilized as electrodes in a solid state electrochemical double layer capacitor (SSEDLC). The fabricated SSEDLC with PVA (polyvinyl alcohol)/H2SO4 gel electrolyte delivered high specific capacitance and energy density of 412 F g(-1) and 9.166 W h kg(-1), respectively, at 1.56 A g(-1). Subsequently, Na2MoO4 (sodium molybdate) added PVA/H2SO4 gel electrolyte was also prepared and applied for SSEDLC, to improve the performance. Surprisingly, 57.2% of specific capacitance (648 F g(-1)) and of energy density (14.4 Wh kg(-1)) was increased while introducing Na2MoO4 as the redox mediator in PVA/H2SO4 gel electrolyte. This improved performance is owed to the redox reaction between Mo(VI)/Mo(V) and Mo(VI)/Mo(IV) redox couples in Na2MoO4/PVA/H2SO4 gel electrolyte. Similarly, the fabricated device shows the excellent capacitance retention of 93% for over 3000 cycles. The present work suggests that the Na2MoO4 added PVA/H2SO4 gel is a potential electrolyte to improve the performance instead of pristine PVA/H2SO4 gel electrolyte. Based on the overall performance, it is strongly believed that the combination of tamarind fruit shell derived activated carbon and Na2MoO4/PVA/H2SO4 gel electrolyte is more attractive in the near future for high performance SSEDLCs.

Biredox ionic liquids: new opportunities toward high performance supercapacitors.

PubMed

Bodin, C; Mourad, E; Zigah, D; Le Vot, S; Freunberger, S A; Favier, F; Fontaine, O

2018-01-01

Nowadays commercial supercapacitors are based on purely capacitive storage at the porous carbons that are used for the electrodes. However, the limits that capacitive storage imposes on energy density calls to investigate new materials to improve the capacitance of the device. This new type of electrodes (e.g., RuO 2 , MnO 2 …) involves pseudo-capacitive faradaic redox processes with the solid material. Ion exchange with solid materials is, however, much slower than the adsorption process in capacitive storage and inevitably leads to significant loss of power. Faradaic process in the liquid state, in contrast can be similarly fast as capacitive processes due to the fast ion transport. Designing new devices with liquid like dynamics and improved specific capacitance is challenging. We present a new approach to increase the specific capacitance using biredox ionic liquids, where redox moieties are tethered to the electrolyte ions, allowing high redox concentrations and significant pseudo-capacitive storage in the liquid state. Anions and cations are functionalized with anthraquinone (AQ) and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) moieties, respectively. Glassy carbon, carbon-onion, and commercial activated carbon electrodes that exhibit different double layer structures and thus different diffusion dynamics were used to simultaneously study the electrochemical response of biredox ionic liquids at the positive and negative electrode.

Biofilm formation and potential for iron cycling in serpentinization-influenced groundwater of the Zambales and Coast Range ophiolites.

PubMed

Meyer-Dombard, D'Arcy R; Casar, Caitlin P; Simon, Alexander G; Cardace, Dawn; Schrenk, Matthew O; Arcilla, Carlo A

2018-05-01

Terrestrial serpentinizing systems harbor microbial subsurface life. Passive or active microbially mediated iron transformations at alkaline conditions in deep biosphere serpentinizing ecosystems are understudied. We explore these processes in the Zambales (Philippines) and Coast Range (CA, USA) ophiolites, and associated surface ecosystems by probing the relevance of samples acquired at the surface to in situ, subsurface ecosystems, and the nature of microbe-mineral associations in the subsurface. In this pilot study, we use microcosm experiments and batch culturing directed at iron redox transformations to confirm thermodynamically based predictions that iron transformations may be important in subsurface serpentinizing ecosystems. Biofilms formed on rock cores from the Zambales ophiolite on surface and in-pit associations, confirming that organisms from serpentinizing systems can form biofilms in subsurface environments. Analysis by XPS and FTIR confirmed that enrichment culturing utilizing ferric iron growth substrates produced reduced, magnetic solids containing siderite, spinels, and FeO minerals. Microcosms and enrichment cultures supported organisms whose near relatives participate in iron redox transformations. Further, a potential 'principal' microbial community common to solid samples in serpentinizing systems was identified. These results indicate collectively that iron redox transformations should be more thoroughly and universally considered when assessing the function of terrestrial subsurface ecosystems driven by serpentinization.

Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

PubMed

Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

2017-01-18

As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

A low cost, all-organic Na-ion Battery Based on Polymeric Cathode and Anode

PubMed Central

Deng, Wenwen; Liang, Xinmiao; Wu, Xianyong; Qian, Jiangfeng; Cao, Yuliang; Ai, Xinping; Feng, Jiwen; Yang, Hanxi

2013-01-01

Current battery systems have severe cost and resource restrictions, difficultly to meet the large scale electric storage applications. Herein, we report an all-organic Na-ion battery using p-dopable polytriphenylamine as cathode and n-type redox-active poly(anthraquinonyl sulphide) as anode, excluding the use of transition-metals as in conventional electrochemical batteries. Such a Na-ion battery can work well with a voltage output of 1.8 V and realize a considerable specific energy of 92 Wh kg−1. Due to the structural flexibility and stability of the redox-active polymers, this battery has a superior rate capability with 60% capacity released at a very high rate of 16 C (3200 mA g−1) and also exhibit an excellent cycling stability with 85% capacity retention after 500 cycles at 8 C rate. Most significantly, this type of all-organic batteries could be made from renewable and earth-abundant materials, thus offering a new possibility for widespread energy storage applications. PMID:24036973

Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

PubMed

Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min

2018-05-01

During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

NASA Astrophysics Data System (ADS)

Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

2005-05-01

The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

Magnetic Resonance Imaging of Polymeric Drug Delivery Systems in Breast Cancer Solid Tumors

DTIC Science & Technology

2007-07-01

isothiocyanatobenzyl-1,4,7,10 tetraazacyclododecane-1,4,7,10 tetraacetic acid (p-SCN-Bz-DOTA) in dry dimethylsulfoxide ( DMSO ). The p-SCN-Bz-DOTA was reacted at 1.2...APMA- benzyl-DOTA, and MA-GFLG-dox in predetermined molar compositions (Appendix 3, Table 1). All polymerization were carried out in acetone / DMSO ...using AIBN as the initiator. The ratio of monomers: initiator: solvent in the feed were kept constant at 12.5: 0.6: 86.9 (weight %), respectively

IMPACT OF REDOX DISEQUILIBRIA ON CONTAMINANT TRANSPORT AND REMEDIATION IN SUBSURFACE SYSTEMS

EPA Science Inventory

Partitioning to mineral surfaces exerts significant control on inorganic contaminant transport in subsurface systems. Remedial technologies for in-situ treatment of subsurface contamination are frequently designed to optimize the efficiency of contaminant partitioning to solid s...

Synthesis of long Prebiotic Oligomers on Mineral Surfaces

NASA Technical Reports Server (NTRS)

Ferris, James P.; Hill, Aubrey R., Jr.; Liu, Rihe; Orgel, Leslie E.

1996-01-01

Most theories of the origin of biological organization assume that polymers with lengths in the range of 30-60 monomers are needed to make a genetic system viable. But it has not proved possible to synthesize plausibly prebiotic polymers this long by condensation in aqueous solution, because hydrolysis competes with polymerization. The potential of mineral surfaces to facilitate prebiotic polymerization was pointed out long ago. Here we describe a system that models prebiotic polymerization by the oligomerization of activated monomers -both nucleotides and amino acids. We find that whereas the reactions in solution produce only short oligomers (the longest typically being a 10-mer), the presence of mineral surfaces (montmorillonite for nucleotides, illite and hydroxylapatite for amino adds) induces the formation of oligomers up to 55 monomers long. These are formed by successive "feedings" with the monomers; polymerization takes place on the mineral surfaces in a manner akin to solid-phase synthesis of biopolymers.

Monodisperse, polymeric microspheres produced by irradiation of slowly thawing frozen drops

NASA Technical Reports Server (NTRS)

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

1991-01-01

Monodisperse, polymeric microspheres are formed by injecting uniformly shaped droplets of radiation polymerizable monomers, preferably a biocompatible monomer, having covalent binding sites such as hydroxyethylmethacrylate, into a zone, impressing a like charge on the droplet so that they mutually repel each other, spheroidizing the droplets within the zone and collecting the droplets in a pool of cryogenic liquid. As the droplets enter the liquid, they freeze into solid, glassy microspheres, which vaporizes a portion of the cryogenic liquid to form a layer. The like-charged microspheres, suspended within the layer, move to the edge of the vessel holding the pool, are discharged, fall and are collected. The collected microspheres are irradiated while frozen in the cryogenic liquid to form latent free radicals. The frozen microspheres are then slowly thawed to activate the free radicals which polymerize the monomer to form evenly-sized, evenly-shaped, monodisperse polymeric microspheres.

Polymeric mechanical amplifiers of immune cytokine-mediated apoptosis

NASA Astrophysics Data System (ADS)

Mitchell, Michael J.; Webster, Jamie; Chung, Amanda; Guimarães, Pedro P. G.; Khan, Omar F.; Langer, Robert

2017-03-01

Physical forces affect tumour growth, progression and metastasis. Here, we develop polymeric mechanical amplifiers that exploit in vitro and in vivo physical forces to increase immune cytokine-mediated tumour cell apoptosis. Mechanical amplifiers, consisting of biodegradable polymeric particles tethered to the tumour cell surface via polyethylene glycol linkers, increase the apoptotic effect of an immune cytokine on tumour cells under fluid shear exposure by as much as 50% compared with treatment under static conditions. We show that targeted polymeric particles delivered to tumour cells in vivo amplify the apoptotic effect of a subsequent treatment of immune cytokine, reduce circulating tumour cells in blood and overall tumour cell burden by over 90% and reduce solid tumour growth in combination with the antioxidant resveratrol. The work introduces a potentially new application for a broad range of micro- and nanoparticles to maximize receptor-mediated signalling and function in the presence of physical forces.

40 CFR 63.10906 - What definitions apply to this subpart?

Code of Federal Regulations, 2010 CFR

2010-07-01

..., plenums, and fans. Chlorinated plastics means solid polymeric materials that contain chlorine in the polymer chain, such as polyvinyl chloride (PVC) and PVC copolymers. Control device means the air pollution...

40 CFR 63.10906 - What definitions apply to this subpart?

Code of Federal Regulations, 2011 CFR

2011-07-01

..., plenums, and fans. Chlorinated plastics means solid polymeric materials that contain chlorine in the polymer chain, such as polyvinyl chloride (PVC) and PVC copolymers. Control device means the air pollution...

Polymer-based protein engineering grown ferrocene-containing redox polymers improve current generation in an enzymatic biofuel cell.

PubMed

Campbell, Alan S; Murata, Hironobu; Carmali, Sheiliza; Matyjaszewski, Krzysztof; Islam, Mohammad F; Russell, Alan J

2016-12-15

Enzymatic biofuel cells (EBFCs) are capable of generating electricity from physiologically present fuels making them promising power sources for the future of implantable devices. The potential application of such systems is limited, however, by inefficient current generation. Polymer-based protein engineering (PBPE) offers a unique method to tailor enzyme function through tunable modification of the enzyme surface with functional polymers. In this study, we report on the modification of glucose oxidase (GOX) with ferrocene-containing redox polymers to increase current generation efficiency in an enzyme-modified anode. Poly(N-(3-dimethyl(ferrocenyl)methylammonium bromide)propyl acrylamide) (pFcAc) was grown from covalently attached, water-soluble initiator molecules on the surface of GOX in a "grafting-from" approach using atom transfer radical polymerization (ATRP). The covalently-coupled ferrocene-containing polymers on the enzyme surface promoted the effective "wiring" of the GOX active site to an external electrode. The resulting GOX-pFcAc conjugates generated over an order of magnitude increase in current generation efficiency and a 4-fold increase in maximum EBFC power density (≈1.7µWcm(-2)) with similar open circuit voltage (0.27V) compared to native GOX when physically adsorbed onto paddle-shaped electrodes made up of electrospun polyacrylonitrile fibers coated with gold nanoparticles and multi-wall carbon nanotubes. The formation of electroactive enzyme-redox polymer conjugates using PBPE represents a powerful new tool for the improvement of mediated enzyme-based bioelectronics without the need for free redox mediators or anode/cathode compartmentalization. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

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

Jin, XF; Zhao, X; Huang, K

A high-fidelity two-dimensional axial symmetrical multi-physics model is described in this paper as an effort to simulate the cycle performance of a recently discovered solid oxide metal-air redox battery (SOMARB). The model collectively considers mass transport, charge transfer and chemical redox cycle kinetics occurring across the components of the battery, and is validated by experimental data obtained from independent research. In particular, the redox kinetics at the energy storage unit is well represented by Johnson-Mehl-Avrami-Kolmogorov (JIVIAK) and Shrinking Core models. The results explicitly show that the reduction of Fe3O4 during the charging cycle limits the overall performance. Distributions of electrodemore » potential, overpotential, Nernst potential, and H-2/H2O-concentration across various components of the battery are also systematically investigated. (C) 2015 Elsevier B.V. All rights reserved.« less

Effect of 457 nm diode-pumped solid state laser on the polymerization composite resins: microhardness, cross-link density, and polymerization shrinkage.

PubMed

Son, Sung-Ae; Park, Jeong-Kil; Jung, Kyoung-Hwa; Ko, Ching-Chang; Jeong, Chang-Mo; Kwon, Yong Hoon

2015-01-01

The purpose of the present study was to test the usefulness of 457 nm diode-pumped solid state (DPSS) laser as a light source to cure composite resins. Five different composite resins were light cured using three different light-curing units (LCUs): a DPSS 457 nm laser (LAS), a light-emitting diode (LED), and quartz-tungsten-halogen (QTH) units. The light intensity of LAS was 560 mW/cm(2), whereas LED and QTH LCUs was ∼900 mW/cm(2). The degree of polymerization was tested by evaluating microhardness, cross-link density, and polymerization shrinkage. Before water immersion, the microhardness of laser-treated specimens ranged from 40.8 to 84.7 HV and from 31.7 to 79.0 HV on the top and bottom surfaces, respectively, and these values were 3.3-23.2% and 2.9-31.1% lower than the highest microhardness obtained using LED or QTH LCUs. Also, laser-treated specimens had lower top and bottom microhardnesses than the other LCUs treated specimens by 2.4-19.4% and 1.4-27.8%, respectively. After ethanol immersion for 24 h, the microhardness of laser-treated specimens ranged from 20.3 to 63.2 HV on top and bottom surfaces, but from 24.9 to 71.5 HV when specimens were cured using the other LCUs. Polymerization shrinkage was 9.8-14.7 μm for laser-treated specimens, and these were significantly similar or lower (10.2-16.0 μm) than those obtained using the other LCUs. The results may suggest that the 457 nm DPSS laser can be used as a light source for light-curing dental resin composites.

A microtitre-based method for measuring the haem polymerization inhibitory activity (HPIA) of antimalarial drugs.

PubMed

Basilico, N; Pagani, E; Monti, D; Olliaro, P; Taramelli, D

1998-07-01

The malaria parasite metabolizes haemoglobin and detoxifies the resulting haem by polymerizing it to form haemozoin (malaria pigment). A polymer identical to haemozoin, beta-haematin, can be obtained in vitro from haematin at acidic pH. Quinoline-containing anti-malarials (e.g. chloroquine) inhibit the formation of either polymer. Haem polymerization is an essential and unique pharmacological target. To identify molecules with haem polymerization inhibitory activity (HPIA) and quantify their potency, we developed a simple, inexpensive, quantitative in-vitro spectrophotometric microassay of haem polymerization. The assay uses 96-well U-bottomed polystyrene microplates and requires 24 h and a microplate reader. The relative amounts of polymerized and unpolymerized haematin are determined, based on solubility in DMSO, by measuring absorbance at 405 nm in the presence of test compounds as compared with untreated controls. The final product (a solid precipitate of polymerized haematin) was validated using infrared spectroscopy and the assay proved reproducible; in this assay, activity could be partly predicted based on the compound's chemical structure. Both water-soluble and water-insoluble compounds can be quantified by this method. Although the throughput of this assay is lower than that of radiometric methods, the assay is easier to set up and cheaper, and avoids the problems related to radioactive waste disposal.

Kinetics of waterborne fluoropolymers prepared by one-step semi-continuous emulsion polymerization of chlorotrifluoroethylene, vinyl acetate, butyl acrylate and Veova 10

NASA Astrophysics Data System (ADS)

Liu, H. Z.; Wang, M. H.; Wang, Z. F.; Bian, J. M.

2018-01-01

Due to using gaseous fluorine monomer with toxicity, waterborne fluoropolymers are synthesized by semi-continuous high-pressure emulsion polymerization method which differs from free-pressure emulsion polymerization. To dates, the research on preparing process and kinetics for high-pressure emulsion polymerization is reported relatively less, which hinders researchers from understanding of mechanisms for monomer-fluorinated emulsion polymerization. The paper also provides a new method by element auxiliary analysis to calculate kinetics parameters of high-pressure emulsion polymerization. Based on aforementioned consideration, waterborne fluoropolymers were prepared by copolymerization of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc), butyl acrylate (BA) and vinyl ester of versatic acid (Veova 10) using potassium persulfate as initiator and mixed surfactants. The kinetics of emulsion polymerization of waterborne fluoropolymers was then investigated. Effects of emulsifier concentration, initiator concentration, and polymerization temperature on polymerization rate (Rp) were evaluated, and relationship was described as Rp∝[I]0.10 and Rp∝[E]0.12. The apparent activation energy was determined to be 33.61 kJ·mol-1. Moreover, the relative conversion rate of CTFE with the other monomers was observed, and results indicated that CTFE monomer more uniformly copolymerized with the other monomers. The resulting emulsion properties and pressure change in an autoclave were evaluated at different stirring rates. The initial reaction time, defined as the beginning time of dropwise addition, was determined by the change in solid content and particle size of emulsion.

Fully-Polymeric pH Sensor Realized by Means of a Single-Step Soft Embossing Technique

PubMed Central

Fanzio, Paola; Chang, Chi-Tung; Skolimowski, Maciej; Tanzi, Simone; Sasso, Luigi

2017-01-01

We present here an electrochemical sensor microsystem for the monitoring of pH. The all-polymeric device is comprised of a cyclic olefin copolymer substrate, a 200 nm-thin patterned layer of conductive polymer (PEDOT), and a 70 nm electropolymerized layer of a pH sensitive conductive polymer (polyaniline). The patterning of the fluidic (microfluidic channels) and conductive (wiring and electrodes) functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH. PMID:28531106

Chemical sensors from the cooperative actuation of multistep electrochemical molecular machines of polypyrrole: potentiostatic study. Trying to replicate muscle’s fatigue signals

NASA Astrophysics Data System (ADS)

Beaumont, Samuel; Otero, Toribio F.

2018-07-01

Polypyrrole film electrodes are constituted by multielectronic electrochemical molecular machines (every polymeric molecule) counterions and water, mimicking the intracellular matrix of muscular cells. The influence of the electrolyte concentration on the reversible oxidation/reduction of polypyrrole films was studied in NaCl aqueous solutions by consecutive square potential waves. The consumed redox charge and the consumed electrical energy change as a function of the concentration. That means that the extension (the consumed charge) of the reaction involving conformational, or allosteric, movements of the reacting polymeric chains (molecular machines) responds to (senses) the chemical energy of the reaction ambient. A theoretical description of the attained empirical results is presented getting the sensing equations and the concomitant sensitivities. Those results could indicate the origin and nature of the neural signals sent to the brain from biological haptic muscles working by cooperative actuation of the actin-myosin molecular machines driven by chemical reactions and sensing, simultaneously, the fatigue state of the muscle.

Fully-Polymeric pH Sensor Realized by Means of a Single-Step Soft Embossing Technique.

PubMed

Fanzio, Paola; Chang, Chi-Tung; Skolimowski, Maciej; Tanzi, Simone; Sasso, Luigi

2017-05-20

We present here an electrochemical sensor microsystem for the monitoring of pH. The all-polymeric device is comprised of a cyclic olefin copolymer substrate, a 200 nm-thin patterned layer of conductive polymer (PEDOT), and a 70 nm electropolymerized layer of a pH sensitive conductive polymer (polyaniline). The patterning of the fluidic (microfluidic channels) and conductive (wiring and electrodes) functional elements was achieved with a single soft PDMS mold via a single embossing step process. A post-processing treatment with ethylene glycol assured the functional enhancement of the electrodes, as demonstrated via an electrical and electrochemical characterization. A surface modification of the electrodes was carried out, based on voltammetric electropolymerization, to obtain a thin layer of polyaniline. The mechanism for pH sensing is based on the redox reactions of the polyaniline layer caused by protonation. The sensing performance of the microsystem was finally validated by monitoring its potentiometric response upon exposure to a relevant range of pH.

Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

PubMed

Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

2015-03-14

The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

Geometric confinement influences cellular mechanical properties I -- adhesion area dependence.

PubMed

Su, Judith; Jiang, Xingyu; Welsch, Roy; Whitesides, George M; So, Peter T C

2007-06-01

Interactions between the cell and the extracellular matrix regulate a variety of cellular properties and functions, including cellular rheology. In the present study of cellular adhesion, area was controlled by confining NIH 3T3 fibroblast cells to circular micropatterned islands of defined size. The shear moduli of cells adhering to islands of well defined geometry, as measured by magnetic microrheometry, was found to have a significantly lower variance than those of cells allowed to spread on unpatterned surfaces. We observe that the area of cellular adhesion influences shear modulus. Rheological measurements further indicate that cellular shear modulus is a biphasic function of cellular adhesion area with stiffness decreasing to a minimum value for intermediate areas of adhesion, and then increasing for cells on larger patterns. We propose a simple hypothesis: that the area of adhesion affects cellular rheological properties by regulating the structure of the actin cytoskeleton. To test this hypothesis, we quantified the volume fraction of polymerized actin in the cytosol by staining with fluorescent phalloidin and imaging using quantitative 3D microscopy. The polymerized actin volume fraction exhibited a similar biphasic dependence on adhesion area. Within the limits of our simplifying hypothesis, our experimental results permit an evaluation of the ability of established, micromechanical models to predict the cellular shear modulus based on polymerized actin volume fraction. We investigated the "tensegrity", "cellular-solids", and "biopolymer physics" models that have, respectively, a linear, quadratic, and 5/2 dependence on polymerized actin volume fraction. All three models predict that a biphasic trend in polymerized actin volume fraction as a function of adhesion area will result in a biphasic behavior in shear modulus. Our data favors a higher-order dependence on polymerized actin volume fraction. Increasingly better experimental agreement is observed for the tensegrity, the cellular solids, and the biopolymer models respectively. Alternatively if we postulate the existence of a critical actin volume fraction below which the shear modulus vanishes, the experimental data can be equivalently described by a model with an almost linear dependence on polymerized actin volume fraction; this observation supports a tensegrity model with a critical actin volume fraction.

New strategy and easy fabrication of solid-state supercapacitor based on polypyrrole and nitrile rubber.

PubMed

Lee, Sangyool; Lee, Youngkwan; Cho, Mi-Suk; Nam, Jae-Do

2008-09-01

Solid state redox supercapacitors were fabricated using a solid polymer electrolyte, nitrile butadiene rubber (NBR)-KCI and chemically deposited polypyrrole (PPy) as the conducting polymer electrodes on both surfaces of a NBR film. The optimal conditions for the preparation of the PPy/NBR electrode were confirmed as functions of the uptake of pyrrole monomer into the NBR matrix as well as the immersion time in an oxidant solution. The morphology of the PPy-NBR-KCI capacitor was observed using scanning electron microscopy. The performance of the capacitors was characterized using a galvanostatic charge-discharge technique.

Enabling catalytic oxidation of Li2O2 at the liquid-solid interface: the evolution of an aprotic Li-O2 battery.

PubMed

Feng, Ningning; He, Ping; Zhou, Haoshen

2015-02-01

We show that by using a suitable soluble redox mediator, the charging overpotential can be reduced and the round-trip efficiency can be improved in an aprotic Li-O2 battery. Not only do we explore a new redox couple, 10-methyl-10H-phenothiazine, as a soluble catalyst that improves the electrochemical performance, but we also propose possible challenges that need to be overcome for the future improvement of aprotic Li-O2 batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-Pot Anchoring of Pd Nanoparticles on Nitrogen-Doped Carbon through Dopamine Self-Polymerization and Activity in the Electrocatalytic Methanol Oxidation Reaction.

PubMed

Li, Xin; Niu, Xiangheng; Zhang, Wenchi; He, Yanfang; Pan, Jianming; Yan, Yongsheng; Qiu, Fengxian

2017-03-09

Exploration of advanced electrocatalysts to promote the sluggish methanol oxidation reaction (MOR) is of vital importance for developing high efficiency and low-cost direct methanol fuel cells. Highly dispersed palladium nanoparticles (Pd NPs) anchored on a nitrogen-doped carbon support were fabricated using a facile one-pot dopamine self-polymerization mediated redox strategy, in which dopamine not only acted as a moderate reductant to induce the formation of Pd NPs during self-polymerization but was also the precursor of the nitrogen-doped carbon support for Pd. The synthesized hybrid features the following characteristics: 1) High dispersity of Pd NPs, which exposed a high abundance of active surfaces and sites for heterogeneous electrocatalysis; 2) metal-support interactions, which may affect the surface chemistry and electron distribution of active Pd NPs; 3) the Pd NPs were partially imbedded or encapsulated into the support, thus reducing the possible agglomeration of Pd NPs during cyclic measurements. The electrocatalyst with such favorable features provided higher mass activity (2.2 times that of commercial Pd/C) and better durability (reduced loss of activity during simulated frequent startup-shutdown operations) for the MOR in alkaline media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2013-01-01

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

Versatile peroxidase as a valuable tool for generating new biomolecules by homogeneous and heterogeneous cross-linking.

PubMed

Salvachúa, Davinia; Prieto, Alicia; Mattinen, Maija-Liisa; Tamminen, Tarja; Liitiä, Tiina; Lille, Martina; Willför, Stefan; Martínez, Angel T; Martínez, María Jesús; Faulds, Craig B

2013-05-10

The modification and generation of new biomolecules intended to give higher molecular-mass species for biotechnological purposes, can be achieved by enzymatic cross-linking. The versatile peroxidase (VP) from Pleurotus eryngii is a high redox-potential enzyme with oxidative activity on a wide variety of substrates. In this study, VP was successfully used to catalyze the polymerization of low molecular mass compounds, such as lignans and peptides, as well as larger macromolecules, such as protein and complex polysaccharides. Different analytical, spectroscopic, and rheological techniques were used to determine structural changes and/or variations of the physicochemical properties of the reaction products. The lignans secoisolariciresinol and hydroxymatairesinol were condensed by VP forming up to 8 unit polymers in the presence of organic co-solvents and Mn(2+). Moreover, 11 unit of the peptides YIGSR and VYV were homogeneously cross-linked. The heterogeneous cross-linking of one unit of the peptide YIGSR and several lignan units was also achieved. VP could also induce gelation of feruloylated arabinoxylan and the polymerization of β-casein. These results demonstrate the efficacy of VP to catalyze homo- and hetero-condensation reactions, and reveal its potential exploitation for polymerizing different types of compounds. Copyright © 2013 Elsevier Inc. All rights reserved.

Melt-processed polymeric cellular dosage forms for immediate drug release.

PubMed

Blaesi, Aron H; Saka, Nannaji

2015-12-28

The present immediate-release solid dosage forms, such as the oral tablets and capsules, comprise granular matrices. While effective in releasing the drug rapidly, they are fraught with difficulties inherent in processing particulate matter. By contrast, liquid-based processes would be far more predictable; but the standard cast microstructures are unsuited for immediate-release because they resist fluid percolation and penetration. In this article, we introduce cellular dosage forms that can be readily prepared from polymeric melts by incorporating the nucleation, growth, and coalescence of microscopic gas bubbles in a molding process. We show that the cell topology and formulation of such cellular structures can be engineered to reduce the length-scale of the mass-transfer step, which determines the time of drug release, from as large as the dosage form itself to as small as the thickness of the cell wall. This allows the cellular dosage forms to achieve drug release rates over an order of magnitude faster compared with those of cast matrices, spanning the entire spectrum of immediate-release and beyond. The melt-processed polymeric cellular dosage forms enable predictive design of immediate-release solid dosage forms by tailoring microstructures, and could be manufactured efficiently in a single step.

Preparation of sulfonated graphene/polypyrrole solid-phase microextraction coating by in situ electrochemical polymerization for analysis of trace terpenes.

PubMed

Zhang, Chengjiang; Zhang, Zhuomin; Li, Gongke

2014-06-13

In this study, a novel sulfonated graphene/polypyrrole (SG/PPy) solid-phase microextraction (SPME) coating was prepared and fabricated on a stainless-steel wire by a one-step in situ electrochemical polymerization method. Crucial preparation conditions were optimized as polymerization time of 15min and SG doping amount of 1.5mg/mL. SG/PPy coating showed excellent thermal stability and mechanical durability with a long lifespan of more than 200 stable replicate extractions. SG/PPy coating demonstrated higher extraction selectivity and capacity to volatile terpenes than commonly-used commercial coatings. Finally, SG/PPy coating was practically applied for the analysis of volatile components from star anise and fennel samples. The majority of volatile components identified were terpenes, which suggested the ultra-high extraction selectivity of SG/PPy coating to terpenes during real analytical projects. Four typical volatile terpenes were further quantified to be 0.2-27.4μg/g from star anise samples with good recoveries of 76.4-97.8% and 0.1-1.6μg/g from fennel samples with good recoveries of 80.0-93.1%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Formulation and characterization of polymeric films containing combinations of antiretrovirals (ARVs) for HIV prevention.

PubMed

Akil, Ayman; Agashe, Hrushikesh; Dezzutti, Charlene S; Moncla, Bernard J; Hillier, Sharon L; Devlin, Brid; Shi, Yuan; Uranker, Kevin; Rohan, Lisa Cencia

2015-02-01

To develop polymeric films containing dual combinations of anti-HIV drug candidate tenofovir, maraviroc and dapivirine for vaginal application as topical microbicides. A solvent casting method was used to manufacture the films. Solid phase solubility was used to identify potential polymers for use in the film formulation. Physical and chemical properties (such as water content, puncture strength and in vitro release) and product stability were determined. The bioactivity of the film products against HIV was assessed using the TZM-bl assay and a cervical explant model. Polymers identified from the solid phase solubility study maintained tenofovir and maraviroc in an amorphous state and prevented drug crystallization. Three combination film products were developed using cellulose polymers and polyvinyl alcohol. The residual water content in all films was <10% (w/w). All films delivered the active agents with release of >50% of film drug content within 30 min. Stability testing confirmed that the combination film products were stable for 12 months at ambient temperature and 6 months under stressed conditions. Antiviral activity was confirmed in TZM-bl and cervical explant models. Polymeric films can be used as a stable dosage form for the delivery of antiretroviral combinations as microbicides.

Technical Update: Johnson Space Center system using a solid electrolytic cell in a remote location to measure oxygen fugacities in CO/CO2 controlled-atmosphere furnaces

NASA Technical Reports Server (NTRS)

Jurewicz, A. J. G.; Williams, R. J.; Le, L.; Wagstaff, J.; Lofgren, G.; Lanier, A.; Carter, W.; Roshko, A.

1993-01-01

Details are given for the design and application of a (one atmosphere) redox-control system. This system differs from that given in NASA Technical Memorandum 58234 in that it uses a single solid-electrolytic cell in a remote location to measure the oxygen fugacities of multiple CO/CO2 controlled-atmosphere furnaces. This remote measurement extends the range of sample-furnace conditions that can be measured using a solid-electrolytic cell, and cuts costs by extending the life of the sensors and by minimizing the number of sensors in use. The system consists of a reference furnace and an exhaust-gas manifold. The reference furnace is designed according to the redox control system of NASA Technical Memorandum 58234, and any number of CO/CO2 controlled-atmosphere furnaces can be attached to the exhaust-gas manifold. Using the manifold, the exhaust gas from individual CO/CO2 controlled atmosphere furnaces can be diverted through the reference furnace, where a solid-electrolyte cell is used to read the ambient oxygen fugacity. The oxygen fugacity measured in the reference furnace can then be used to calculate the oxygen fugacity in the individual CO/CO2 controlled-atmosphere furnace. A BASIC computer program was developed to expedite this calculation.

USING MOLECULAR PROBES TO STUDY INTERFACIAL REDOX REACTION AT FE-BEARING SMECTITES

EPA Science Inventory

The interfacial electron transfer of clay-water systems has a wide range of significance in geochemical and biogeochernical environments. However the mechanism of interfacial electron transport is poorly understood. The electron transfer mechanism at the solid-water interfaces of...

NANOSTRUCTURED POROUS SILICON AND LUMINESCENT POLYSILOLES AS CHEMICAL SENSORS FOR CARCINOGENIC CHROMIUM(VI) AND ARSENIC(V)

EPA Science Inventory

The chief goal is to develop new selective solid state sensors for carcinogenic and toxic chromium(VI) and arsenic(V) in water based on redox quenching of the luminescence from nanostructured porous silicon and polysiloles.

Dry entrapment of enzymes by epoxy or polyester resins hardened on different solid supports.

PubMed

Barig, Susann; Funke, Andreas; Merseburg, Andrea; Schnitzlein, Klaus; Stahmann, K-Peter

2014-06-10

Embedding of enzymes was performed with epoxy or polyester resin by mixing in a dried enzyme preparation before polymerization was started. This fast and low-cost immobilization method produced enzymatically active layers on different solid supports. As model enzymes the well-characterized Thermomyces lanuginosus lipase and a new threonine aldolase from Ashbya gossypii were used. It was shown that T. lanuginosus lipase recombinantly expressed in Aspergillus oryzae is a monomeric enzyme with a molecular mass of 34kDa, while A. gossypii threonine aldolase expressed in Escherichia coli is a pyridoxal-5'-phosphate binding homotetramer with a mass of 180kDa. The enzymes were used freeze dried, in four different preparations: freely diffusing, adsorbed on octyl sepharose, as well as cross-linked enzyme aggregates or as suspensions in organic solvent. They were mixed with standard two-component resins and prepared as layers on solid supports made of different materials e.g. metal, glass, polyester. Polymerization led to encapsulated enzyme preparations showing activities comparable to literature values. Copyright © 2014 Elsevier Inc. All rights reserved.

Simple fabrication of solid phase microextraction fiber employing nitrogen-doped ordered mesoporous polymer by in situ polymerization.

PubMed

Zheng, Juan; Liang, Yeru; Liu, Shuqin; Jiang, Ruifen; Zhu, Fang; Wu, Dingcai; Ouyang, Gangfeng

2016-01-04

A combination of nitrogen-doped ordered mesoporous polymer (NOMP) and stainless steel wires led to highly sensitive, selective, and stable solid phase microextraction (SPME) fibers by in situ polymerization for the first time. The ordered structure of synthesized NOMP coating was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD), and microscopy analysis by scanning electron microscopy (SEM) confirmed a homogenous morphology of the NOMP-coated fiber. The NOMP-coated fiber was further applied for the extraction of organochlorine pesticides (OCPs) with direct-immersion solid-phase microextraction (DI-SPME) method followed by gas chromatography-mass spectrometry (GC-MS) quantification. Under the optimized conditions, low detection limits (0.023-0.77 ng L(-1)), a wide linear range (9-1500 ng L(-1)), good repeatability (3.5-8.1%, n=6) and excellent reproducibility (1.5-8.3%, n=3) were achieved. Moreover, the practical feasibility of the proposed method was evaluated by determining OCPs in environmental water samples with satisfactory recoveries. Copyright © 2015 Elsevier B.V. All rights reserved.

Collapse of surface nanobubbles.

PubMed

Chan, Chon U; Chen, Longquan; Arora, Manish; Ohl, Claus-Dieter

2015-03-20

Surface attached nanobubbles populate surfaces submerged in water. These nanobubbles have a much larger contact angle and longer lifetime than predicted by classical theory. Moreover, it is difficult to distinguish them from hydrophobic droplets, e.g., polymeric contamination, using standard atomic force microscopy. Here, we report fast dynamics of a three phase contact line moving over surface nanobubbles, polymeric droplets, and hydrophobic particles. The dynamics is distinct: across polymeric droplets the contact line quickly jumps and hydrophobic particles pin the contact line, while surface nanobubbles rapidly shrink once merging with the contact line, suggesting a method to differentiate nanoscopic gaseous, liquid, and solid structures. Although the collapse process of surface nanobubbles occurs within a few milliseconds, we show that it is dominated by microscopic dynamics rather than bulk hydrodynamics.

High temperature hydrothermal vent fluids in Yellowstone Lake: Observations and insights from in-situ pH and redox measurements

NASA Astrophysics Data System (ADS)

Tan, Chunyang; Cino, Christie D.; Ding, Kang; Seyfried, William E.

2017-09-01

ROV investigation of hydrothermal fluids issuing from vents on the floor of Yellowstone lake revealed temperatures in excess of 170 °C - the highest temperature yet reported for vent fluids within Yellowstone National Park (YNP). The study site is east of Stevenson Island at depth of approximately 100-125 m. In-situ pH and redox measurements of vent fluids were made using solid state sensors designed to sustain the elevated temperatures and pressures. YSZ membrane electrode with Ag/Ag2O internal element and internal pressure balanced Ag/AgCl reference electrode were used to measure pH, while a platinum electrode provided redox constraints. Lab verification of the pH sensor confirmed excellent agreement with Nernst law predictions, especially at temperatures in excess of 120 °C. In-situ pH values of between 4.2 and 4.5 were measured for the vent fluids at temperatures of 120 to 150 °C. The slightly acidic vent fluids are likely caused by CO2 enrichment in association with magmatic degassing effects that occur throughout YNP. This is consistent with results of simple model calculations and direct observation of CO2 bubbles in the immediate vicinity of the lake floor vents. Simultaneous redox measurements indicated moderate to highly reducing conditions (- 0.2 to - 0.3 V). As typical of measurements of this kind, internal and external redox disequilibria likely preclude unambiguous determination of redox controlling reactions. Redox disequilibria, however, can be expected to drive microbial metabolism and diversity in the near vent environment. Thus, the combination of in-situ pH and redox sensor deployments may ultimately provide the requisite framework to better understand the microbiology of the newly discovered hot vents on Yellowstone lake floor.

High-capacity electrode materials for rechargeable lithium batteries: Li3NbO4-based system with cation-disordered rocksalt structure.

PubMed

Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu; Shiiba, Hiromasa; Ogawa, Masahiro; Nakayama, Keisuke; Ohta, Toshiaki; Endo, Daisuke; Ozaki, Tetsuya; Inamasu, Tokuo; Sato, Kei; Komaba, Shinichi

2015-06-23

Rechargeable lithium batteries have rapidly risen to prominence as fundamental devices for green and sustainable energy development. Lithium batteries are now used as power sources for electric vehicles. However, materials innovations are still needed to satisfy the growing demand for increasing energy density of lithium batteries. In the past decade, lithium-excess compounds, Li2MeO3 (Me = Mn(4+), Ru(4+), etc.), have been extensively studied as high-capacity positive electrode materials. Although the origin as the high reversible capacity has been a debatable subject for a long time, recently it has been confirmed that charge compensation is partly achieved by solid-state redox of nonmetal anions (i.e., oxide ions), coupled with solid-state redox of transition metals, which is the basic theory used for classic lithium insertion materials, such as LiMeO2 (Me = Co(3+), Ni(3+), etc.). Herein, as a compound with further excess lithium contents, a cation-ordered rocksalt phase with lithium and pentavalent niobium ions, Li3NbO4, is first examined as the host structure of a new series of high-capacity positive electrode materials for rechargeable lithium batteries. Approximately 300 mAh ⋅ g(-1) of high-reversible capacity at 50 °C is experimentally observed, which partly originates from charge compensation by solid-state redox of oxide ions. It is proposed that such a charge compensation process by oxide ions is effectively stabilized by the presence of electrochemically inactive niobium ions. These results will contribute to the development of a new class of high-capacity electrode materials, potentially with further lithium enrichment (and fewer transition metals) in the close-packed framework structure with oxide ions.

In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

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

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

2016-11-07

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy.more » SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquife

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

Campbell, K M; K Kukkadapu, R K; Qafoku, N P

2012-05-23

Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology and redox processes that occur in these zones, several cores from a region of naturally occurring reducing conditions in a U-contaminated aquifer (Rifle, CO) were examined. Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for U and Fe content, oxidation state, and mineralogy; reduced S phases; and solid-phase organic C content using a suite of analyticalmore » and spectroscopic techniques on bulk sediment and size fractions. Solid-phase U concentrations were higher in the naturally reduced zone, with a high proportion of the U present as U(IV). The sediments were also elevated in reduced S phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and SO4 reduction has occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentrations of solid-phase organic C and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic C concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic C for maintaining reducing conditions and U immobilization.« less

Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

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

Campbell, Kate M.; Kukkadapu, Ravi K.; Qafoku, Nikolla

2012-05-23

Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology, and redox processes that occur in these zones, we examined several cores from a region of naturally occurring reducing conditions in a uranium-contaminated aquifer (Rifle, CO). Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for uranium and iron content, oxidation state, and mineralogy, reduced sulfur phases, and solid phase organic carbon content using a suite ofmore » analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase uranium concentrations were higher in the naturally reduced zone, with a high proportion of the uranium present as reduced U(IV). The sediments were also elevated in reduced sulfur phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and sulfate reduction occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentration of solid phase organic carbon and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic carbon concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic carbon for maintaining reducing conditions and uranium immobilization.« less

Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

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

Campbell, K. M.; Kukkadapu, R. K.; Qafoku, N. P.

2012-08-01

Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology and redox processes that occur in these zones, several cores from a region of naturally occurring reducing conditions in a U-contaminated aquifer (Rifle, CO) were examined. Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for U and Fe content, oxidation state, and mineralogy; reduced S phases; and solid-phase organic C content using a suite of analyticalmore » and spectroscopic techniques on bulk sediment and size fractions. Solid-phase U concentrations were higher in the naturally reduced zone, with a high proportion of the U present as U(IV). The sediments were also elevated in reduced S phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and SO 4 reduction has occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentrations of solid-phase organic C and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic C concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic C for maintaining reducing conditions and U immobilization.« less

Mechanistic insights for block copolymer morphologies: how do worms form vesicles?

PubMed

Blanazs, Adam; Madsen, Jeppe; Battaglia, Giuseppe; Ryan, Anthony J; Armes, Steven P

2011-10-19

Amphiphilic diblock copolymers composed of two covalently linked, chemically distinct chains can be considered to be biological mimics of cell membrane-forming lipid molecules, but with typically more than an order of magnitude increase in molecular weight. These macromolecular amphiphiles are known to form a wide range of nanostructures (spheres, worms, vesicles, etc.) in solvents that are selective for one of the blocks. However, such self-assembly is usually limited to dilute copolymer solutions (<1%), which is a significant disadvantage for potential commercial applications such as drug delivery and coatings. In principle, this problem can be circumvented by polymerization-induced block copolymer self-assembly. Here we detail the synthesis and subsequent in situ self-assembly of amphiphilic AB diblock copolymers in a one pot concentrated aqueous dispersion polymerization formulation. We show that spherical micelles, wormlike micelles, and vesicles can be predictably and efficiently obtained (within 2 h of polymerization, >99% monomer conversion) at relatively high solids in purely aqueous solution. Furthermore, careful monitoring of the in situ polymerization by transmission electron microscopy reveals various novel intermediate structures (including branched worms, partially coalesced worms, nascent bilayers, "octopi", "jellyfish", and finally pure vesicles) that provide important mechanistic insights regarding the evolution of the particle morphology during the sphere-to-worm and worm-to-vesicle transitions. This environmentally benign approach (which involves no toxic solvents, is conducted at relatively high solids, and requires no additional processing) is readily amenable to industrial scale-up, since it is based on commercially available starting materials.

Poly(ornithine-co-arginine-co-glycine-co-aspartic Acid): Preparation via NCA Polymerization and its Potential as a Polymeric Tumor-Penetrating Agent.

PubMed

Yu, Haiyang; Tang, Zhaohui; Zhang, Dawei; Song, Wantong; Duan, Taicheng; Gu, Jingkai; Chen, Xuesi

2015-06-01

A novel random copolypeptide of ornithine, arginine, glycine, and aspartic acid [Poly(ornithine-co-arginine-co-glycine-co-aspartic acid), Poly(O,R,G,D)] has been prepared through ring-opening polymerization of N-δ-carbobenzoxy-l-ornithine N-carboxyanhydride [Orn(Cbz)-NCA)], l-glycine N-carboxyanhydride (Gly-NCA) and β-benzyl l-aspartate N-carboxyanhydride [Asp(Bn)-NCA], following by subsequent deprotection and guanidization. The structure of Poly(O,R,G,D) was confirmed by nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). Low cytotoxicity of Poly(O,R,G,D) was confirmed from MTT assay. The Poly(O,R,G,D) contain some internal sequences of RXXR (X = O, R, G, or D) that could be proteolytically cleaved to expose the cryptic CendR element and bind to Neuropilin-1. This would lead to vascular and tissue permeabilization. Therefore trypsin-cleaved Poly(O,R,G,D) increase the vascular leakage of Evans blue from dermal microvessels at the injection site in vivo skin permeability assay. The intratumoral injection of the Poly(O,R,G,D) significantly enhanced the concentration of cisplatin-loaded nanoparticles in MCF-7 solid tumors. These results show that Poly(O,R,G,D) could increase the vascular leakage and tissue penetration of nanoparticles in a solid tumor and can be used as a potential polymeric tumor-penetrating agent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selenium content and oxidation states in fly ashes from western U.S. coals

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

Mattigod, Shas V; Quinn, Thomas R

2003-08-01

A selective extraction scheme was developed for the determination of the oxidation states of Se species in coal ashes. As compared to HF dissolution, extractions with 70% HC1O4 mobilized 90 to 100% of all compound and redox forms of Se from four of the five fly ashes. Extractions with 16M HNO3 did not mobilize all forms of Se as effectively as perchloric acid. Both oxidized forms of Se (IV and VI) were completely mobilized by 12M HCl extraction. Deionized-distilled water was not an effective extractant for mobilizing all compound forms of Se(IV) from fly ashes. Extraction data (70% HClO4, 16Mmore » HNO3, 12M HCl, DI water) indicated that the solid:solution ratio is a critical factor in Se extractability from fly ashes. Maximum extractions in all cases were obtained only with very high (1:500) solid:solution ratios. Extraction times from 1.5 to 25 hours did not significantly change Se extractability with any of the extractants except with 12M HCl, which required a minimum reaction time of 48 hours to attain maximum Se extractability. Reaction times shorter than the critical time and low solid:solution ratios significantly affected Se extractability from these fly ashes. Measurements of Se content and redox state in particle size and density fractions five western United States coal ashes indicated that typically, the Se content increased with decreasing particle size.. However, no consistent trend in Se concentration between the light and heavy density fractions of <2.7-m size fraction was observed. Selenium redox state data indicated that only Se(0) and Se(IV) forms were present in these five coal ashes. The presence of Se(IV) is significant since it is much more easily mobilized than the elemental form. Examination of fly ashes by the proposed scheme to determine Se redox species could permit better estimation of the Se content of plants grown on fly ash amended soils.« less

Persistent free radicals, heavy metals and PAHs generated in particulate soot emissions and residue ash from controlled combustion of common types of plastic.

PubMed

Valavanidis, Athanasios; Iliopoulos, Nikiforos; Gotsis, George; Fiotakis, Konstantinos

2008-08-15

The production and use of polymeric materials worldwide has reached levels of 150 million tonnes per year, and the majority of plastic materials are discarded in waste landfills where are burned generating toxic emissions. In the present study we conducted laboratory experiments for batch combustion/burning of commercial polymeric materials, simulating conditions of open fire combustion, with the purpose to analyze their emissions for chemical characteristics of toxicological importance. We used common types of plastic materials: poly(vinyl chloride) (PVC), low and high density poly(ethylene) (LDPE, HDPE), poly(styrene) (PS), poly(propylene) (PP) and poly(ethylene terephthalate) (PET). Samples of particulate smoke (soot) collected on filters and residue solid ash produced by controlled burning conditions at 600-750 degrees C are used for analysis. Emissions of particulate matter, persistent free radicals embedded in the carbonaceous polymeric matrix, heavy metals, other elements and PAHs were determined in both types of samples. Results showed that all plastics burned easily generating charred residue solid ash and black airborne particulate smoke. Persistent carbon- and oxygen-centered radicals, known for their toxic effects in inhalable airborne particles, were detected in both particulate smoke emissions and residue solid ash. Concentrations of heavy metals and other elements (determined by Inductively Coupled Plasma Emission Spectrometry, ICP, method) were measured in the airborne soot and residue ash. Toxic heavy metals, such as Pb, Zn, Cr, Ni, and Cd were relatively at were found at low concentrations. High concentrations were found for some lithophilic elements, such as Na, Ca, Mg, Si and Al in particulate soot and residue solid ash. Measurements of PAHs showed that low molecular weight PAHs were at higher concentrations in the airborne particulate soot than in the residue solid ash for all types of plastic. Higher-ringed PAHs were detected at higher concentrations in the residue solid ash of PVC as compared to those from the other types of plastic. The open-air burning of plastic material and their toxic emissions is of growing concern in areas of municipal solid waste where open-fires occur intentionally or accidentally. Another problem is building fires in which victims may suffer severe smoke inhalation from burning plastic materials in homes and in working places.

Fluorescence from polystyrene - Photochemical processes in polymeric systems, 7

NASA Technical Reports Server (NTRS)

Gupta, M. C.; Gupta, A.

1983-01-01

Results are presented for measurements of the fluorescence spectra of polystyrene in dilute solution and in pure solid films. It is determined that a major potential source of experimental error is the concurrent photooxidative degradation in air which may obscure fluorescence emission from monomeric sites in solid films at 25 C. The fluorescence spectra of oriented films are evaluated in terms of the monomer to excimer fluorescence intensity ratio and the excimer 'red shift'. The monomer to excimer fluorescence intensity ratio is determined to be significantly higher in fluid solution than in solid film.

Formation of Novel Polydiacetylenes: Synthesis of Poly(iodoethynyliododiacetylene) and Towards the Formation of Conjugated Ladder Polydiacetylenes

NASA Astrophysics Data System (ADS)

Freitag, Matthew

Polydiacetylenes (PDAs) are 1-dimensional polymers with a carbon-rich ene-yne backbone. Materials scientists are interested in PDAs because they are semiconductors, they have large multiphoton absorptions, and they can be prepared as ordered assemblies in the solid-state. Polydiacetylenes are formed from the topochemical 1,4-polymerization of a monomer unit made up of at least two sequential alkynes. This work describes attempts to form novel polydiacetylenes from several higher order polyyne monomers, as well as efforts to alter the morphology of known polydiacetylenes into thin films. The first project described here examined the formation of cocrystals of diiodohexatriyne with a bis(alkylnitrile) oxalamide host. Diiodohexatriyne undergoes 1,4-topochemical polymerization, with mild heating, to form poly(iodoethynyliododiacetylene), PIEDA. Polymerization was followed by extensive characterization through Raman spectroscopy, solid-state 13C MAS-NMR, and X-ray crystallography. This work represents the first ordered single-crystal to single-crystal 1,4-topochemical polymerization of a triyne, demonstrated through X-ray diffraction. The second project described efforts towards post-polymerization modification on PIEDA. Despite some success in model studies, isolated PIEDA was found to be too unstable to undergo controlled post-polymerization modification. The third project of this work described the demonstration of the formation of thin films of another PDA, polydiiododiacetylene (PIDA). Thin films of PIDA cocrystals could serve as components in solar cells or photovoltaic devices. Using lower concentration and allowing evaporation to occur in a fume hood, nanometer thick films were formed. However, thin films of PIDA cocrystals were too heterogeneous to be used within devices. The fourth project described here examined the preparation of cocrystals of bis(iodobutadiynyl)benzene monomer with several oxalamide hosts. The goal of this project is formation of conjugated ladder polydiacetylenes which have been theorized to have a lower band-gap than analogous linear polydiacetylenes. Cocrystals of monomer bis(iodobutadiynyl)benzene were formed with a variety of oxalamide hosts. Monomer cocrystals were heated at high temperatures and gave Raman signal consistent with polydiacetylene formation. Attempts to analyze heated cocrystals through single crystal X-ray diffraction have failed due to increased mosaicity. Other methods of inducing polymerization have been investigated but no ordered polymerization could be demonstrated. Halogen bonding has been demonstrated to be a reliable interaction for aligning these monomers. However, the polymerization and characterization of resultant polymer remains challenging due to the multiple reaction pathways of these materials.

A Membrane-Free Ferrocene-Based High-Rate Semiliquid Battery.

PubMed

Ding, Yu; Zhao, Yu; Yu, Guihua

2015-06-10

We report here a ferrocene-based membrane-free, high-rate semiliquid battery that takes advantage of a highly soluble ferrocene/ferrocenium redox couple in nonaqueous phase. The designed battery exhibits stable capacity retention up to 94% of theoretical capacity of ferrocene (145 mAh g(-1)) at a broad current rate up to 60 C owing to rapid mass transport in a liquid phase and fast redox kinetics. The diffusion coefficient and the standard reaction constant are determined to be in the order of 10(-6) cm(2) s(-1) and 10(-1) cm s(-1), respectively, orders of magnitude greater than those in a solid-phase electrode and those in conventional redox flow batteries. Additionally, the battery demonstrates power density and energy density exceeding 1400 W L(-1) and 40 Wh L(-1), respectively, and stable cyclability with capacity retention of ∼80% for 500 cycles. Compared with state-of-the-art energy storage technologies such as Li-ion batteries or conventional redox flow batteries, the proposed liquid battery shows the potential to be an efficient energy storage system with exceptionally high power and reasonable energy density.

Heavy metal distributions in Peru Basin surface sediments in relation to historic, present and disturbed redox environments

NASA Astrophysics Data System (ADS)

Koschinsky, Andrea

Heavy metal distributions in deep-sea surface sediments and pore water profiles from five areas in the Peru Basin were investigated with respect to the redox environment and diagenetic processes in these areas. The 10-20-cm-thick Mn oxide-rich and minor metal-rich top layer is underlain by an increase in dissolved Mn and Ni concentrations resulting from the reduction of the MnO 2 phase below the oxic zone. The mobilised associated metals like Co, Zn and Cu are partly immobilised by sorption on clay, organic or Fe compounds in the post-oxic environment. Enrichment of dissolved Cu, Zn, Ni, Co, Pb, Cd, Fe and V within the upper 1-5 cm of the oxic zone can be attributed to the degradation of organic matter. In a core from one area at around 22-25 cm depth, striking enrichments of these metals in dissolved and solid forms were observed. Offset distributions between oxygen penetration and Mn reduction and the thickness of the Mn oxide-rich layer indicate fluctuations of the Mn redox boundary on a short-term time scale. Within the objectives of the German ATESEPP research programme, the effect of an industrial impact such as manganese nodule mining on the heavy metal cycle in the surface sediment was considered. If the oxic surface were to be removed or disturbed, oxygen would penetrate deep into the formerly suboxic sediment and precipitate Mn 2+ and metals like Ni and Co which are preferably scavenged by MnO 2. The solid enrichments of Cd, V, and other metals formed in post-oxic environments would move downward with the new redox boundary until a new equilibrium between oxygen diffusion and consumption is reached.

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.

Novel, Solvent Free, Single Ion Conductive Polymer Electrolytes (Warsaw-2001)

DTIC Science & Technology

2004-10-18

application in lithium and lithium - ion batteries , characterized by limited participation of anions in the transport of electrical charge. Studies...with studies on novel chemical energy conversion and storage devices mainly lithium or lithium ion batteries and fuel cells [1]. Our work within...this part of the project dealt with these novel ideas in the field of lithium or lithium - ion batteries based on polymeric solid electrolytes. The solid

Sodium Sulfur Battery Cell Experiment (NaSBE)

NASA Technical Reports Server (NTRS)

Garner, J. Christopher

1997-01-01

The Ford Motor Company published papers describing new types of secondary battery comprised of: solid, sodium ion conducting electrolyte; liquid metal electrode; redox electrode; operating temperature between 300 and 400 deg. C; specific energy of 150 Wh/kg; and a nominal voltage of 2.0 V.

A Broad Stability Investigation of Nb-Doped SrCoO 2.5+δ as a Reversible Oxygen Electrode for Intermediate-Temperature Solid Oxide Fuel Cells

DOE PAGES

Wang, Jie; Jiang, Long; Xiong, Xiaolei; ...

2016-06-10

The present work reports a systematic study on the structural, thermal, electrical and electrochemical stability of SrCo 1–xNb xO 2.5+δ series as a potential reversible oxygen-electrode for intermediate-temperature solid oxide fuel cells. The identified best composition is x = 0.10, which exhibits a stable pseudo primitive cubic structure at <700°C and a reversible oxygen redox reaction at 350°C. The conductivity of this material is p-type and also exhibits a peak at 350°C, implying that the electron hole conduction is closely associated with the oxygen nonstoichiometry. Electrochemical impedance spectroscopy analysis indicates a low polarization resistance rate-limited by a slower surface Omore » 2 dissociation step. Altogether, the material is thermally stable and oxygen redox reversible below 700°C, above which a catalytically less active brownmillerite SrCoO 2.5 is formed.« less

Durability of symmetric-structured metal-supported solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Tucker, Michael C.

2017-11-01

Symmetric-structure metal-supported solid oxide fuel cells (MS-SOFC) with YSZ electrolyte are fabricated with porous YSZ backbone electrodes, stainless steel supports, and infiltrated catalysts on both anode and cathode side. Durability towards aggressive thermal and redox cycling, and long-term operation is assessed. Many sealing material candidates are screened for compatibility with the cell materials and operating conditions, and a commercial sealing glass, GM31107, is selected. LSM/SDCN cells are then subjected to 200 very fast thermal cycles and 20 complete redox cycles, with minimal impact to cell performance. LSM/SDCN and SDCN/SDCN cells are operated for more than 1200 h at 700 °C. The seal and cell hermeticity is maintained, and cell ohmic impedance does not change significantly during operation. Electrode polarization increases during operation, leading to significant degradation of the cell performance. In-operando EIS and post-mortem SEM/EDS analysis suggest that catalyst coarsening and cathode Cr deposition are the dominant degradation modes.

Oxidative Dissolution of Arsenopyrite by Mesophilic and Moderately Thermophilic Acidophiles †

PubMed Central

Tuovinen, Olli H.; Bhatti, Tariq M.; Bigham, Jerry M.; Hallberg, Kevin B.; Garcia, Oswaldo; Lindström, E. Börje

1994-01-01

The purpose of this work was to determine solution- and solid-phase changes associated with the oxidative leaching of arsenopyrite (FeAsS) by Thiobacillus ferrooxidans and a moderately thermoacidophilic mixed culture. Jarosite [KFe3(SO4)2(OH)6], elemental sulfur (S0), and amorphous ferric arsenate were detected by X-ray diffraction as solid-phase products. The oxidation was not a strongly acid-producing reaction and was accompanied by a relatively low redox level. The X-ray diffraction lines of jarosite increased considerably when ferrous sulfate was used as an additional substrate for T. ferroxidans. A moderately thermoacidophilic mixed culture oxidized arsenopyrite faster at 45°C than did T. ferroxidans at 22°C, and the oxidation was accompanied by a nearly stoichiometric release of Fe and As. The redox potential was initially low but subsequently increased during arsenopyrite oxidation by the thermoacidophiles. Jarosite, S0, and amorphous ferric arsenate were also formed under these conditions. PMID:16349379

Application and future of solid foams

NASA Astrophysics Data System (ADS)

Bienvenu, Yves

2014-10-01

To conclude this series of chapters on solid foam materials, a review of industrial current applications and of mid-term market perspectives centred on manmade foams is given, making reference to natural cellular materials. Although the polymeric foam industrial development overwhelms the rest and finds applications on many market segments, more attention will be paid to the emerging market of inorganic-especially metallic-foams (and cellular materials) and their applications, present or upcoming. It is shown that the final applications of solid foams are primarily linked to transport and the present-day development of the different classes of solid foams is contrasted between functional applications and structural applications. xml:lang="fr"

Ceramic and polymeric solid electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

Lithium-ion batteries are important for energy storage in a wide variety of applications including consumer electronics, transportation and large-scale energy production. The performance of lithium-ion batteries depends on the materials used. One critical component is the electrolyte, which is the focus of this paper. In particular, inorganic ceramic and organic polymer solid-electrolyte materials are reviewed. Solid electrolytes provide advantages in terms of simplicity of design and operational safety, but typically have conductivities that are lower than those of organic liquid electrolytes. This paper provides a comparison of the conductivities of solid-electrolyte materials being used or developed for use in lithium-ion batteries.

A multi-electron redox mediator for redox-targeting lithium-sulfur flow batteries

NASA Astrophysics Data System (ADS)

Li, Guochun; Yang, Liuqing; Jiang, Xi; Zhang, Tianran; Lin, Haibin; Yao, Qiaofeng; Lee, Jim Yang

2018-02-01

The lithium-sulfur flow battery (LSFB) is a new addition to the rechargeable lithium flow batteries (LFBs) where sulfur or a sulfur compound is used as the cathode material against the lithium anode. We report here our evaluation of an organic sulfide - dimethyl trisulfide (DMTS), as 1) a catholyte of a LFB and 2) a multi-electron redox mediator for discharging and charging a solid sulfur cathode without any conductive additives. The latter configuration is also known as the redox-targeting lithium-sulfur flow battery (RTLSFB). The LFB provides an initial discharge capacity of 131.5 mAh g-1DMTS (1.66 A h L-1), which decreases to 59 mAh g-1DMTS (0.75 A h L-1) after 40 cycles. The RTLSFB delivers a significantly higher application performance - initial discharge capacity of 1225.3 mAh g-1sulfur (3.83 A h L-1), for which 1030.9 mAh g-1sulfur (3.23 A h L-1) is still available after 40 cycles. The significant increase in the discharge and charge duration of the LFB after sulfur addition indicates that DMTS is better used as a redox mediator in a RTLSFB than as a catholyte in a LFB.

Quantification of the degradation of Ni-YSZ anodes upon redox cycling

NASA Astrophysics Data System (ADS)

Song, Bowen; Ruiz-Trejo, Enrique; Bertei, Antonio; Brandon, Nigel P.

2018-01-01

Ni-YSZ anodes for Solid Oxide Fuel Cells are vulnerable to microstructural damage during redox cycling leading to a decrease in the electrochemical performance. This study quantifies the microstructural changes as a function of redox cycles at 800 °C and associates it to the deterioration of the mechanical properties and polarisation resistance. A physically-based model is used to estimate the triple-phase boundary (TPB) length from impedance spectra, and satisfactorily matches the TPB length quantified by FIB-SEM tomography: within 20 redox cycles, the TPB density decreases from 4.63 μm-2 to 1.06 μm-2. Although the polarisation resistance increases by an order of magnitude after 20 cycles, after each re-reduction the electrode polarisation improves consistently due to the transient generation of Ni nanoparticles around the TPBs. Nonetheless, the long-term degradation overshadows this transient improvement due to the nickel agglomeration. In addition, FIB-SEM tomography reveals fractures along YSZ grain boundaries, Ni-YSZ detachment and increased porosity in the composite that lead to irreversible mechanical damage: the elastic modulus diminishes from 36.4 GPa to 20.2 GPa and the hardness from 0.40 GPa to 0.15 GPa. These results suggest that microstructural, mechanical and electrochemical properties are strongly interdependent in determining the degradation caused by redox cycling.

Side wire feed for welding apparatus

NASA Technical Reports Server (NTRS)

Arnett, J. C.

1974-01-01

Coaxial electrode arrangement has solid central electrode, insulated outer electrode, and transverse channel for feeding wire through tip of electrode assembly. Polymeric insulation is thrust aside by pressure, which is provided by separately operated mechanism acting through central electrode.

Determination of acrylamide in brewed coffee and coffee powder using polymeric ionic liquid-based sorbent coatings in solid-phase microextraction coupled to gas chromatography-mass spectrometry.

PubMed

Cagliero, Cecilia; Ho, Tien D; Zhang, Cheng; Bicchi, Carlo; Anderson, Jared L

2016-06-03

This study describes a simple and rapid sampling method employing a polymeric ionic liquid (PIL) sorbent coating in direct immersion solid-phase microextraction (SPME) for the trace-level analysis of acrylamide in brewed coffee and coffee powder. The crosslinked PIL sorbent coating demonstrated superior sensitivity in the extraction of acrylamide compared to all commercially available SPME coatings. A spin coating method was developed to evenly distribute the PIL coating on the SPME support and reproducibly produce fibers with a large film thickness. Ninhydrin was employed as a quenching reagent during extraction to inhibit the production of interfering acrylamide. The PIL fiber produced a limit of quantitation for acrylamide of 10μgL(-1) and achieved comparable results to the ISO method in the analysis of six coffee powder samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Arya, Anil; Sharma, Sweety; Sharma, A. L., E-mail: alsharmaiitkgp@gmail.com

Blend polymer electrolytes are prepared for salt concentration (Ö/Li = 4) with the constant ratio (0.5 gm) of PEO and PAN using solution casting technique. The prepared free standing solid polymeric film is characterized by Field Emission Scanning Electron Microscopy (FESEM) which confirms the homogeneous distribution of dissociated salt in blend polymer matrix. After addition of salt the ionic conductivity value is found to be of the order of 7.13 × 10{sup −5} Scm{sup −1} which is three orders higher when compared with pure blend polymer films. The microscopic interaction among the polymer-ion, ion-ion has been confirmed by the Fouriermore » Transform Infrared (FTIR) Spectroscopy. A very fine correlation has been built in the electrical conductivity and FTIR result. On the basis of above finding, a prepared free standing solid polymeric film appears to be appropriate for the energy storage/conversion device applications.« less

A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

PubMed

Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

2014-03-17

This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimisation of the synthesis of vancomycin-selective molecularly imprinted polymer nanoparticles using automatic photoreactor

PubMed Central

2014-01-01

A novel optimized protocol for solid-state synthesis of molecularly imprinted polymer nanoparticles (nanoMIPs) with specificity for antibiotic vancomycin is described. The experimental objective was optimization of the synthesis parameters (factors) affecting the yield of obtained nanoparticles which have been synthesized using the first prototype of an automated solid-phase synthesizer. Applications of experimental design (or design of experiments) in optimization of nanoMIP yield were carried out using MODDE 9.0 software. The factors chosen in the model were the amount of functional monomers in the polymerization mixture, irradiation time, temperature during polymerization, and elution temperature. In general, it could be concluded that the irradiation time is the most important and the temperature was the least important factor which influences the yield of nanoparticles. Overall, the response surface methodology proved to be an effective tool in reducing time required for optimization of complex experimental conditions. PMID:24685151

Optimisation of the synthesis of vancomycin-selective molecularly imprinted polymer nanoparticles using automatic photoreactor.

PubMed

Muzyka, Kateryna; Karim, Khalku; Guerreiro, Antonio; Poma, Alessandro; Piletsky, Sergey

2014-03-31

A novel optimized protocol for solid-state synthesis of molecularly imprinted polymer nanoparticles (nanoMIPs) with specificity for antibiotic vancomycin is described. The experimental objective was optimization of the synthesis parameters (factors) affecting the yield of obtained nanoparticles which have been synthesized using the first prototype of an automated solid-phase synthesizer. Applications of experimental design (or design of experiments) in optimization of nanoMIP yield were carried out using MODDE 9.0 software. The factors chosen in the model were the amount of functional monomers in the polymerization mixture, irradiation time, temperature during polymerization, and elution temperature. In general, it could be concluded that the irradiation time is the most important and the temperature was the least important factor which influences the yield of nanoparticles. Overall, the response surface methodology proved to be an effective tool in reducing time required for optimization of complex experimental conditions.

Optimisation of the synthesis of vancomycin-selective molecularly imprinted polymer nanoparticles using automatic photoreactor

NASA Astrophysics Data System (ADS)

Muzyka, Kateryna; Karim, Khalku; Guerreiro, Antonio; Poma, Alessandro; Piletsky, Sergey

2014-03-01

A novel optimized protocol for solid-state synthesis of molecularly imprinted polymer nanoparticles (nanoMIPs) with specificity for antibiotic vancomycin is described. The experimental objective was optimization of the synthesis parameters (factors) affecting the yield of obtained nanoparticles which have been synthesized using the first prototype of an automated solid-phase synthesizer. Applications of experimental design (or design of experiments) in optimization of nanoMIP yield were carried out using MODDE 9.0 software. The factors chosen in the model were the amount of functional monomers in the polymerization mixture, irradiation time, temperature during polymerization, and elution temperature. In general, it could be concluded that the irradiation time is the most important and the temperature was the least important factor which influences the yield of nanoparticles. Overall, the response surface methodology proved to be an effective tool in reducing time required for optimization of complex experimental conditions.

Physical aging in pharmaceutical polymers and the effect on solid oral dosage form stability.

PubMed

Kucera, Shawn A; Felton, Linda A; McGinity, James W

2013-12-05

The application of a polymeric film to a solid oral dosage form can be an effective technique to modify drug release. Most polymers used for such purposes are amorphous in nature and are subject to physical aging. This physical aging phenomenon has been shown to cause changes not only in the mechanical and drug release properties of polymeric films, but also the permeability of these films due to a densification and decrease in free volume of the polymer as the material relaxes to an equilibrated thermodynamic state. Temperature, humidity, and additional excipients in the coating formulations have been shown to influence the aging process. This review article discusses the process of physical aging in films prepared from aqueous dispersions, describes various analytical techniques that can be used to investigate the aging process, and highlights strategies to prevent such aging. Copyright © 2013 Elsevier B.V. All rights reserved.

Tunable thermal expansion in framework materials through redox intercalation

PubMed Central

Chen, Jun; Gao, Qilong; Sanson, Andrea; Jiang, Xingxing; Huang, Qingzhen; Carnera, Alberto; Rodriguez, Clara Guglieri; Olivi, Luca; Wang, Lei; Hu, Lei; Lin, Kun; Ren, Yang; Lin, Zheshuai; Wang, Cong; Gu, Lin; Deng, Jinxia; Attfield, J. Paul; Xing, Xianran

2017-01-01

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework-type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. Redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion. PMID:28181576

Tunable thermal expansion in framework materials through redox intercalation

NASA Astrophysics Data System (ADS)

Chen, Jun; Gao, Qilong; Sanson, Andrea; Jiang, Xingxing; Huang, Qingzhen; Carnera, Alberto; Rodriguez, Clara Guglieri; Olivi, Luca; Wang, Lei; Hu, Lei; Lin, Kun; Ren, Yang; Lin, Zheshuai; Wang, Cong; Gu, Lin; Deng, Jinxia; Attfield, J. Paul; Xing, Xianran

2017-02-01

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework-type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. Redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.

Porous Ni-Fe alloys as anode support for intermediate temperature solid oxide fuel cells: I. Fabrication, redox and thermal behaviors

NASA Astrophysics Data System (ADS)

Wang, Xin; Li, Kai; Jia, Lichao; Zhang, Qian; Jiang, San Ping; Chi, Bo; Pu, Jian; Jian, Li; Yan, Dong

2015-03-01

Porous Ni-Fe anode supports for intermediate solid oxide fuel cells are prepared by reducing the sintered NiO-(0-50 wt. %) Fe2O3 composites in H2, their microstructure, redox and thermal expansion/cycling characteristics are systematically investigated. The sintered NiO-Fe2O3 composites are consisted of NiO and NiFe2O4, and are fully reducible to porous metallic Ni-Fe alloys in H2 at temperatures between 600 and 750 °C. The porous structure contains pores in bimodal distribution with larger pores between the sintered particles and smaller ones inside the particles. The oxidation resistance of the Ni-Fe alloy anode supports at 600 and 750 °C is increased by the addition of Fe, their oxidation kinetics obeys a multistage parabolic law in the form of (Percentageweightgain /Specificsurfacearea) 2 =kp · t , where kp is the rate constant and t the oxidation time. The dimension of the Ni-Fe anode supports is slightly changed without disintegrating their structure, and Fe addition is beneficial to the redox stability. The TEC of the Ni-Fe alloy anode supports decreases with the increase of Fe content. The anode supports containing Fe is less stable in dimension during thermal cycles due to the continuous sintering, but the dimension change after thermal cycles is within 1%.

ATP and Mg2+ Promote the Reversible Oligomerization and Aggregation of Chloroplast 2-Cys Peroxiredoxin*

PubMed Central

Aran, Martín; Ferrero, Diego; Wolosiuk, Alejandro; Mora-García, Santiago; Wolosiuk, Ricardo A.

2011-01-01

2-Cys peroxiredoxins (2-Cys Prxs) are ubiquitous peroxidases with important roles in cellular antioxidant defense and hydrogen peroxide-mediated signaling. Post-translational modifications of conserved cysteines cause the transition from low to high molecular weight oligomers, triggering the functional change from peroxidase to molecular chaperone. However, it remains unclear how non-covalent interactions of 2-Cys Prx with metabolites modulate the quaternary structure. Here, we disclose that ATP and Mg2+ (ATP/Mg) promote the self-polymerization of chloroplast 2-Cys Prx (polypeptide 23.5 kDa) into soluble higher order assemblies (>2 MDa) that proceed to insoluble aggregates beyond 5 mm ATP. Remarkably, the withdrawal of ATP or Mg2+ brings soluble oligomers and insoluble aggregates back to the native conformation without compromising the associated functions. As confirmed by transmission electron microscopy, ATP/Mg drive the toroid-like decamers (diameter 13 nm) to the formation of large sphere-like particles (diameter ∼30 nm). Circular dichroism studies on ATP-labeled 2-Cys Prx reveal that ATP/Mg enhance the proportion of β-sheets with the concurrent decrease in the content of α-helices. In line with this observation, the formation of insoluble aggregates is strongly prevented by 2,2,2-trifluoroethanol, a cosolvent employed to induce α-helical conformations. We further find that the response of self-polymerization to ATP/Mg departs abruptly from that of the associated peroxidase and chaperone activities when two highly conserved residues, Arg129 and Arg152, are mutated. Collectively, our data uncover that non-covalent interactions of ATP/Mg with 2-Cys Prx modulate dynamically the quaternary structure, thereby coupling the non-redox chemistry of cell energy with redox transformations at cysteine residues. PMID:21525006

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.

Redox and catalysis 'all-in-one' infinite coordination polymer for electrochemical immunosensor of tumor markers.

PubMed

Zhang, Bing; Liu, Bingqian; Chen, Guonan; Tang, Dianping

2015-02-15

Prostate-specific antigen (PSA), as a glycoprotein enzyme encoded in humans by the KLK3 gene, is one of the most important biomarkers for the diagnosis and prognosis of prostate cancer. Herein, a new electrochemical immunosensor for sensitive determination of PSA was designed by using redox and catalysis 'all-in-one' infinite coordination polymer (PtNP@ICP) as signal tag on the polyamidoamine dendrimers modified electrode interface. To construct such 'all-in-one' PtNP@ICP nanostructures, the coordination polymerization was fully carried between metal ions and polydentate bridging ligands, and the PtNP was encapsulated into the ICP in the process of polymerization. The prepared PtNP@ICP nanocatalyst was characterized by transmission electron microscope (TEM), energy dispersive X-ray spectrometry (EDX), ultraviolet and visible (UV-vis) spectrophotometry and Fourier transform infrared spectroscope (FTIR). And the synthesized PtNP@ICP was utilized as signal tag for the label of PSA. With a sandwich-type immunoassay format, the conjugated signal tag on the transducer increased with the increasing PSA concentration in the sample thus enhancing the signal of the electrochemical immunosensor due to the catalytic reduction toward H2O2 of the enveloped PtNP. Under optimal conditions, the current was proportional to the logarithm of PSA concentration ranging from 0.001 to 60 ng/mL. The detection limit (LOD) was 0.3 pg/mL at 3 sB. The immunosensor displayed an acceptable reproducibility, stability and selectivity. In addition, the methodology was evaluated with human serum specimens receiving good correlation with results from commercialized enzyme-linked immunosorbent assay (ELISA) method. Copyright © 2014 Elsevier B.V. All rights reserved.

Monomeric cocoa catechins enhance β-cell function by increasing mitochondrial respiration.

PubMed

Rowley, Thomas J; Bitner, Benjamin F; Ray, Jason D; Lathen, Daniel R; Smithson, Andrew T; Dallon, Blake W; Plowman, Chase J; Bikman, Benjamin T; Hansen, Jason M; Dorenkott, Melanie R; Goodrich, Katheryn M; Ye, Liyun; O'Keefe, Sean F; Neilson, Andrew P; Tessem, Jeffery S

2017-11-01

A hallmark of type 2 diabetes (T2D) is β-cell dysfunction and the eventual loss of functional β-cell mass. Therefore, mechanisms that improve or preserve β-cell function could be used to improve the quality of life of individuals with T2D. Studies have shown that monomeric, oligomeric and polymeric cocoa flavanols have different effects on obesity, insulin resistance and glucose tolerance. We hypothesized that these cocoa flavanols may have beneficial effects on β-cell function. INS-1 832/13-derived β-cells and primary rat islets cultured with a monomeric catechin-rich cocoa flavanol fraction demonstrated enhanced glucose-stimulated insulin secretion, while cells cultured with total cocoa extract and with oligomeric or polymeric procyanidin-rich fraction demonstrated no improvement. The increased glucose-stimulated insulin secretion in the presence of the monomeric catechin-rich fraction corresponded with enhanced mitochondrial respiration, suggesting improvements in β-cell fuel utilization. Mitochondrial complex III, IV and V components are up-regulated after culture with the monomer-rich fraction, corresponding with increased cellular ATP production. The monomer-rich fraction improved cellular redox state and increased glutathione concentration, which corresponds with nuclear factor, erythroid 2 like 2 (Nrf2) nuclear localization and expression of Nrf2 target genes including nuclear respiratory factor 1 (Nrf1) and GA binding protein transcription factor alpha subunit (GABPA), essential genes for increasing mitochondrial function. We propose a model by which monomeric cocoa catechins improve the cellular redox state, resulting in Nrf2 nuclear migration and up-regulation of genes critical for mitochondrial respiration, glucose-stimulated insulin secretion and ultimately improved β-cell function. These results suggest a mechanism by which monomeric cocoa catechins exert their effects as an effective complementary strategy to benefit T2D patients. Copyright © 2017 Elsevier Inc. All rights reserved.

Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

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

Fendorf, Scott

2016-04-05

Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of thismore » project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites—inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation mechanism may help to explain U retention in some geologic materials, improving our understanding of U-based geochronology and the redox status of ancient geochemical environments. Additionally, U(VI) may be incorporated within silicate minerals though encapsulation of U-bearing iron oxides, leading to a redox stable solid. Our research detailing previously unrecognized mechanism of U incorporation within sediment minerals may even lead to new approaches for in situ contamination remediation techniques, and will help refine models of U fate and transport in reduced subsurface zones.« less

COMPARISON OF MICROBIAL POPULATIONS IN A CONVENTIONAL AND BIOREACTING MUNICIPAL SOLID WASTE LANDFILLS

EPA Science Inventory

Landfills are the ultimate reactors for biodegradation as they contain nutrients, bacteria, and various redox conditions which, then, change over time. Enhancement of the landill environment to optimize the rates of biodegradation and to ensure more rapid stabilization of the was...

DNA interactions of non-chelating tinidazole-based coordination compounds and their structural, redox and cytotoxic properties.

PubMed

Castro-Ramírez, Rodrigo; Ortiz-Pastrana, Naytzé; Caballero, Ana B; Zimmerman, Matthew T; Stadelman, Bradley S; Gaertner, Andrea A E; Brumaghim, Julia L; Korrodi-Gregório, Luís; Pérez-Tomás, Ricardo; Gamez, Patrick; Barba-Behrens, Norah

2018-05-23

Novel tinidazole (tnz) coordination compounds of different geometries were synthesised, whose respective solid-state packing appears to be driven by inter- and intramolecular lone pairπ interactions. The copper(ii) compounds exhibit interesting redox properties originating from both the tnz and the metal ions. These complexes interact with DNA through two distinct ways, namely via electrostatic interactions or/and groove binding, and they can mediate the generation of ROS that damage the biomolecule. Cytotoxic studies revealed an interesting activity of the dinuclear compound [Cu(tnz)2(μ-Cl)Cl]2 7, which is further more efficient towards cancer cells, compared with normal cells.

Preparation of epoxy-acrylate copolymer/nano-silica via Pickering emulsion polymerization and its application as printing binder

NASA Astrophysics Data System (ADS)

Gao, Dangge; Chang, Rui; Lyu, Bin; Ma, Jianzhong; Duan, Xiying

2018-03-01

This paper presents a facile and efficient synthesis method to fabricate epoxy-acrylate copolymer/nano-silica latex via Pickering emulsion polymerization stabilized by silica sol. The effects of solid contents, silica concentration and polymerization time on emulsion polymerization were studied. The core-shell epoxy-acrylate copolymer/nano-silica was obtained with average diameter 690 nm, was observed by Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS). The formation mechanism of epoxy-acrylate copolymer/nano-silica emulsion polymerization was proposed through observing the morphology of latex particles at different polymerization time. Fourier Transformation Infrared (FT-IR) and Thermogravimetric Analysis (TGA) were used to study structure and thermostability of the composites. Morphology of the latex film was characterized by Scanning Electron Microscope (SEM). The results indicated that nano-silica particles existed in the composite emulsion and could improve the thermal stability of the film. The epoxy-acrylate copolymer/nano-silica latex was used as binder applied to cotton fabric for pigment printing. The application results demonstrated that Pickering emulsion stabilized by silica sol has good effects in the pigment printing binder without surfactant. Compared with commodity binder, the resistance to wet rubbing fastness and soaping fastness were improved half grade.

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.

Use of polyurethane foam and 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline for determination of nitrite by diffuse reflectance spectroscopy and colorimetry.

PubMed

Apyari, V V; Dmitrienko, S G; Ostrovskaya, V M; Anaev, E K; Zolotov, Y A

2008-07-01

Polyurethane foam (PUF) has been suggested as a solid polymeric reagent for determination of nitrite. The determination is based on the diazotization of end toluidine groups of PUF with nitrite in acidic medium followed by coupling of polymeric diazonium cation with 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline. The intensely colored polymeric azodye formed in this reaction can be used as a convenient analytic form for the determination of nitrite by diffuse reflectance spectroscopy (c (min) = 0.7 ng mL(-1)). The possibility of using a desktop scanner, digital camera, and computer data processing for the numerical evaluation of the color intensity of the polymeric azodye has been investigated. A scanner and digital camera can be used for determination of nitrite with the same sensitivity and reproducibility as with diffuse reflectance spectroscopy. The approach developed was applied for determination of nitrite in river water and human exhaled breath condensate.

A Hydrogel of Ultrathin Pure Polyaniline Nanofibers: Oxidant-Templating Preparation and Supercapacitor Application.

PubMed

Zhou, Kun; He, Yuan; Xu, Qingchi; Zhang, Qin'e; Zhou, An'an; Lu, Zihao; Yang, Li-Kun; Jiang, Yuan; Ge, Dongtao; Liu, Xiang Yang; Bai, Hua

2018-05-15

Although challenging, fabrication of porous conducting polymeric materials with excellent electronic properties is crucial for many applications. We developed a fast in situ polymerization approach to pure polyaniline (PANI) hydrogels, with vanadium pentoxide hydrate nanowires as both the oxidant and sacrifice template. A network comprised of ultrathin PANI nanofibers was generated during the in situ polymerization, and the large aspect ratio of these PANI nanofibers allowed the formation of hydrogels at a low solid content of 1.03 wt %. Owing to the ultrathin fibril structure, PANI hydrogels functioning as a supercapacitor electrode display a high specific capacitance of 636 F g -1 , a rate capability, and good cycling stability (∼83% capacitance retention after 10,000 cycles). This method was also extended to the preparation of polypyrrole and poly(3,4-ethylenedioxythiophene) hydrogels. This template polymerization method represents a rational strategy for design of conducing polymer networks, which can be readily integrated in high-performance devices or a further platform for functional composites.

The kinetics of polyurethane structural foam formation: Foaming and polymerization

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

Rao, Rekha R.; Mondy, Lisa A.; Long, Kevin N.

We are developing kinetic models to understand the manufacturing of polymeric foams, which evolve from low viscosity Newtonian liquids, to bubbly liquids, finally producing solid foam. Closed-form kinetics are formulated and parameterized for PMDI-10, a fast curing polyurethane, including polymerization and foaming. PMDI- 10 is chemically blown, where water and isocyanate react to form carbon dioxide. The isocyanate reacts with polyol in a competing reaction, producing polymer. Our approach is unique, though it builds on our previous work and the polymerization literature. This kinetic model follows a simplified mathematical formalism that decouples foaming and curing, including an evolving glass transitionmore » temperature to represent vitrification. This approach is based on IR, DSC, and volume evolution data, where we observed that the isocyanate is always in excess and does not affect the kinetics. Finally, the kinetics are suitable for implementation into a computational fluid dynamics framework, which will be explored in subsequent papers.« less

Spiral actin-polymerization waves can generate amoeboidal cell crawling

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

Dreher, A.; Aranson, I. S.; Kruse, K.

2014-05-01

Amoeboidal cell crawling on solid substrates is characterized by protrusions that seemingly appear randomly along the cell periphery and drive the cell forward. For many cell types, it is known that the protrusions result from polymerization of the actin cytoskeleton. However, little is known about how the formation of protrusions is triggered and whether the appearance of subsequent protrusions is coordinated. Recently, the spontaneous formation of actin-polymerization waves was observed. These waves have been proposed to orchestrate the cytoskeletal dynamics during cell crawling. Here, we study the impact of cytoskeletal polymerization waves on cell migration using a phase-field approach. Inmore » addition to directionally moving cells, we find states reminiscent of amoeboidal cell crawling. In this framework, new protrusions are seen to emerge from a nucleation process, generating spiral actin waves in the cell interior. Nucleation of new spirals does not require noise, but occurs in a state that is apparently displaying spatio-temporal chaos.« less

Phosphine polymerization by nitric oxide: experimental characterization and theoretical predictions of mechanism.

PubMed

Zhao, Yi-Lei; Flora, Jason W; Thweatt, William David; Garrison, Stephen L; Gonzalez, Carlos; Houk, K N; Marquez, Manuel

2009-02-02

A yellow solid material [P(x)H(y)] has been obtained in the reaction of phosphine (PH(3)) and nitric oxide (NO) at room temperature and characterized by thermogravimetric analysis mass spectrometry (TGA-MS) and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. In this work using complete basis set (CBS-QB3) methods a plausible mechanism has been investigated for phosphine polymerization in the presence of nitric oxide (NO). Theoretical explorations with the ab initio method suggest (a) instead of the monomer the nitric oxide dimer acts as an initial oxidant, (b) the resulting phosphine oxides (H(3)P=O <--> H(3)P(+)O(-)) in the gas phase draw each other via strong dipolar interactions between the P-O groups, and (c) consequently an autocatalyzed polymerization occurs among the phosphine oxides, forming P-P chemical bonds and losing water. The possible structures of polyhydride phosphorus polymer were discussed. In the calculations a series of cluster models was computed to simulate polymerization.

Synthesis of surface-anchored DNA-polymer bioconjugates using reversible addition-fragmentation chain transfer polymerization.

PubMed

He, Peng; He, Lin

2009-07-13

We report here an approach to grafting DNA-polymer bioconjugates on a planar solid support using reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, a trithiocarbonate compound as the RAFT chain transfer agent (CTA) is attached to the distal point of a surface-immobilized oligonucleotide. Initiation of RAFT polymerization leads to controlled growth of polymers atop DNA molecules on the surface. Growth kinetics of poly(monomethoxy-capped oligo(ethylene glycol) methacrylate) atop DNA molecules is investigated by monitoring the change of polymer film thickness as a function of reaction time. The reaction conditions, including the polymerization temperature, the initiator concentration, the CTA surface density, and the selection of monomers, are varied to examine their impacts on the grafting efficiency of DNA-polymer conjugates. Comparing to polymer growth atop small molecules, the experimental results suggest that DNA molecules significantly accelerate polymer growth, which is speculated as a result of the presence of highly charged DNA backbones and purine/pyrimidine moieties surrounding the reaction sites.

The kinetics of polyurethane structural foam formation: Foaming and polymerization

DOE PAGES

Rao, Rekha R.; Mondy, Lisa A.; Long, Kevin N.; ...

2017-02-15

We are developing kinetic models to understand the manufacturing of polymeric foams, which evolve from low viscosity Newtonian liquids, to bubbly liquids, finally producing solid foam. Closed-form kinetics are formulated and parameterized for PMDI-10, a fast curing polyurethane, including polymerization and foaming. PMDI- 10 is chemically blown, where water and isocyanate react to form carbon dioxide. The isocyanate reacts with polyol in a competing reaction, producing polymer. Our approach is unique, though it builds on our previous work and the polymerization literature. This kinetic model follows a simplified mathematical formalism that decouples foaming and curing, including an evolving glass transitionmore » temperature to represent vitrification. This approach is based on IR, DSC, and volume evolution data, where we observed that the isocyanate is always in excess and does not affect the kinetics. Finally, the kinetics are suitable for implementation into a computational fluid dynamics framework, which will be explored in subsequent papers.« less

Synthesis of Pyridine– and Pyrazine–BF 3 Complexes and Their Characterization in Solution and Solid State

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

Chénard, Etienne; Sutrisno, Andre; Zhu, Lingyang

2016-03-31

Following the discovery of the redox-active 1,4- bis-BF 3-quinoxaline complex, we undertook a structure- activity study with the objective to understand the active nature of the quinoxaline complex. Through systematic synthesis and characterization, we have compared complexes prepared from pyridine and pyrazine derivatives, as heterocyclic core analogues. This paper reports the structural requirements that give rise to the electrochemical features of the 1,4-bis-BF 3-quinoxaline adduct. Using solution and solidstate NMR spectroscopy, the role of aromatic ring fusion and nitrogen incorporation in bonding and electronics was elucidated. We establish the boron atom location and its interaction with its environment from 1Dmore » and 2D solution NMR, X-ray diffraction analysis, and 11B solid-state NMR experiments. Crystallographic analysis of single crystals helped to correlate the boron geometry with 11B quadrupolar coupling constant (CQ) and asymmetry parameter (ηQ), extracted from 11B solid-state NMR spectra. Additionally, computations based on density functional theory were performed to predict electrochemical behavior of the BF 3-heteroaromatic complexes. We then experimentally measured electrochemical potential using cyclic voltammetry and found that the redox potentials and CQ values are similarly affected by electronic changes in the complexes.« less

Synthesis and hydration behavior of calcium zirconium aluminate (Ca{sub 7}ZrAl{sub 6}O{sub 18}) cement

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

Kang, Eun-Hee; Yoo, Jun-Sang; Kim, Bo-Hye

2014-02-15

Calcium zirconium aluminate (Ca{sub 7}ZrAl{sub 6}O{sub 18}) cements were prepared by solid state reaction and polymeric precursor methods, and their phase evolution, morphology, and hydration behavior were investigated. In polymeric precursor method, a nearly single phase Ca{sub 7}ZrAl{sub 6}O{sub 18} was obtained at relatively lower temperature (1200 °C) whereas in solid state reaction, a small amount of CaZrO{sub 3} coexisted with Ca{sub 7}ZrAl{sub 6}O{sub 18} even at higher temperature (1400 °C). Unexpectedly, Ca{sub 7}ZrAl{sub 6}O{sub 18} synthesized by polymeric precursor process was the large-sized and rough-shaped powder. The planetary ball milling was employed to control the particle size and shape.more » The hydration behavior of Ca{sub 7}ZrAl{sub 6}O{sub 18} was similar to that of Ca{sub 3}Al{sub 2}O{sub 6} (C3A), but the hydration products were Ca{sub 3}Al{sub 2}O{sub 6}·6H{sub 2}O (C3AH6) and several intermediate products. Thus, Zr (or ZrO{sub 2}) stabilized the intermediate hydration products of C3A.« less

Formulation and Characterization of Polymeric Films Containing Combinations of Antiretrovirals (ARVs) for HIV Prevention

PubMed Central

Akil, Ayman; Agashe, Hrushikesh; Dezzutti, Charlene S.; Moncla, Bernard J.; Hillier, Sharon L.; Devlin, Brid; Shi, Yuan; Uranker, Kevin; Rohan, Lisa Cencia

2014-01-01

Purpose To develop polymeric films containing dual combinations of anti-HIV drug candidate tenofovir, maraviroc and dapivirine for vaginal application as topical microbicides. Methods A solvent casting method was used to manufacture the films. Solid phase solubility was used to identify potential polymers for use in the film formulation. Physical and chemical properties (such as water content, puncture strength and in vitro release) and product stability were determined. The bioactivity of the film products against HIV was assessed using the TZM-bl assay and a cervical explant model. Results Polymers identified from the solid phase solubility study maintained tenofovir and maraviroc in an amorphous state and prevented drug crystallization. Three combination film products were developed using cellulose polymers and polyvinyl alcohol. The residual water content in all films was < 10% (w/w). All films delivered the active agents with release of > 50% of film drug content within 30 minutes. Stability testing confirmed that the combination film products were stable for 12 months at ambient temperature and 6 months under stressed conditions. Antiviral activity was confirmed in TZM-bl and cervical explant models. Conclusions Polymeric films can be used as a stable dosage form for the delivery of antiretroviral combinations as microbicides. PMID:25079391

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

PubMed

Feng, Juanjuan; Sun, Min; Xu, Lili; Wang, Shuai; Liu, Xia; Jiang, Shengxiang

2012-12-14

Because of the occurrence of ion exchange between high-ionic-strength solution and anions of polymeric ionic liquids (PILs), PILs based solid-phase microextraction (SPME) fibers were rarely used in direct immersion mode to high-salt-added samples. In this work, a novel double-confined PIL sorbent was prepared by co-polymerization of cation and anion of 1-vinyl-3-octylimidzaolium p-styrenesulfonate (VOIm(+)SS(-)). The poly(VOIm(+)-SS(-)) was chemically bonded onto functionalized stainless steel wire via surface radical chain-transfer reaction. Stability of poly(VOIm(+)-SS(-)) in high-ionic-strength solution was investigated and compared with that of poly(1-vinyl-3-octylimidzaolium benzenesulfonate) (poly(VOIm(+)BS(-))) by elemental analysis of sulfur element, and results turned out that the poly(VOIm(+)-SS(-)) was more stable. Coupled to gas chromatography (GC), the poly(VOIm(+)-SS(-)) fiber was used to extract three sorts of compounds including anilines, phenols and phthalate esters in aqueous solution. The as-established method showed good linearity, low detection limits, and acceptable repeatability. The direct immersion SPME-GC method was applied to determine the model phthalate esters in bottled mineral water. The determination results were satisfactory. Copyright © 2012 Elsevier B.V. All rights reserved.

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

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

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

1964-01-01

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

Construction of Well-Defined Redox-Responsive CO2 -Based Polycarbonates: Combination of Immortal Copolymerization and Prereaction Approach.

PubMed

Liu, Shunjie; Zhao, Xun; Guo, Hongchen; Qin, Yusheng; Wang, Xianhong; Wang, Fosong

2017-05-01

Due to the axial group initiation in traditional (salen)CoX/quaternary ammonium catalyst system, it is difficult to construct single active center propagating polycarbonates for copolymerization of CO 2 /epoxides. Here a redox-responsive poly(vinyl cyclohexene carbonate) (PVCHC) with detachable disulfide-bond backbone is synthesized in a controllable manner using (salen)CoTFA/[bis(triphenylphosphine)iminium, [PPN]TFA binary catalyst, where the axial group initiation is depressed by judiciously choosing 3,3'-dithiodipropionic acid as starter. While for those comonomers failing to obtain polycarbonate with unimodal gel permeation chromatography (GPC) curve, a versatile method is developed by combination of immortal copolymerization and prereaction approach, and functional aliphatic polycarbonates having well-defined architecture and narrow polydispersity can be prepared. The resulting PVCHC can be further functionalized with alkenes by versatile cross-metathesis reaction to tune the physicochemical properties. The combination of immortal polymerization and prereaction approach creates a powerful platform for controllable synthesis of functional CO 2 -based polycarbonates. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nuclear Localizing Peptide-Conjugated, Redox-Sensitive Polymersomes for Delivering Curcumin and Doxorubicin to Pancreatic Cancer Microtumors.

PubMed

Anajafi, Tayebeh; Yu, Junru; Sedigh, Abbas; Haldar, Manas K; Muhonen, Wallace W; Oberlander, Seth; Wasness, Heather; Froberg, Jamie; Molla, Md Shahjahan; Katti, Kalpana S; Choi, Yongki; Shabb, John B; Srivastava, D K; Mallik, Sanku

2017-06-05

Improving the therapeutic index of anticancer agents is an enormous challenge. Targeting decreases the side effects of the therapeutic agents by delivering the drugs to the intended destination. Nanocarriers containing the nuclear localizing peptide sequences (NLS) translocate to the cell nuclei. However, the nuclear localization peptides are nonselective and cannot distinguish the malignant cells from the healthy counterparts. In this study, we designed a "masked" NLS peptide which is activated only in the presence of overexpressed matrix metalloproteinase-7 (MMP-7) enzyme in the pancreatic cancer microenvironment. This peptide is conjugated to the surface of redox responsive polymersomes to deliver doxorubicin and curcumin to the pancreatic cancer cell nucleus. We have tested the formulation in both two- and three-dimensional cultures of pancreatic cancer and normal cells. Our studies revealed that the drug-encapsulated polymeric vesicles are significantly more toxic toward the cancer cells (shrinking the spheroids up to 49%) compared to the normal cells (shrinking the spheroids up to 24%). This study can lead to the development of other organelle targeted drug delivery systems for various human malignancies.

One-pot synthesis of redox-responsive polymers-coated mesoporous silica nanoparticles and their controlled drug release.

PubMed

Sun, Jiao-Tong; Piao, Ji-Gang; Wang, Long-Hai; Javed, Mohsin; Hong, Chun-Yan; Pan, Cai-Yuan

2013-09-01

A versatile one-pot strategy for the preparation of reversibly cross-linked polymer-coated mesoporous silica nanoparticles (MSNs) via surface reversible addition-fragmentation chain transfer (RAFT) polymerization is presented for the first time in this paper. The less reactive monomer oligo(ethylene glycol) acrylate (OEGA) and the more reactive cross-linker N,N'-cystaminebismethacrylamide (CBMA) are chosen to be copolymerized on the external surfaces of RAFT agent-functionalized MSNs to form the cross-linked polymer shells. Owing to the reversible cleavage and restoration of disulfide bonds via reduction/oxidation reactions, the polymer shells can control the on/off switching of the nanopores and regulate the drug loading and release. The redox-responsive release of doxorubicin (DOX) from this drug carrier is realized. The protein adsorption, in vitro cytotoxicity assays, and endocytosis studies demonstrate that this biocompatible vehicle is a potential candidate for delivering drugs. It is expected that this versatile grafting strategy may help fabricate satisfying MSN-based drug delivery systems for clinical application. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Alternative to the Ionic Model

ERIC Educational Resources Information Center

Sanderson, R. T.

1975-01-01

Describes the "coordinated polymeric model," which yields more accurate energy calculations than the "ionic model" for compounds which exhibit considerable covalency. The dichotomy between ionic and covalent bonding is thus largely broken down for solids which are nonmolecular in the crystalline state. (MLH)

Chemical Shuttle Additives in Lithium Ion Batteries

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

Patterson, Mary

2013-03-31

The goals of this program were to discover and implement a redox shuttle that is compatible with large format lithium ion cells utilizing LiNi{sub 1/3}Mn{sub 1/3}Co{sub 1/3}O{sub 2} (NMC) cathode material and to understand the mechanism of redox shuttle action. Many redox shuttles, both commercially available and experimental, were tested and much fundamental information regarding the mechanism of redox shuttle action was discovered. In particular, studies surrounding the mechanism of the reduction of the oxidized redox shuttle at the carbon anode surface were particularly revealing. The initial redox shuttle candidate, namely 2-(pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole (BDB) supplied by Argonne National Laboratory (ANL, Lemont,more » Illinois), did not effectively protect cells containing NMC cathodes from overcharge. The ANL-RS2 redox shuttle molecule, namely 1,4-bis(2-methoxyethoxy)-2,5-di-tert-butyl-benzene, which is a derivative of the commercially successful redox shuttle 2,5-di-tert-butyl-1,4-dimethoxybenzene (DDB, 3M, St. Paul, Minnesota), is an effective redox shuttle for cells employing LiFePO{sub 4} (LFP) cathode material. The main advantage of ANL-RS2 over DDB is its larger solubility in electrolyte; however, ANL-RS2 is not as stable as DDB. This shuttle also may be effectively used to rebalance cells in strings that utilize LFP cathodes. The shuttle is compatible with both LTO and graphite anode materials although the cell with graphite degrades faster than the cell with LTO, possibly because of a reaction with the SEI layer. The degradation products of redox shuttle ANL-RS2 were positively identified. Commercially available redox shuttles Li{sub 2}B{sub 12}F{sub 12} (Air Products, Allentown, Pennsylvania and Showa Denko, Japan) and DDB were evaluated and were found to be stable and effective redox shuttles at low C-rates. The Li{sub 2}B{sub 12}F{sub 12} is suitable for lithium ion cells utilizing a high voltage cathode (potential that is higher than NMC) and the DDB is useful for lithium ion cells with LFP cathodes (potential that is lower than NMC). A 4.5 V class redox shuttle provided by Argonne National Laboratory was evaluated which provides a few cycles of overcharge protection for lithium ion cells containing NMC cathodes but it is not stable enough for consideration. Thus, a redox shuttle with an appropriate redox potential and sufficient chemical and electrochemical stability for commercial use in larger format lithium ion cells with NMC cathodes was not found. Molecular imprinting of the redox shuttle molecule during solid electrolyte interphase (SEI) layer formation likely contributes to the successful reduction of oxidized redox shuttle species at carbon anodes. This helps to understand how a carbon anode covered with an SEI layer, that is supposed to be electrically insulating, can reduce the oxidized form of a redox shuttle.« less

Preparation of ellagic acid molecularly imprinted polymeric microspheres based on distillation-precipitation polymerization for the efficient purification of a crude extract.

PubMed

Zhang, Hua; Zhao, Shangge; Zhang, Lu; Han, Bo; Yao, Xincheng; Chen, Wen; Hu, Yanli

2016-08-01

Molecularly imprinted polymeric microspheres with a high recognition ability toward the template molecule, ellagic acid, were synthesized based on distillation-precipitation polymerization. The as-obtained polymers were characterized by scanning electron microscopy, infrared spectroscopy, and thermogravimetric analysis. Static, dynamic, and selective binding tests were adopted to study the binding properties and the molecular recognition ability of the prepared polymers for ellagic acid. The results indicated that the maximum static adsorption capacity of the prepared polymers toward ellagic acid was 37.07 mg/g and the adsorption equilibrium time was about 100 min when the concentration of ellagic acid was 40 mg/mL. Molecularly imprinted polymeric microspheres were also highly selective toward ellagic acid compared with its analogue quercetin. It was found that the content of ellagic acid in the pomegranate peel extract was enhanced from 23 to 86% after such molecularly imprinted solid-phase extraction process. This work provides an efficient way for effective separation and enrichment of ellagic acid from complex matrix, which is especially valuable in industrial production. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New generation of electrochemical immunoassay based on polymeric nanoparticles for early detection of breast cancer

PubMed Central

Mouffouk, Fouzi; Aouabdi, Sihem; Al-Hetlani, Entesar; Serrai, Hacene; Alrefae, Tareq; Leo Chen, Liaohai

2017-01-01

Screening and early diagnosis are the key factors for the reduction of mortality rate and treatment cost of cancer. Therefore, sensitive and selective methods that can reveal the low abundance of cancer biomarkers in a biological sample are always desired. Here, we report the development of a novel electrochemical biosensor for early detection of breast cancer by using bioconjugated self-assembled pH-responsive polymeric micelles. The micelles were loaded with ferrocene molecules as “tracers” to specifically target cell surface-associated epithelial mucin (MUC1), a biomarker for breast and other solid carcinoma. The synthesis of target-specific, ferrocene-loaded polymeric micelles was confirmed, and the resulting sensor was capable of detecting the presence of MUC1 in a sample containing about 10 cells/mL. Such a high sensitivity was achieved by maximizing the loading capacity of ferrocene inside the polymeric micelles. Every single event of binding between the antibody and antigen was represented by the signal of hundreds of thousands of ferrocene molecules that were released from the polymeric micelles. This resulted in a significant increase in the intensity of the ferrocene signal detected by cyclic voltammetry. PMID:28450780

The electrochemical fluorination of polymeric materials for high energy density aqueous and non-aqueous battery and fuel cell separators

NASA Technical Reports Server (NTRS)

Liu, C. C.

1983-01-01

A computerized system was established and the electrochemical fluorination of trichloroethylene, polyacrylic acid and polyvinyl alcohol in anhydrous hydrogen fluoride was attempted. Both solid substrates as well as membranes were used. Some difficulties were found in handling and analyzing the solid substrates and membranes. Further studies are needed in this area. A microprocessor aided electrochemical fluorination system capable of obtaining highly reproducible experimental results was established.

Photopolymerization of N,N-dimethylaminobenzyl alcohol as amine co-initiator for light-cured dental resins.

PubMed

Schroeder, Walter F; Cook, Wayne D; Vallo, Claudia I

2008-05-01

The present study was carried out in order to assess the suitability of N,N-dimethylaminobenzyl alcohol (DMOH) as co-initiator of camphorquinone (CQ) and 1-phenyl-1,2-propanedione (PPD) in light-cured dental resins. DMOH was synthesized and used as co-initiator for the photopolymerization of a model resin based on {2,2-bis[4-(2-hydroxy-3-methacryloxyprop-1-oxy)phenyl]propane} (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA). Experimental formulations containing CQ or PPD in combination with DMOH at different concentrations were studied. The photopolymerization was carried out by means of a commercial light-emitting diode (LED) curing unit. The evolution of double bonds consumption versus irradiation time was followed by near-infrared spectroscopy (NIR). The photon absorption efficiency (PAE) of the photopolymerization process was calculated from the spectral distribution of the LED unit and the molar absorption coefficient distributions of PPD and CQ. DMOH is an efficient photoreducer of CQ and PPD resulting in higher polymerization rate and higher double bond conversion compared with dimethylaminoethylmethacrylate. The PAE for PPD was higher than that for CQ. However, the polymerization initiated by PPD progressed at a lower rate and exhibited lower values of final conversion compared with the resins containing CQ. This observation indicates that the lower polymerization rate of the PPD/amine system should be explained in terms of the mechanism of generating primary radicals by PPD, which is less efficient compared with CQ. The DMOH/benzoyl peroxide redox system, has recently been proposed as a more biocompatible accelerator for the polymerization of bone cements based on poly(methyl methacrylate), because cytotoxity tests have demonstrated that DMOH possesses better biocompatibility properties compared with traditional tertiary amines. The results obtained in the present study reveal the suitability of the CQ/DMOH initiator system for the polymerization of light-cured dental composites.

Polymeric ionic liquid coatings versus commercial solid-phase microextraction coatings for the determination of volatile compounds in cheeses.

PubMed

Trujillo-Rodríguez, María J; Yu, Honglian; Cole, William T S; Ho, Tien D; Pino, Verónica; Anderson, Jared L; Afonso, Ana M

2014-04-01

The extraction performance of four polymeric ionic liquid (PIL)-based solid-phase microextraction (SPME) coatings has been studied and compared to that of commercial SPME coatings for the extraction of 16 volatile compounds in cheeses. The analytes include 2 free fatty acids, 2 aldehydes, 2 ketones and 10 phenols and were determined by headspace (HS)-SPME coupled to gas chromatography (GC) with flame-ionization detection (FID). The PIL-based coatings produced by UV co-polymerization were more efficient than PIL-based coatings produced by thermal AIBN polymerization. Partition coefficients of analytes between the sample and the coating (Kfs) were estimated for all PIL-based coatings and the commercial SPME fiber showing the best performance among the commercial fibers tested: carboxen-polydimethylsyloxane (CAR-PDMS). For the PIL-based fibers, the highest K(fs) value (1.96 ± 0.03) was obtained for eugenol. The normalized calibration slope, which takes into account the SPME coating thickness, was also used as a simpler approximate tool to compare the nature of the coating within the determinations, with results entirely comparable to those obtained with estimated K(fs) values. The PIL-based materials obtained by UV co-polymerization containing the 1-vinyl-3-hexylimidazolium chloride IL monomer and 1,12-di(3-vinylimiazolium)dodecane dibromide IL crosslinker exhibited the best performance in the extraction of the select analytes from cheeses. Despite a coating thickness of only 7 µm, this copolymeric sorbent coating was capable of quantitating analytes in HS-SPME in a 30 to 2000 µg L(-1) concentration range, with correlation coefficient (R) values higher than 0.9938, inter-day precision values (as relative standard deviation in %) varying from 6.1 to 20%, and detection limits down to 1.6 µg L(-1). Copyright © 2013 Elsevier B.V. All rights reserved.

Electron transfer from a solid-state electrode assisted by methyl viologen sustains efficient microbial reductive dechlorination of TCE.

PubMed

Aulenta, Federico; Catervi, Alessandro; Majone, Mauro; Panero, Stefania; Reale, Priscilla; Rossetti, Simona

2007-04-01

The ability to transfer electrons, via an extracellular path, to solid surfaces is typically exploited by microorganisms which use insoluble electron acceptors, such as iron-or manganese-oxides or inert electrodes in microbial fuel cells. The reverse process, i.e., the use of solid surfaces or electrodes as electron donors in microbial respirations, although largely unexplored, could potentially have important environmental applications, particularly for the removal of oxidized pollutants from contaminated groundwater or waste streams. Here we show, for the first time, that an electrochemical cell with a solid-state electrode polarized at -500 mV (vs standard hydrogen electrode), in combination with a low-potential redox mediator (methyl viologen), can efficiently transfer electrochemical reducing equivalents to microorganisms which respire using chlorinated solvents. By this approach, the reductive transformation of trichloroethene, a toxic yet common groundwater contaminant, to harmless end-products such as ethene and ethane could be performed. Furthermore, using a methyl-viologen-modified electrode we could even demonstrate that dechlorinating bacteria were able to accept reducing equivalents directly from the modified electrode surface. The innovative concept, based on the stimulation of dechlorination reactions through the use of solid-state electrodes (we propose for this process the acronym BEARD: Bio-Electrochemically Assisted Reductive Dechlorination), holds promise for in situ bioremediation of chlorinated-solvent-contaminated groundwater, and has several potential advantages over traditional approaches based on the subsurface injection of organic compounds. The results of this study raise the possibility that immobilization of selected redox mediators may be a general strategy for stimulating and controlling a range of microbial reactions using insoluble electrodes as electron donors.

Synthesis of wheat straw cellulose-g-poly (potassium acrylate)/PVA semi-IPNs superabsorbent resin.

PubMed

Liu, Jia; Li, Qian; Su, Yuan; Yue, Qinyan; Gao, Baoyu; Wang, Rui

2013-04-15

To better use wheat straw and minimize its negative impact on environment, a novel semi-interpenetrating polymer networks (semi-IPNs) superabsorbent resin (SAR) composed of wheat straw cellulose-g-poly (potassium acrylate) (WSC-g-PKA) network and linear polyvinyl alcohol (PVA) was prepared by polymerization in the presence of a redox initiating system. The structure and morphology of semi-IPNs SAR were characterized by means of FTIR, SEM and TGA, which confirmed that WSC and PVA participated in the graft polymerization reaction with acrylic acid (AA). The factors that can influence the water absorption of the semi-IPNs SAR were investigated and optimized, including the weight ratios of AA to WSC and PVA to WSC, the content of initiator and crosslinker, neutralization degree (ND) of AA, reaction temperature and time. The semi-IPNs SAR prepared under optimized synthesis condition gave the best water absorption of 266.82 g/g in distilled water and 34.32 g/g in 0.9 wt% NaCl solution. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of silicate module of water glass on rheological parameters of poly(sodium acrylate)/sodium silicate hydrogels

NASA Astrophysics Data System (ADS)

Mastalska-Popiawska, J.; Izak, P.

2017-01-01

The poly(sodium acrylate)/sodium silicate hydrogels were synthesized in the presence of sodium thiosulphate and potassium persulphate as the redox initiators and N,N’-methylene-bisacrylamide as the cross-linking monomer. 20 wt% aqueous solution of sodium acrylate was polymerized together with water glass with different silicate modules (M) from 1.74 to 2.29, in three mass ratio of the monomer solution to the water glass 2:1, 1:1 and 1:2. Such obtained hybrid composites were rheologically tested using the oscillation method. It allowed to designate the crossover point during polymerization, as well as to define the viscoelastic properties of the casted hydrogel samples one week after the reaction. The obtained results of the oscillation measurements showed that cross-linking reaction proceeds very quickly and the lower the silicate module is, the process starts faster. After the completion of the reaction the silicate-polymer hydrogels are strongly elastic materials and the highest elasticity characterizes systems with the mass ratio 1:2, i.e. with the highest water glass content.

Fast and easy enzyme immobilization by photoinitiated polymerization for efficient bioelectrochemical devices.

PubMed

Suraniti, Emmanuel; Studer, Vincent; Sojic, Neso; Mano, Nicolas

2011-04-01

Immobilization and electrical wiring of enzymes is of particular importance for the elaboration of efficient biosensors and can be cumbersome. Here, we report a fast and easy protocol for enzyme immobilization, and as a proof of concept, we applied it to the immobilization of bilirubin oxidase, a labile enzyme. In the first step, bilirubin oxidase is mixed with a redox hydrogel "wiring" the enzyme reaction centers to electrodes. Then, this adduct is covered by an outer layer of PEGDA made by photoinitiated polymerization of poly(ethylene-glycol) diacrylate (PEGDA) and a photoclivable precursor, DAROCUR. This two-step protocol is 18 times faster than the current state-of-the-art protocol and leads to currents 25% higher. In addition, the outer layer of PEGDA acts as a protective layer increasing the lifetime of the electrode by 100% when operating continuously for 2000 s and by 60% when kept in dry state for 24 h. This new protocol is particularly appropriate for labile enzymes that quickly denaturate. In addition, by tuning the ratio PEGDA/DAROCUR, it is possible to make the enzyme electrodes even more active or more stable.

Preparation of crosslinked amphiphilic silver nanogel as thin film corrosion protective layer for steel.

PubMed

Atta, Ayman M; El-Mahdy, Gamal A; Al-Lohedan, Hamad A; Ezzat, Abdelrahman O

2014-07-17

Monodisperse silver nanoparticles were synthesized by a new developed method via reaction of AgNO3 and oleic acid with the addition of a trace amount of Fe3+ ions. Emulsion polymerization at room temperature was employed to prepare a core-shell silver nanoparticle with controllable particle size. N,N'-methylenebisacrylamide (MBA) and potassium peroxydisulfate (KPS) were used as a crosslinker, and as redox initiator system, respectively for crosslinking polymerization. The structure and morphology of the silver nanogels were characterized by Fourier transform infrared spectroscopy (FTIR), transmission and scanning electron microscopy (TEM and SEM). The effectiveness of the synthesized compounds as corrosion inhibitors for steel in 1 M HCl was investigated by various electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Monolayers of silver nanoparticle were self-assembled on the fresh active surface of the steel electrode and have been tested as a corrosion inhibitor for steel in 1 M HCl solution. The results of polarization measurements showed that nanogel particles act as a mixed type inhibitor.

Rechargeable quasi-solid state lithium battery with organic crystalline cathode

PubMed Central

Hanyu, Yuki; Honma, Itaru

2012-01-01

Utilization of metal-free low-cost high-capacity organic cathodes for lithium batteries has been a long-standing goal, but critical cyclability problems owing to dissolution of active materials into the electrolyte have been an inevitable obstacle. For practical utilisation of numerous cathode-active compounds proposed over the past decades, a novel battery construction strategy is required. We have designed a solid state cell that accommodates organic cathodic reactions in solid phase. The cell was successful at achieving high capacity exceeding 200 mAh/g with excellent cycleability. Further investigations confirmed that our strategy is effective for numerous other redox-active organic compounds. This implies hundreds of compounds dismissed before due to low cycleability would worth a re-visit under solid state design. PMID:22693655

Preparation, characterization, and activity of α-Ti(HPO4)2 supported metallocene catalysts

NASA Astrophysics Data System (ADS)

Shi, Yasai; Yuan, Yuan; Xu, Qinghong; Yi, Jianjun

2016-10-01

A series of heterogeneous catalysts by loading metallocenes on surface of α-Ti(HPO4)2, a kind of solid acid, has been synthesized. Polymerization of alkenes, including ethylene and propylene, based on participation of the heterogeneous catalysts were studied and the results were compared to metallocenes supported on silica gel, α-Zr(HPO4)2 and clay. Higher catalytic activity, larger polymer molecular weight and narrow distribution of polymer molecular weight were obtained. Acidic strength of the support and its influence to metallocenes were studied to discover intrinsic factors in the polymerizations.

ELECTRICAL LEAK LOCATION METHOD FOR GEOMEMBRANE LINERS

EPA Science Inventory

Geomembrane liners are sheets of polymeric materials used to prevent leakage of waste from and infiltration of rainwater into solid waste landfills and surface impoundments. The method described consists of voltage applied between the liner and the earth under the liner which pro...

Synthesis of 3'-, or 5'-, or internal methacrylamido-modified oligonucleotides

DOEpatents

Golova, Julia B.; Chernov, Boris K.

2010-04-27

New modifiers were synthesized for incorporation of a methacrylic function in 3'-, 5'- and internal positions of oligonucleotides during solid phase synthesis. A modifier was used for synthesis of 5'-methacrylated oligonucleotides for preparation of microarrays by a co-polymerization method.

A solid ceramic electrolyte system for measuring redox conditions in high temperature gas mixing studies

NASA Technical Reports Server (NTRS)

Williams, R. J.

1972-01-01

The details of the construction and operation of a gas mixing furnace are presented. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a standard vertical-quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the highinput impedance electronics necessary for measurements and a simplified version of standard gas mixing apparatus. The calibration and maintenance of the system are discussed.

High Power Storage System Based on Thin Film Solid Ionics.

DTIC Science & Technology

1988-02-01

linear sweep voltametry (LSV) technique (Dahn and Hearing, 1981). We observe that in non-annealed film the peak at 1.2 V Is very strong compared to that...1.8V. The redox stability range has been determined by cyclic voltametry for different preparation conditions of the films. Lithium solid state hybrid...Fig. 6 Linear sweep voltagrams at 7gV/s rate of InSe films prepared at Ts=RT (a) non-annealed, (b) annealed at 475 K during 64 hours. 11 1 -’ 1 J, -I

Bloch surface waves confined in one dimension with a single polymeric nanofibre

NASA Astrophysics Data System (ADS)

Wang, Ruxue; Xia, Hongyan; Zhang, Douguo; Chen, Junxue; Zhu, Liangfu; Wang, Yong; Yang, Erchan; Zang, Tianyang; Wen, Xiaolei; Zou, Gang; Wang, Pei; Ming, Hai; Badugu, Ramachandram; Lakowicz, Joseph R.

2017-02-01

Polymeric fibres with small radii (such as ≤125 nm) are delicate to handle and should be laid down on a solid substrate to obtain practical devices. However, placing these nanofibres on commonly used glass substrates prevents them from guiding light. In this study, we numerically and experimentally demonstrate that when the nanofibre is placed on a suitable dielectric multilayer, it supports a guided mode, a Bloch surface wave (BSW) confined in one dimension. The physical origin of this new mode is discussed in comparison with the typical two-dimensional BSW mode. Polymeric nanofibres are easily fabricated to contain fluorophores, which make the dielectric nanofibre and multilayer configuration suitable for developing a large range of new nanometric scale devices, such as processor-memory interconnections, devices with sensitivity to target analytes, incident polarization and multi-colour BSW modes.

Nanoporous polymeric nanofibers based on selectively etched PS-b-PDMS block copolymers.

PubMed

Demirel, Gokcen B; Buyukserin, Fatih; Morris, Michael A; Demirel, Gokhan

2012-01-01

One-dimensional nanoporous polymeric nanofibers have been fabricated within an anodic aluminum oxide (AAO) membrane by a facile approach based on selective etching of poly(dimethylsiloxane) (PDMS) domains in polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) block copolymers that had been formed within the AAO template. It was observed that prior to etching, the well-ordered PS-b-PDMS nanofibers are solid and do not have any porosity. The postetched PS nanofibers, on the other hand, had a highly porous structure having about 20-50 nm pore size. The nanoporous polymeric fibers were also employed as a drug carrier for the native, continuous, and pulsatile drug release using Rhodamine B (RB) as a model drug. These studies showed that enhanced drug release and tunable drug dosage can be achieved by using ultrasound irradiation. © 2011 American Chemical Society

Preparation of Paraffin@Poly(styrene-co-acrylic acid) Phase Change Nanocapsules via Combined Miniemulsion/Emulsion Polymerization.

PubMed

Zhang, Feng; Liu, Tian-Yu; Hou, Gui-Hua; Guan, Rong-Feng; Zhang, Jun-Hao

2018-06-01

The fast development of solid-liquid phase change materials calls for nanomaterials with large specific surface area for rapid heat transfer and encapsulation of phase change materials to prevent potential leakage. Here we report a combined miniemulsion/emulsion polymerization method to prepare poly(styrene-co-acrylic acid)-encapsulated paraffin (paraffin@P(St-co-AA)) nanocapsules. The method could suppress the shortcomings of common miniemulsion polymerization (such as evaporation of monomer and decomposition of initiator during ultrasonication). The paraffin@P(St-co-AA) nanocapsules are uniform in size and the polymer shell can be controlled by the weight ratio of St to paraffin. The phase change behavior of the nanocapsules is similar to that of pure paraffin. We believe our method can also be utilized to synthesize other core-shell phase change materials.

Solid state polymerization and crystallography of polyimide precursors. Ph.D. Thesis - Va. Univ.

NASA Technical Reports Server (NTRS)

Wakelyn, N. T.

1974-01-01

Although the production of crystallinity in a polymeric system has historically led to commerically useful properties, the polyimides, prized for their high temperature characteristics, as customarily synthesized by melt or solution casting, are amorphous. It is shown that polymide containing residual crystallinity can be synthesized by isothermal annealing of crystals of the salt of the diisopropyl ester of pyromellitic acid and phenylene diamine. The reaction is topochemical in that the geometry of the polymer product is dependent upon that of the crystalline precursor. Infrared spectroscopy reveals the presence of imide absorption in the polymer, while powder diffractometry suggests residual crystallinity. Single crystal X-ray analysis of the monomer yields a structure of chains of alternating acid and base suggesting that the monomer is amenable to polymerization with a minimum of geometrical disruption.

A New Composite Electrode Applied for Studying the Electrochemistry of Insoluble Particles: α-HgS.

PubMed

Yang, Minjun; Compton, Richard G

2018-05-22

The redox chemistry of solid α-HgS particles is revealed using a carbon/PVDF composite containing α-HgS, carbon black, polyvinylidene fluoride (PVDF). The electrochemical behaviour of the carbon/PVDF composite is first characterised with three water insoluble organic solids. Then the reduction of solid α-HgS particles is investigated and found to occur at a high negative potential, -1.82 V versus saturated mercury sulphate reference electrode, to form metallic mercury and sulphide ions. The subsequent oxidation of metallic mercury and sulphide occurs at +0.24 and -0.49 V versus MSE respectively. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A review of lithium and non-lithium based solid state batteries

NASA Astrophysics Data System (ADS)

Kim, Joo Gon; Son, Byungrak; Mukherjee, Santanu; Schuppert, Nicholas; Bates, Alex; Kwon, Osung; Choi, Moon Jong; Chung, Hyun Yeol; Park, Sam

2015-05-01

Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.

Crystal-field-driven redox reactions: How common minerals split H2O and CO2 into reduced H2 and C plus oxygen

NASA Technical Reports Server (NTRS)

Freund, F.; Batllo, F.; Leroy, R. C.; Lersky, S.; Masuda, M. M.; Chang, S.

1991-01-01

It is difficult to prove the presence of molecular H2 and reduced C in minerals containing dissolved H2 and CO2. A technique was developed which unambiguously shows that minerals grown in viciously reducing environments contain peroxy in their crystal structures. The peroxy represent interstitial oxygen atoms left behind when the solute H2O and/or CO2 split off H2 and C as a result of internal redox reactions, driven by the crystal field. The observation of peroxy affirms the presence of H2 and reduced C. It shows that the solid state is indeed an unusual reaction medium.

Evaluation of the effects of polymeric chitosan/tripolyphosphate and solid lipid nanoparticles on germination of Zea mays, Brassica rapa and Pisum sativum.

PubMed

Nakasato, Daniele Y; Pereira, Anderson E S; Oliveira, Jhones L; Oliveira, Halley C; Fraceto, Leonardo F

2017-08-01

Although the potential toxicity of many metallic and carbon nanoparticles to plants has been reported, few studies have evaluated the phytotoxic effects of polymeric and solid lipid nanoparticles. The present work described the preparation and characterization of chitosan/tripolyphosphate (CS/TPP) nanoparticles and solid lipid nanoparticles (SLN) and evaluated the effects of different concentrations of these nanoparticles on germination of Zea mays, Brassica rapa, and Pisum sativum. CS/TPP nanoparticles presented an average size of 233.6±12.1nm, polydispersity index (PDI) of 0.30±0.02, and zeta potential of +21.4±1.7mV. SLN showed an average size of 323.25±41.4nm, PDI of 0.23±0.103, and zeta potential of -13.25±3.2mV. Nanotracking analysis enabled determination of concentrations of 1.33×10 10 (CS/TPP) and 3.64×10 12 (SLN) nanoparticles per mL. At high concentrations, CS/TPP nanoparticles caused complete inhibition of germination, and thus negatively affected the initial growth of all tested species. Differently, SLN presented no phytotoxic effects. The different size and composition and the opposite charges of SLN and CS/TPP nanoparticles could be associated with the differential phytotoxicity of these nanomaterials. The present study reports the phytotoxic potential of polymeric CS/TPP nanoparticles towards plants, indicating that further investigation is needed on the effects of such formulations intended for future use in agricultural systems, in order to avoid damage to the environment. Copyright © 2017 Elsevier Inc. All rights reserved.

Matrix-assisted laser desorption/ionization mass spectrometric analysis of poly(3,4-ethylenedioxythiophene) in solid-state dye-sensitized solar cells: comparison of in situ photoelectrochemical polymerization in aqueous micellar and organic media.

PubMed

Zhang, Jinbao; Ellis, Hanna; Yang, Lei; Johansson, Erik M J; Boschloo, Gerrit; Vlachopoulos, Nick; Hagfeldt, Anders; Bergquist, Jonas; Shevchenko, Denys

2015-04-07

Solid-state dye-sensitized solar cells (sDSCs) are devoid of such issues as electrolyte evaporation or leakage and electrode corrosion, which are typical for traditional liquid electrolyte-based DSCs. Poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most popular and efficient p-type conducting polymers that are used in sDSCs as a solid-state hole-transporting material. The most convenient way to deposit this insoluble polymer into the dye-sensitized mesoporous working electrode is in situ photoelectrochemical polymerization. Apparently, the structure and the physicochemical properties of the generated conducting polymer, which determine the photovoltaic performance of the corresponding solar cell, can be significantly affected by the preparation conditions. Therefore, a simple and fast analytical method that can reveal information on polymer chain length, possible chemical modifications, and impurities is strongly required for the rapid development of efficient solar energy-converting devices. In this contribution, we applied matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) for the analysis of PEDOT directly on sDSCs. It was found that the PEDOT generated in aqueous micellar medium possesses relatively shorter polymeric chains than the PEDOT deposited from an organic medium. Furthermore, the micellar electrolyte promotes a transformation of one of the thiophene terminal units to thiophenone. The introduction of a carbonyl group into the PEDOT molecule impedes the growth of the polymer chain and reduces the conductivity of the final polymer film. Both the simplicity of sample preparation (only application of the organic matrix onto the solar cell is needed) and the rapidity of analysis hold the promise of making MALDI MS an essential tool for the physicochemical characterization of conducting polymer-based sDSCs.

Modeling normal shock velocity curvature relations for heterogeneous explosives

NASA Astrophysics Data System (ADS)

Yoo, Choong-Shik; Tomasino, Dane; Smith, Jesse; Kim, Minseob

2017-01-01

Many simple molecules such as N2 and CO2 have the potential to form extended "polymeric" solids under extreme conditions, which can store a large sum of chemical energy in its three-dimensional network structures made of strong covalent bonds. Diatomic nitrogen is particularly of interest because of the uniquely large energy difference between the single (160 kJ/mol) and triple (950 kJ/mol) bonds. As such, the transformation of singly bonded polymeric nitrogen back to triply bonded diatomic nitrogen molecules can release large energy ( 33 kJ/cm3 - three times that of HMX) without any negative environmental impact. Therefore, the goal of the present study has been to investigate the transformation of nitrogen and nitrogen-rich compounds to new singly bonded nitrogen-rich solids at high pressures and temperatures, using heated diamond anvil cells, Raman spectroscopy, and third-generation synchrotron x-ray diffraction. Recently, we have found a new form of singly bonded layered polymeric nitrogen (LP-N), synthesized in the stability pressure-temperature field higher than that of cg-N. This new phase is characterized by a 2D layered structure similar to the predicted Pba2 and two colossal Raman bands, arising from two groups of highly polarized nitrogen atoms. This result also provides a new constraint for the nitrogen phase diagram, highlighting an unusual symmetry lowering 3D cg- to 2D LP-N transition and thereby the enhanced electrostatic contribution to the stabilization of this densely packed LP-N. In this paper, we will review this finding of LP-N, update the phase diagram of nitrogen, and offer a chemistry view of pressure-induced transformations in dense molecular solids.

Determining the pH of Mars from the Viking labelled release reabsorption effect

NASA Technical Reports Server (NTRS)

Plumb, Robert C.

1992-01-01

The acid-base properties and redox potentials of solids are two of the more fundamental chemical parameters characterizing a material. Knowledge of these parameters for martian regolith fines would be of considerable value in determining what specific compounds are present and making judgements on what reactions are possible.

Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

NASA Technical Reports Server (NTRS)

Freund, Friedemann

1991-01-01

Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

Electroactive and biocompatible functionalization of graphene for the development of biosensing platforms.

PubMed

Halder, Arnab; Zhang, Minwei; Chi, Qijin

2017-01-15

Design and synthesis of low-cost, highly stable, electroactive and biocompatible material is one of the key steps for the advancement of electrochemical biosensing systems. To this end, we have explored a facile way for the successful synthesis of redox active and bioengineering of reduced graphene oxide (RGO) for the development of versatile biosensing platform. A highly branched polymer (PEI) is used for reduction and simultaneous derivation of graphene oxide (GO) to form a biocompatible polymeric matrix on RGO nanosheet. Ferrocene redox moieties are then wired onto RGO nanosheets through the polymer matrix. The as-prepared functional composite is electrochemically active and enables to accommodate enzymes stably. For proof-of-concept studies, two crucial redox enzymes for biosensors (i.e. cholesterol oxidase and glucose oxidase) are targeted. The enzyme integrated and RGO supported biosensing hybrid systems show high stability, excellent selectivity, good reproducibility and fast sensing response. As measured, the detection limit of the biosensors for glucose and cholesterol is 5µM and 0.5µM (S/N=3), respectively. The linear response range of the biosensor is from 0.1 to 15.5mM for glucose and from 2.5 to 25µM for cholesterol. Furthermore, this biosensing platform shows good anti-interference ability and reasonable stability. The nanohybrid biosensing materials can be combined with screen-printed electrodes, which are successfully used for measuring the glucose and cholesterol level of real human serum samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

PubMed Central

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

2015-01-01

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

Catalyst surfaces for the chromous/chromic redox couple

NASA Technical Reports Server (NTRS)

Giner, J. D.; Cahill, K. J. (Inventor)

1980-01-01

An electricity producing cell of the reduction-oxidation (REDOX) type is described. The cell is divided into two compartments by a membrane, each compartment containing a solid inert electrode. A ferrous/ferric couple in a chloride solution serves as a cathode fluid which is circulated through one of the compartments to produce a positive electric potential disposed therein. A chromic/chromous couple in a chloride solution serves as an anode fluid which is circulated through the second compartment to produce a negative potential on an electrode disposed therein. The electrode is an electrically conductive, inert material plated with copper, silver or gold. A thin layer of lead plates onto the copper, silver or gold layer when the cell is being charged, the lead ions being available from lead chloride which was added to the anode fluid. If the REDOX cell is then discharged, the current flows between the electrodes causing the lead to deplate from the negative electrode and the metal coating on the electrode will act as a catalyst to cause increased current density.

Room temperature, hybrid sodium-based flow batteries with multi-electron transfer redox reactions

DOE PAGES

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; ...

2015-06-11

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volumemore » of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multielectron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. Furthermore, the critical barriers to mature this new HNFBs have also been explored.« less

Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing

DOE PAGES

Prabhakaran, Venkateshkumar; Mehdi, B. Layla; Ditto, Jeffrey J.; ...

2016-04-21

Here, the rational design of improved electrode-electrolyte interfaces (EEI) for energy storage is critically dependent on a molecular-level understanding of ionic interactions and nanoscale phenomena. The presence of non-redox active species at EEI has been shown to strongly influence Faradaic efficiency and long-term operational stability during energy storage processes. Herein, we achieve substantially higher performance and long-term stability of EEI prepared with highly-dispersed discrete redox-active cluster anions (50 ng of pure ~0.7 nm size molybdenum polyoxometalate anions (POM) anions on 25 mg (≈ 0.2 wt%) carbon nanotube (CNT) electrodes) by complete elimination of strongly coordinating non-redox species through ion soft-landingmore » (SL). For the first time, electron microscopy provides atomically-resolved images of individual POM species directly on complex technologically relevant CNT electrodes. In this context, SL is established as a versatile approach for the controlled design of novel surfaces for both fundamental and applied research in energy storage.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

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

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Tunable thermal expansion in framework materials through redox intercalation

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

Chen, Jun; Gao, Qilong; Sanson, Andrea

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present, offering a potential route for control. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF 3, doped with 10% Fe to enable reduction. Themore » small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. As a result, redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.« less

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

PubMed Central

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; Li, Jinyang; Schwab, Mark J.; Brudvig, Gary W.; Taylor, André D.

2016-01-01

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme's oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage. PMID:27759005

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

DOE PAGES

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; ...

2016-10-19

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasingmore » dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.« less

Tunable thermal expansion in framework materials through redox intercalation

DOE PAGES

Chen, Jun; Gao, Qilong; Sanson, Andrea; ...

2017-02-09

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present, offering a potential route for control. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF 3, doped with 10% Fe to enable reduction. Themore » small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. As a result, redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.« less

Monolithic microfluidic concentrators and mixers

DOEpatents

Frechet, Jean M.; Svec, Frantisek; Yu, Cong; Rohr, Thomas

2005-05-03

Microfluidic devices comprising porous monolithic polymer for concentration, extraction or mixing of fluids. A method for in situ preparation of monolithic polymers by in situ initiated polymerization of polymer precursors within microchannels of a microfluidic device and their use for solid phase extraction (SPE), preconcentration, concentration and mixing.

Radical polymerization of capillary bridges between micron-sized particles in liquid bulk phase as a low temperature route to produce porous solid materials.

PubMed

Hauf, Katharina; Riazi, Kamran; Willenbacher, Norbert; Koos, Erin

2017-10-01

We present a generic and versatile low temperature route to produce macro-porous bodies with porosity and pore size distribution that are adjustable in a wide range. Capillary suspensions, where the minor fluid is a monomer, are used as pre-cursors. The monomer is preferentially located between the particles, creating capillary bridges, resulting in a strong, percolating network. Thermally induced polymerization of these bridges at temperatures below 100 °C for less than 5 hours and subsequent removal of the bulk fluid yields macroscopic, self-supporting solid bodies with high porosity. This process is demonstrated using methylmethacrylate and hydroxyethylmethacrlyate with glass particles as a model system. The produced PMMA had a molecular weight of about 500.000 g/mol and dispersity about three. Application specific porous bodies, including PMMA particles connected by PMMA bridges, micron-sized capsules containing phase change material with high inner surface, and porous graphite membranes with high electrical conductivity, are also shown.

High degree of polymerization in a fullerene-containing supramolecular polymer.

PubMed

Isla, Helena; Pérez, Emilio M; Martín, Nazario

2014-05-26

Supramolecular polymers based on dispersion forces typically show lower molecular weights (MW) than those based on hydrogen bonding or metal-ligand coordination. We present the synthesis and self-assembling properties of a monomer featuring two complementary units, a C60 derivative and an exTTF-based macrocycle, that interact mainly through π-π, charge-transfer, and van der Waals interactions. Thanks to the preorganization in the host part, a remarkable log K(a)=5.1±0.5 in CHCl3 at room temperature is determined for the host-guest couple. In accordance with the large binding constant, the monomer self-assembles in the gas phase, in solution, and in the solid state to form linear supramolecular polymers with a very high degree of polymerization. A MW above 150 kDa has been found experimentally in solution, while in the solid state the monomer forms extraordinarily long, straight, and uniform fibers with lengths reaching several microns. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radical polymerization of capillary bridges between micron-sized particles in liquid bulk phase as a low temperature route to produce porous solid materials

PubMed Central

Hauf, Katharina; Riazi, Kamran; Willenbacher, Norbert; Koos, Erin

2018-01-01

We present a generic and versatile low temperature route to produce macro-porous bodies with porosity and pore size distribution that are adjustable in a wide range. Capillary suspensions, where the minor fluid is a monomer, are used as pre-cursors. The monomer is preferentially located between the particles, creating capillary bridges, resulting in a strong, percolating network. Thermally induced polymerization of these bridges at temperatures below 100 °C for less than 5 hours and subsequent removal of the bulk fluid yields macroscopic, self-supporting solid bodies with high porosity. This process is demonstrated using methylmethacrylate and hydroxyethylmethacrlyate with glass particles as a model system. The produced PMMA had a molecular weight of about 500.000 g/mol and dispersity about three. Application specific porous bodies, including PMMA particles connected by PMMA bridges, micron-sized capsules containing phase change material with high inner surface, and porous graphite membranes with high electrical conductivity, are also shown. PMID:29503494

Influence of solids retention time on membrane fouling: characterization of extracellular polymeric substances and soluble microbial products.

PubMed

Duan, Liang; Tian, Zhiyong; Song, Yonghui; Jiang, Wei; Tian, Yuan; Li, Shan

2015-01-01

The objective of this study was to investigate the influence of solids retention time (SRT) on membrane fouling and the characteristics of biomacromolecules. Four identical laboratory-scale membrane bioreactors (MBRs) were operated with SRTs for 10, 20, 40 and 80 days. The results indicated that membrane fouling occurred faster and more readily under short SRTs. Fouling resistance was the primary source of filtration resistance. The modified fouling index (MFI) results suggested that the more ready fouling at short SRTs could be attributed to higher concentrations of soluble microbial products (SMP). Fourier transform infrared (FTIR) spectra indicated that the SRT had a weak influence on the functional groups of the total extracellular polymeric substances (TEPS) and SMP. However, the MBR under a short SRT had more low-molecular-weight (MW) compounds (<1 kDa) and fewer high-MW compounds (>100 kDa). Aromatic protein and tryptophan protein-like substances were the dominant groups in the TEPS and SMP, respectively.

The effect of solids retention times on the characterization of extracellular polymeric substances and soluble microbial products in a submerged membrane bioreactor.

PubMed

Duan, Liang; Song, Yonghui; Yu, Huibin; Xia, Siqing; Hermanowicz, Slawomir W

2014-07-01

In this study, the effect of solids retention times (SRTs) on extracellular polymeric substances (EPS) and soluble microbial products (SMPs) were investigated in a membrane bioreactor (MBR) at SRTs of 10, 5 and 3 days. The results showed that more carbohydrates and proteins were accumulated at short SRT, which can due to the higher biomass activity in the reactor. The molecular weight (MW) distribution analysis suggested that macromolecules (MW>30 kDa) and small molecules (MW<1 kDa) were the dominant fraction of EPS and SMP, respectively. The reactor at shorter SRT had more small molecules and less macromolecules of carbohydrates. The MW distribution of total organic carbon (TOC) suggested that other organic moieties were exuded by microbes into the solution. The shorter SRT had more undefined microbial by-product-like substances and different O − H bonds in hydroxyl functional groups. Copyright © 2014 Elsevier Ltd. All rights reserved.

Increasing the wear resistance of ultra-high molecular weight polyethylene by adding solid lubricating fillers

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

Panin, S. V., E-mail: svp@ispms.tsc.ru; Kornienko, L. A.; Poltaranin, M. A.

2014-11-14

In order to compare effectiveness of adding solid lubricating fillers for polymeric composites based on ultra-high molecular weight polyethylene (UHMWPE) with graphite, molybdenum disulfide and polytetrafluoroethylene, their tribotechnical characteristics under dry friction, boundary lubrication and abrasive wearing were investigated. The optimal weight fractions of fillers in terms of improving wear resistance have been determined. The supramolecular structure and topography of wear track surfaces of UHMWPE-based composites with different content of fillers have been studied.

Materials Science and Engineering-1989 Publications (Naval Research Laboratory)

DTIC Science & Technology

1991-03-29

34 D.G. Cory, J.B. Miller, A.N. Garroway "Acousto-Optic and Linear Electro-Optic Journal of Magnetic Resonance, 85, 219 Properties of Organic Polymeric...34Demonstration of Indirect Detection of ൕC Refocused Gradient Imaging of Solids" 14N Overtone NMR Transitions" J.B. Miller, A.N. Garroway A.N. Garroway , J.B...Conductive Polymer Solids" Chemical Vapor Sensors" J.B. Miller, A.N. Garroway J.F. Giuiani, T.M. Keller Journal of Magnetic Resonance, 85, 255 Journal of

RAFT Aqueous Dispersion Polymerization Yields Poly(ethylene glycol)-Based Diblock Copolymer Nano-Objects with Predictable Single Phase Morphologies

PubMed Central

2013-01-01

A poly(ethylene glycol) (PEG) macromolecular chain transfer agent (macro-CTA) is prepared in high yield (>95%) with 97% dithiobenzoate chain-end functionality in a three-step synthesis starting from a monohydroxy PEG113 precursor. This PEG113-dithiobenzoate is then used for the reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). Polymerizations conducted under optimized conditions at 50 °C led to high conversions as judged by 1H NMR spectroscopy and relatively low diblock copolymer polydispersities (Mw/Mn < 1.25) as judged by GPC. The latter technique also indicated good blocking efficiencies, since there was minimal PEG113 macro-CTA contamination. Systematic variation of the mean degree of polymerization of the core-forming PHPMA block allowed PEG113-PHPMAx diblock copolymer spheres, worms, or vesicles to be prepared at up to 17.5% w/w solids, as judged by dynamic light scattering and transmission electron microscopy studies. Small-angle X-ray scattering (SAXS) analysis revealed that more exotic oligolamellar vesicles were observed at 20% w/w solids when targeting highly asymmetric diblock compositions. Detailed analysis of SAXS curves indicated that the mean number of membranes per oligolamellar vesicle is approximately three. A PEG113-PHPMAx phase diagram was constructed to enable the reproducible targeting of pure phases, as opposed to mixed morphologies (e.g., spheres plus worms or worms plus vesicles). This new RAFT PISA formulation is expected to be important for the rational and efficient synthesis of a wide range of biocompatible, thermo-responsive PEGylated diblock copolymer nano-objects for various biomedical applications. PMID:24400622

Kinetics and equilibria of redox systems at temperatures as low as 300°C

NASA Astrophysics Data System (ADS)

Burkhard, Dorothee J. M.; Ulmer, Gene C.

1995-05-01

ZrO 2 oxygen sensors, gas mixtures, and conventional solid buffers have been used for decades to either control or measure oxygen fugacity (ƒ O 2) at high temperatures. In dry systems below ca. 700°C these techniques were used cautiously, if at all, due to doubt that there was any equilibration at lower temperatures. We have re-investigated these three types of redox systems in a study where each system (two different Y 2O 3ZrO 2 cells, four different gas mixtures, and four different dry solid buffers) was simultaneously cross-checked with the other to temperatures below 300°C and compared to JANAF data, extrapolated down to low temperatures. Steady and reproducible readings were observed down to T ≤ 300°C, from which we infer fast kinetics for all three systems. Specifically, we find equilibration of various CO 2H 2 gas mixtures over the entire temperature range and to much lower temperature than previously predicted. We assign the reactivity (decomposition) of CO 2 at low T to the catalytic action of Pt, whereby chemisorption of H 2 on the platinum surface enhances the reactivity with CO 2. This catalytic reactivity is diminished over time due to a long-term irreversible reaction of Pt with H 2. Subsequent embrittling and aging after prolonged exposure to H 2 explains erroneously high emf readings. Oxygen sensing of ZrO 2 cells is linear in 1/ T-log ƒ O 2 space and Nernstian at high temperatures. However, for cells with a specific and complex trace element chemistry, one may observe a non-Nernstian behavior in the low T range, i.e., below 470° or lower, probably caused by partially blocked O 2- migration, dependent on the H 2 content in the gas mixture. Linearity and reproducibility of this deviation still allows, however, a useable calibration. Solid buffers of the metal-metal oxide type are known to alloy with noble metals and we therefore used AgPd electrodes, for consistency in all studies, including (IW), (IM), (FMQ), and (NNO). Whereas (IW) and (IM) can be used in the temperature range of consideration, (FMQ) and (NNO) react sluggishly. Complex defect structure of (FMQ) and age alteration of Ni surfaces by chemisorption of oxygen and/or AgNi alloying of (NNO) may be the reason. Fast kinetics and successful redox sensing of CO 2H 2 gas mixtures, of ZrO 2 cells and of at least some solid buffers are therefore promising for future research on low- T redox equilibria.

Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies.

PubMed

Chen, Chunmei; Kukkadapu, Ravi K; Lazareva, Olesya; Sparks, Donald L

2017-07-18

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57 Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic (XAS) techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplains, which exhibited a succession of oxic, anoxic, and suboxic-oxic zones with increasing depth along the vertical profiles. The incised stream channel is bounded on the east by a narrow floodplain and a steep hillslope, and on the west by a broad floodplain. In the eastern floodplain, the anoxic conditions at the intermediate horizon (55-80 cm) coincided with lower Fe(III)-oxides (particularly ferrihydrite), in concurrence with a greater reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II), relative to the oxic near-surface and sandy gravel layers. In addition, the anoxic conditions in the eastern floodplain coincided with increased crystallinity of goethite, relative to the oxic layers. In the most reduced intermediate sediments at 80-120 cm of the western floodplain, no Fe(III)-oxides were detected, concurrent with the greatest PS-Fe(III) reduction (PS-Fe(II)/Fe(III) ratio ≈ 1.2 (Mössbauer) or 0.8 (XAS)). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a much less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

THE ROLE OF 4-HYDROXYPHENYLPYRUVATE DIOXYGENASE IN ENHANCEMENT OF SOLID-PHASE ELECTRON TRANSFER BY SHEWANELLA ONEIDENSIS MR-1

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

Turick, C; Amy Ekechukwu, A

2007-06-01

While mechanistic details of dissimilatory metal reduction are far from being understood, it is postulated that the electron transfer to solid metal oxides is mediated by outer membrane-associated c-type cytochromes and redox active electron shuttling compounds. This study focuses on the production of homogensitate in Shewanella oneidensis MR-1, an intermediate of tyrosine degradation pathway, which is a precursor of a redox cycling metabolite, pyomelanin. In this study, we determined that two enzymes involved in this pathway, 4-hydroxyphenylpyruvate dioxygenase (4HPPD) and homogentisate 1,2-dioxygenase are responsible for homogentisate production and oxidation, respectively. Inhibition of 4-HPPD activity with the specific inhibitor sulcotrione (2-(2-chloro-4-methanemore » sulfonylbenzoyl)-1,3-cyclohexanedione), and deletion of melA, a gene encoding 4-HPPD, resulted in no pyomelanin production by S. oneidensis MR-1. Conversely, deletion of hmgA which encodes the putative homogentisate 1,2-dioxygenase, resulted in pyomelanin overproduction. The efficiency and rates, with which MR-1 reduces hydrous ferric oxide, were directly linked to the ability of mutant strains to produce pyomelanin. Electrochemical studies with whole cells demonstrated that pyomelanin substantially increases the formal potential (E{sup o}{prime}) of S. oneidensis MR-1. Based on this work, environmental production of pyomelanin likely contributes to an increased solid-phase metal reduction capacity in Shewanella oneidensis.« less

[Utilization of polymeric micelle magnetic resonance imaging (MRI) contrast agent for theranostic system].

PubMed

Shiraishi, Kouichi

2013-01-01

We applied a polymeric micelle carrier system for the targeting of a magnetic resonance imaging (MRI) contrast agent. Prepared polymeric micelle MRI contrast agent exhibited a long circulation characteristic in blood, and considerable amount of the contrast agent was found to accumulate in colon 26 solid tumor by the EPR effect. The signal intensities of tumor area showed 2-folds increase in T1-weighted images at 24 h after i.v. injection. To observe enhancement of the EPR effect by Cderiv pretreatment on tumor targeting, we used the contrast agent for the evaluation by means of MRI. Cderiv pretreatment significantly enhanced tumor accumulation of the contrast agent. Interestingly, very high signal intensity in tumor region was found at 24 h after the contrast agent injection in Cderiv pretreated mice. The contrast agent visualized a microenvironmental change in tumor. These results indicate that the contrast agent exhibits potential use for tumor diagnostic agent. To combine with a polymeric micelle carrier system for therapeutic agent, the usage of the combination makes a new concept of "theranostic" for a better cancer treatment.

Polymeric behavior evaluation of PVP K30-poloxamer binary carrier for solid dispersed nisoldipine by experimental design.

PubMed

Kyaw Oo, May; Mandal, Uttam K; Chatterjee, Bappaditya

2017-02-01

High melting point polymeric carrier without plasticizer is unacceptable for solid dispersion (SD) by melting method. Combined polymer-plasticizer carrier significantly affects drug solubility and tableting property of SD. To evaluate and optimize the combined effect of a binary carrier consisting PVP K30 and poloxamer 188, on nisoldipine solubility and tensile strength of amorphous SD compact (SD compact ) by experimental design. SD of nisoldpine (SD nisol ) was prepared by melt mixing with different PVP K30 and poloxamer amount. A 3 2 factorial design was employed using nisoldipine solubility and tensile strength of SD compact as response variables. Statistical optimization by design expert software, and SD nisol characterization using ATR FTIR, DSC and microscopy were done. PVP K30:poloxamer, at a ratio of 3.73:6.63, was selected as the optimized combination of binary polymeric carrier resulting nisoldipine solubility of 115 μg/mL and tensile strength of 1.19 N/m 2 . PVP K30 had significant positive effect on both responses. Increase in poloxamer concentration after a certain level decreased nisoldipine solubility and tensile strength of SD compact . An optimized PVP K30-poloxamer binary composition for SD carrier was developed. Tensile strength of SD compact can be considered as a response for experimental design to optimize SD.

Porphyrin framework solids. Synthesis and structure of hybrid coordination polymers of tetra(carboxyphenyl)porphyrins and lanthanide-bridging ions.

PubMed

Muniappan, Sankar; Lipstman, Sophia; George, Sumod; Goldberg, Israel

2007-07-09

New types of porphyrin-based framework solids were constructed by reacting meso-tetra(3-carboxyphenyl)porphyrin and meso-tetra(4-carboxyphenyl)metalloporphyrins with common salts of lanthanide metal ions. The large size, high coordination numbers and strong affinity for oxo ligands of the latter, combined with favorable hydrothermal reaction conditions, allowed the formation of open three-dimensional single-framework architectures by coordination polymerization, in which the tetradentate porphyrin units are intercoordinated by multinuclear assemblies of the bridging metal ions. The latter serve as construction pillars of the supramolecular arrays, affording stable structures. Several modes of coordination polymerization were revealed by single-crystal X-ray diffraction. They differ by the spatial functionality of the porphyrin building blocks, the coordination patterns of the lanthanide-carboxylate assemblies, and the topology of the resulting frameworks. The seven new reported structures exhibit periodically spaced 0.4-0.6 nm wide channel voids that perforate the respective crystalline polymeric architectures and are accessible to solvent components. Materials based on the m-carboxyphenyl derivative reveal smaller channels than those based on the p-carboxyphenyl analogues. An additional complex of the former with a smaller third-row transition metal (Co) is characterized by coordination connectivity in two dimensions only. Thermal and powder-diffraction analyses confirm the stability of the lanthanide-TmCPP (TmCPP=tetra(m-carboxyphenyl)porphyrin) frameworks.

Charge transfer kinetics at the solid-solid interface in porous electrodes

NASA Astrophysics Data System (ADS)

Bai, Peng; Bazant, Martin Z.

2014-04-01

Interfacial charge transfer is widely assumed to obey the Butler-Volmer kinetics. For certain liquid-solid interfaces, the Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report a simple method to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures. The fitted reorganization energy matches the Born solvation energy for electron transfer from carbon to the iron redox site. The kinetics are thus limited by electron transfer at the solid-solid (carbon-LixFePO4) interface rather than by ion transfer at the liquid-solid interface, as previously assumed. The proposed experimental method generalizes Chidsey’s method for phase-transforming particles and porous electrodes, and the results show the need to incorporate Marcus kinetics in modelling batteries and other electrochemical systems.

Magnetic Resonance Imaging of Polymeric Drug Delivery Systems in Breast Cancer Solid Tumors

DTIC Science & Technology

2007-12-01

University of Maryland, Baltimore Baltimore, MD 21201- 1082 REPORT DATE: December 2007 TYPE OF REPORT: Annual Summary Addendum...Baltimore, MD 21201- 1082 9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR’S ACRONYM(S) U.S. Army Medical

Terraced spreading of simple liquids on solid surfaces

NASA Technical Reports Server (NTRS)

Yang, Ju-Xing; Koplik, Joel; Banavar, Jayanth R.

1992-01-01

We have studied the spreading of liquid drops on a solid surface by molecular-dynamics simulations of coexisting three-phase Lennard-Jones systems of liquid, vapor, and solid. We consider both spherically symmetric atoms and diatomic molecules, and a range of interaction strengths. As the attraction between liquid and solid increases we observe a smooth transition in spreading regimes, from partial to complete to terraced wetting. In the terraced case, where distinct monomolecular layers spread with different velocities, the layers are ordered but not solid, with substantial molecular diffusion both within and between layers. The quantitative behavior resembles recent experimental findings, but the detailed dynamics differ. In particular, the layers exhibit an unusual spreading law, where their radii vary in time as R-squared approximately equal to log10t, which disagrees with experiments on polymeric liquids as well as recent calculations.

Experimental evaluation and simulation of volumetric shrinkage and warpage on polymeric composite reinforced with short natural fibers

NASA Astrophysics Data System (ADS)

Santos, Jonnathan D.; Fajardo, Jorge I.; Cuji, Alvaro R.; García, Jaime A.; Garzón, Luis E.; López, Luis M.

2015-09-01

A polymeric natural fiber-reinforced composite is developed by extrusion and injection molding process. The shrinkage and warpage of high-density polyethylene reinforced with short natural fibers of Guadua angustifolia Kunth are analyzed by experimental measurements and computer simulations. Autodesk Moldflow® and Solid Works® are employed to simulate both volumetric shrinkage and warpage of injected parts at different configurations: 0 wt.%, 20 wt.%, 30 wt.% and 40 wt.% reinforcing on shrinkage and warpage behavior of polymer composite. Become evident the restrictive effect of reinforcing on the volumetric shrinkage and warpage of injected parts. The results indicate that volumetric shrinkage of natural composite is reduced up to 58% with fiber increasing, whereas the warpage shows a reduction form 79% to 86% with major fiber content. These results suggest that it is a highly beneficial use of natural fibers to improve the assembly properties of polymeric natural fiber-reinforced composites.

Engineering topochemical polymerizations using block copolymer templates.

PubMed

Zhu, Liangliang; Tran, Helen; Beyer, Frederick L; Walck, Scott D; Li, Xin; Agren, Hans; Killops, Kato L; Campos, Luis M

2014-09-24

With the aim to achieve rapid and efficient topochemical polymerizations in the solid state, via solution-based processing of thin films, we report the integration of a diphenyldiacetylene monomer and a poly(styrene-b-acrylic acid) block copolymer template for the generation of supramolecular architectural photopolymerizable materials. This strategy takes advantage of non-covalent interactions to template a topochemical photopolymerization that yields a polydiphenyldiacetylene (PDPDA) derivative. In thin films, it was found that hierarchical self-assembly of the diacetylene monomers by microphase segregation of the block copolymer template enhances the topochemical photopolymerization, which is complete within a 20 s exposure to UV light. Moreover, UV-active cross-linkable groups were incorporated within the block copolymer template to create micropatterns of PDPDA by photolithography, in the same step as the polymerization reaction. The materials design and processing may find potential uses in the microfabrication of sensors and other important areas that benefit from solution-based processing of flexible conjugated materials.

Bloch surface waves confined in one dimension with a single polymeric nanofibre

PubMed Central

Wang, Ruxue; Xia, Hongyan; Zhang, Douguo; Chen, Junxue; Zhu, Liangfu; Wang, Yong; Yang, Erchan; Zang, Tianyang; Wen, Xiaolei; Zou, Gang; Wang, Pei; Ming, Hai; Badugu, Ramachandram; Lakowicz, Joseph R.

2017-01-01

Polymeric fibres with small radii (such as ≤125 nm) are delicate to handle and should be laid down on a solid substrate to obtain practical devices. However, placing these nanofibres on commonly used glass substrates prevents them from guiding light. In this study, we numerically and experimentally demonstrate that when the nanofibre is placed on a suitable dielectric multilayer, it supports a guided mode, a Bloch surface wave (BSW) confined in one dimension. The physical origin of this new mode is discussed in comparison with the typical two-dimensional BSW mode. Polymeric nanofibres are easily fabricated to contain fluorophores, which make the dielectric nanofibre and multilayer configuration suitable for developing a large range of new nanometric scale devices, such as processor–memory interconnections, devices with sensitivity to target analytes, incident polarization and multi-colour BSW modes. PMID:28155871

Photophysical and lasing properties of new analogs of the boron-dipyrromethene laser dye pyrromethene 567 incorporated into or covalently bounded to solid matrices of poly(methyl methacrylate).

PubMed

López Arbeloa, F; Bañuelos Prieto, J; López Arbeloa, I; Costela, A; García-Moreno, I; Gómez, C; Amat-Guerri, F; Liras, M; Sastre, R

2003-07-01

The photophysical, lasing and thermostability properties of newly synthesized analogs of the commercial dye pyrromethene 567 (PM567) have been measured in polymeric matrices of poly(methyl methacrylate) both when used as a dopant and when covalently bounded to the polymeric chain. These analogs have an acetoxy or a polymerizable methacryloyloxy group at the end of a polymethylene chain at Position 8 of the PM567 chromophore core. Clear correlations between photophysical and lasing characteristics are observed. Linking chain lengths with three or more methylene units give the highest fluorescence quantum yields (as high as 0.89) and lasing efficiencies (as high as 41%). The covalent linkage of the chromophore to the polymeric chain via the methacryloyloxy group improves the photostability of the PM567 chromophore.

Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane

DOE PAGES

Sun, Jiangman; Dong, Xiao; Wang, Yajie; ...

2017-05-02

Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Moreover, following this route produces a pure cis-isomer and more surprisingly, predictsmore » that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure.« less

Tumor environment changed by combretastatin derivative (Cderiv) pretreatment that leads to effective tumor targeting, MRI studies, and antitumor activity of polymeric micelle carrier systems.

PubMed

Shiraishi, Kouichi; Harada, Yoshiko; Kawano, Kumi; Maitani, Yoshie; Hori, Katsuyoshi; Yanagihara, Kazuyoshi; Takigahira, Misato; Yokoyama, Masayuki

2012-01-01

To evaluate effect of a vascular disrupting agent, a combretastatin derivative (Cderiv), on tumor targeting for polymeric micelle carrier systems, containing either a diagnostic MRI contrast agent or a therapeutic anticancer drug. Cderiv was pre-administered 72 h before polymeric micelle MRI contrast agent injection. Accumulation of the MRI contrast agent in colon 26 murine tumor was evaluated with or without pretreatment of Cderiv by ICP and MRI. Significantly higher accumulation of the MRI contrast agent was found in tumor tissues when Cderiv was administered at 72 h before MRI contrast agent injection. T(1)-weighted images of the tumor exhibited substantial signal enhancement in tumor area at 24 h after the contrast agent injection. In T(1)-weighted images, remarkable T(1)-signal enhancements were observed in part of tumor, not in whole tumor. These results indicate that Cderiv pretreatment considerably enhanced the permeability of the tumor blood vessels. Antitumor activity of adriamycin encapsulated polymeric micelles with the Cderiv pretreatment suppressed tumor growth in 44As3 human gastric scirrhous carcinoma-bearing nude mice. Pretreatment of Cderiv enhanced tumor permeability, resulting in higher accumulation of polymeric micelle carrier systems in solid tumors.

Synthesis of High Molecular Weight Poly(glycerol monomethacrylate) via RAFT Emulsion Polymerization of Isopropylideneglycerol Methacrylate

PubMed Central

2018-01-01

High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA–PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions. PMID:29805184

Microstructural effects in drug release by solid and cellular polymeric dosage forms: A comparative study.

PubMed

Blaesi, Aron H; Saka, Nannaji

2017-11-01

In recent studies, we have introduced melt-processed polymeric cellular dosage forms to achieve both immediate drug release and predictable manufacture. Dosage forms ranging from minimally-porous solids to highly porous, open-cell and thin-walled structures were prepared, and the drug release characteristics investigated as the volume fraction of cells and the excipient molecular weight were varied. In the present study, both minimally-porous solid and cellular dosage forms consisting of various weight fractions of Acetaminophen drug and polyethylene glycol (PEG) excipient are prepared and analyzed. Microstructures of the solid forms and the cell walls range from single-phase solid solutions of the excipient and a small amount of drug molecules to two-phase composites of the excipient and tightly packed drug particles. Results of dissolution experiments show that the minimally-porous solid forms disintegrate and release drug by slow surface erosion. The erosion rate decreases as the drug weight fraction is increased. By contrast, the open-cell structures disintegrate rapidly by viscous exfoliation, and the disintegration time is independent of drug weight fraction. Drug release models suggest that the solid forms erode by convective mass transfer of the faster-eroding excipient if the drug volume fraction is small. At larger drug volume fractions, however, the slower-eroding drug particles hinder access of the free-flowing fluid to the excipient, thus slowing down erosion of the composite. Conversely, the disintegration rate of the cellular forms is limited by diffusion of the dissolution fluid into the excipient phase of the thin cell walls. Because the wall thickness is of the order of the drug particle size, and the particles are enveloped by the excipient during melt-processing, the drug particles cannot hinder diffusion through the excipient across the walls. Thus the disintegration time of the cellular forms is mostly unaffected by the volume fraction of drug in the walls. Copyright © 2017 Elsevier B.V. All rights reserved.

The Effect That Comparing Molecular Animations of Varying Accuracy Has on Students' Submicroscopic Explanations

ERIC Educational Resources Information Center

Kelly, Resa M.; Akaygun, Sevil; Hansen, Sarah J. R.; Villalta-Cerdas, Adrian

2017-01-01

In this qualitative study, we examined how a group of seventeen first semester General Chemistry students responded when they were shown contrasting molecular animations of a reduction-oxidation (redox) reaction between solid copper and aqueous silver nitrate for which they first viewed a video of the actual experiment. The animations contrasted…

Transition metal redox switches for reversible "on/off" and "slow/fast" single-molecule magnet behaviour in dysprosium and erbium bis-diamidoferrocene complexes.

PubMed

Dickie, Courtney M; Laughlin, Alexander L; Wofford, Joshua D; Bhuvanesh, Nattamai S; Nippe, Michael

2017-12-01

Single-molecule magnets (SMMs) are considered viable candidates for next-generation data storage and quantum computing. Systems featuring switchability of their magnetization dynamics are particularly interesting with respect to accessing more complex logic gates and device architectures. Here we show that transition metal based redox events can be exploited to enable reversible switchability of slow magnetic relaxation of magnetically anisotropic lanthanide ions. Specifically, we report anionic homoleptic bis-diamidoferrocene complexes of Dy 3+ (oblate) and Er 3+ (prolate) which can be reversibly oxidized by one electron to yield their respective charge neutral redox partners (Dy: [1] - , 1 ; Er: [2] - , 2 ). Importantly, compounds 1 and 2 are thermally stable which allowed for detailed studies of their magnetization dynamics. We show that the Dy 3+ [1] - / 1 system can function as an "on"/"off" or a "slow"/"fast" redox switchable SMM system in the absence or presence of applied dc fields, respectively. The Er 3+ based [2] - / 2 system features "on"/"off" switchability of SMM properties in the presence of applied fields. Results from electrochemical investigations, UV-vis-NIR spectroscopy, and 57 Fe Mössbauer spectroscopy indicate the presence of significant electronic communication between the mixed-valent Fe ions in 1 and 2 in both solution and solid state. This comparative evaluation of redox-switchable magnetization dynamics in low coordinate lanthanide complexes may be used as a potential blueprint toward the development of future switchable magnetic materials.

Redox processes as revealed by voltammetry in the surface sediments of the Gotland Basin, Baltic Sea

NASA Astrophysics Data System (ADS)

Yücel, Mustafa; Dale, Andy; Sommer, Stefan; Pfannkuche, Olaf

2014-05-01

Sulfur cycling in marine sediments undergoes dramatic changes with changing redox conditions of the overlying waters. The upper sediments of the anoxic Gotland Basin, central Baltic Sea represent a dynamic redox environment with extensive mats of sulfide oxidizing bacteria covering the seafloor beneath the chemocline. In order to investigate sulfur redox cycling at the sediment-water interface, sediment cores were sampled over a transect covering 65 - 174 m water depth in August-September 2013. High resolution (0.25 mm minimum) vertical microprofiles of electroactive redox species including dissolved sulfide and iron were obtained with solid state Au-Hg voltammetric microelectrodes. This approach enabled a fine-scale comparison of porewater profiles across the basin. The steepest sulfide gradients (i.e. the highest sulfide consumption) occurred within the upper 10 mm in sediments covered by surficial mats (2.10 to 3.08 mmol m-2 day-1). In sediments under permanently anoxic waters (>140m), voltammetric signals for Fe(II) and aqueous FeS were detected below a subsurface maximum in dissolved sulfide, indicating a Fe flux originating from older, deeper sedimentary layers. Our results point to a unique sulfur cycling in the Gotland basin seafloor where sulfide accumulation is moderated by sulfide oxidation at the sediment surface and by FeS precipitation in deeper sediment layers. These processes may play an important role in minimizing benthic sulfide fluxes to bottom waters around the major basins of the Baltic Sea.

Adhesion between polymers and evaporated gold and nickel films

NASA Technical Reports Server (NTRS)

Yamada, Y.; Wheeler, D. R.; Buckley, D. H.

1984-01-01

To obtain information on the adhesion between metal films and polymeric solids, the adhesion force was measured by means of a tensile pull test. It was found that the adhesion strengths between polymeric solids and gold films evaporated on polymer substrates were (1.11 + or - 0.53) multiplied by 10(6) N/M(2) on PTFE, about 5.49 multiplied by 10(6) N/m(2) on UHMWPE, and 6.54x10(6) on 6/6 nylon. The adhesion strengths for nickel films evaporated on PTFE, UHMWPE, and 6/6 nylon were found to be a factor of 1.7 higher than those for the gold coated PTFE, UHMWPE, and 6/6 nylon. To confirm quantitatively the effect of electron irradiation on the adhesion strength between a PTFE solid and metal films, a tensile pull test was performed on the irradiated PTFE specimens, which were prepared by evaporating nickel or gold on PTFE surfaces irradiated by 2-keV electrons for various times. After irradiation, the adhesion strength increased to (4.92 + or - 0.92)x10(6) N/m(2) for nickel coated PTFE and (1.82 + or - 0.48)x10(6) N/m(2) for gold coated PTFE. The improvement in adhesion for nickel is higher than that for gold.

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

NASA Astrophysics Data System (ADS)

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

1998-06-01

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

Top-down Approach for the Direct Synthesis, Patterning, and Operation of Artificial Micromuscles on Flexible Substrates.

PubMed

Maziz, Ali; Plesse, Cédric; Soyer, Caroline; Cattan, Eric; Vidal, Frédéric

2016-01-27

Recent progress in the field of microsystems on flexible substrates raises the need for alternatives to the stiffness of classical actuation technologies. This paper reports a top-down process to microfabricate soft conducting polymer actuators on substrates on which they ultimately operate. The bending microactuators were fabricated by sequentially stacking layers using a layer polymerization by layer polymerization of conducting polymer electrodes and a solid polymer electrolyte. Standalone microbeams thinner than 10 μm were fabricated on SU-8 substrates associated with a bottom gold electrical contact. The operation of microactuators was demonstrated in air and at low voltage (±4 V).

Immobilization of Escherichia coli cells with penicillin-amidohydrolase activity on solid polymeric carriers.

PubMed

Zurková, E; Drobník, J; Kálal, J; Svec, F; Tyrácková, V; Vojtísek, V; Zeman, R

1983-09-01

Whole cells of Escherichia coli containing the enzyme penicillinamidohydrolase EC 3.5.1.11 were immobilized on the surface of modified macroporous copolymers of glycidylmethacrylate with ethylenedimethacrylate and of copolymers of methacrylaldehyde (MA) with divinylbenzene (DVB) by means of glutaraldehyde. These polymeric carriers were modified before cell binding by using ammonia or polyamines, especially ethylenediamine and hexamethylenediamine (HMDA). The highest specific activity and the largest yield in cell immobilization were achieved with the macroporous copolymer of MA and DVB modified with HMDA. The material thus obtained was used in repeated conversions of benzylpenicillin to 6-aminopenicillanic acid in a stirred batch reactor.

Pathogenic Roles for Fungal Melanins

PubMed Central

Jacobson, Eric S.

2000-01-01

Melanins represent virulence factors for several pathogenic fungi; the number of examples is growing. Thus, albino mutants of several genera (in one case, mutated precisely in the melanizing enzyme) exhibit decreased virulence in mice. We consider the phenomenon in relation to known chemical properties of melanin, beginning with biosynthesis from ortho-hydroquinone precursors which, when oxidized enzymatically to quinones, polymerize spontaneously to melanin. It follows that melanizing intermediates are cross-linking reagents; melanization stabilizes the external cell wall against hydrolysis and is thought to determine semipermeability in the osmotic ram (the appressorium) of certain plant pathogens. Polymeric melanins undergo reversible oxidation-reduction reactions between cell wall-penetrating quinone and hydroquinone oxidation states and thus represent polymeric redox buffers; using strong oxidants, it is possible to titrate the melanin on living cells and thereby demonstrate protection conferred by melanin in several species. The amount of buffering per cell approximately neutralizes the amount of oxidant generated by a single macrophage. Moreover, the intermediate oxidation state, the semiquinone, is a very stable free radical and is thought to trap unpaired electrons. We have suggested that the oxidation state of external melanin may be regulated by external Fe(II). An independent hypothesis holds that in Cryptococcus neoformans, an important function of the melanizing enzyme (apart from melanization) is the oxidation of Fe(II) to Fe(III), thereby forestalling generation of the harmful hydroxyl radical from H2O2. Thus, problems in fungal pathogenesis have led to evolving hypotheses regarding melanin functioning. PMID:11023965

High energy density redox flow device

DOEpatents

Chiang, Yet -Ming; Carter, W. Craig; Duduta, Mihai; Limthongkul, Pimpa

2015-10-06

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

High energy density redox flow device

DOEpatents

Chiang, Yet-Ming; Carter, William Craig; Duduta, Mihai; Limthongkul, Pimpa

2014-05-13

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

Alkaline quinone flow battery.

PubMed

Lin, Kaixiang; Chen, Qing; Gerhardt, Michael R; Tong, Liuchuan; Kim, Sang Bok; Eisenach, Louise; Valle, Alvaro W; Hardee, David; Gordon, Roy G; Aziz, Michael J; Marshak, Michael P

2015-09-25

Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy. Copyright © 2015, American Association for the Advancement of Science.

A Multi-Parametric Device with Innovative Solid Electrodes for Long-Term Monitoring of pH, Redox-Potential and Conductivity in a Nuclear Waste Repository

PubMed Central

Daoudi, Jordan; Betelu, Stephanie; Tzedakis, Theodore; Bertrand, Johan; Ignatiadis, Ioannis

2017-01-01

We present an innovative electrochemical probe for the monitoring of pH, redox potential and conductivity in near-field rocks of deep geological radioactive waste repositories. The probe is composed of a monocrystalline antimony electrode for pH sensing, four AgCl/Ag-based reference or Cl− selective electrodes, one Ag2S/Ag-based reference or S2− selective electrode, as well as four platinum electrodes, a gold electrode and a glassy-carbon electrode for redox potential measurements. Galvanostatic electrochemistry impedance spectroscopy using AgCl/Ag-based and platinum electrodes measure conductivity. The use of such a multi-parameter probe provides redundant information, based as it is on the simultaneous behaviour under identical conditions of different electrodes of the same material, as well as on that of electrodes made of different materials. This identifies the changes in physical and chemical parameters in a solution, as well as the redox reactions controlling the measured potential, both in the solution and/or at the electrode/solution interface. Understanding the electrochemical behaviour of selected materials thus is a key point of our research, as provides the basis for constructing the abacuses needed for developing robust and reliable field sensors. PMID:28608820

Effect of Humic Acid on As Redox Transformation and Kinetic Adsorption onto Iron Oxide Based Adsorbent (IBA)

PubMed Central

Fakour, Hoda; Lin, Tsair-Fuh

2014-01-01

Due to the importance of adsorption kinetics and redox transformation of arsenic (As) during the adsorption process, the present study elucidated natural organic matter (NOM) effects on As adsorption-desorption kinetics and speciation transformation. The experimental procedures were conducted by examining interactions of arsenate and arsenite with different concentrations of humic acid (HA) as a model representative of NOM, in the presence of iron oxide based adsorbent (IBA), as a model solid surface in three environmentally relevant conditions, including the simultaneous adsorption of both As and HA onto IBA, HA adsorption onto As-presorbed IBA, and As adsorption onto HA-presorbed IBA. Experimental adsorption-desorption data were all fitted by original and modified Lagergren pseudo-first and -second order adsorption kinetic models, respectively. Weber’s intraparticle diffusion was also used to gain insight into the mechanisms and rate controlling steps, which the results suggested that intraparticle diffusion of As species onto IBA is the main rate-controlling step. Different concentrations of HA mediated the redox transformation of As species, with a higher oxidation ability than reduction. The overall results indicated the significant effect of organic matter on the adsorption kinetics and redox transformation of As species, and consequently, the fate, transport and mobility of As in different environmentally relevant conditions. PMID:25325357

A Multi-Parametric Device with Innovative Solid Electrodes for Long-Term Monitoring of pH, Redox-Potential and Conductivity in a Nuclear Waste Repository.

PubMed

Daoudi, Jordan; Betelu, Stephanie; Tzedakis, Theodore; Bertrand, Johan; Ignatiadis, Ioannis

2017-06-13

We present an innovative electrochemical probe for the monitoring of pH, redox potential and conductivity in near-field rocks of deep geological radioactive waste repositories. The probe is composed of a monocrystalline antimony electrode for pH sensing, four AgCl/Ag-based reference or Cl - selective electrodes, one Ag₂S/Ag-based reference or S 2- selective electrode, as well as four platinum electrodes, a gold electrode and a glassy-carbon electrode for redox potential measurements. Galvanostatic electrochemistry impedance spectroscopy using AgCl/Ag-based and platinum electrodes measure conductivity. The use of such a multi-parameter probe provides redundant information, based as it is on the simultaneous behaviour under identical conditions of different electrodes of the same material, as well as on that of electrodes made of different materials. This identifies the changes in physical and chemical parameters in a solution, as well as the redox reactions controlling the measured potential, both in the solution and/or at the electrode/solution interface. Understanding the electrochemical behaviour of selected materials thus is a key point of our research, as provides the basis for constructing the abacuses needed for developing robust and reliable field sensors.

Carbon nanosheets-based supercapacitors: Design of dual redox additives of 1, 4-dihydroxyanthraquinone and hydroquinone for improved performance

NASA Astrophysics Data System (ADS)

Xu, Dong; Sun, Xiao Na; Hu, Wei; Chen, Xiang Ying

2017-07-01

Using thiocarbanilide and Mg(OH)2 powders as carbon precursor and template, respectively, novel 2D carbon nanosheets with large area have been produced. Next, based on the cooperative effect, 1, 4-dihydroxyanthraquinone (DQ) and hydroquinone (HQ) regarded as efficient dual redox additives have been incorporated into the electrode carbon material and H2SO4 electrolyte, respectively, to largely elevate the capacitive performance of supercapacitors. More importantly, the cooperative effect results from the redox processes of DQ and HQ consecutively occurring in the electrode carbon material and aqueous H2SO4 electrolyte, respectively. Besides, the molar ratio of DQ and HQ exerts a crucial role in the determination of the electrochemical behaviors and eventually the optimum condition is the mass ratio of 1:1 concerning the DQ and porous carbon within solid electrode while retaining the HQ concentration as 20 mmol L-1 in 1 mol L-1 H2SO4 electrolyte. As a result, the maximum specific capacitance is achieved of 239 F g-1 at 3 A g-1, and furthermore the maximum energy density up to 21.1 Wh kg-1 is almost 3.5 times larger than that of the one without introducing any redox additive.

Flux Decoupling and Chemical Diffusion in Redox Dynamics in Aluminosilicate Melts and Glasses (Invited)

NASA Astrophysics Data System (ADS)

Cooper, R. F.

2010-12-01

Measurements of redox dynamics in silicate melts and glasses suggest that, for many compositions and for many external environments, the reaction proceeds and is rate-limited by the diffusive flux of divalent-cation network modifiers. Application of ion-backscattering spectrometry either (i) on oxidized or reduced melts (subsequently quenched before analysis) or (ii) on similarly reacted glasses, both of basalt-composition polymerization, demonstrates that the network modifiers move relative to the (first-order-rigid) aluminosilicate network. Thus, the textures associated with such reactions are often surprising, and frequently include metastable or unstable phases and/or spatial compositional differences. This response is only possible if the motion of cations can be decoupled from that of anions. In many cases, decoupling is accomplished by the presence in the melt/glass of transition-metal cations, whose heterovalency creates distortions in the electronic band structure resulting in electronic defects: electron “holes” in the valence band or electrons in the conduction band. (The prevalence of holes or electrons being a function of bulk chemistry and oxygen activity.) These electronic species make the melt/glass a “defect semiconductor.” Because (a) the critical issue in reaction dynamics is the transport coefficient (the product of species mobility and species concentration) and (b) the electronic species are many orders of magnitude more mobile than are the ions, very low concentrations of transition-metal ions are required for flux decoupling. For example, 0.04 at% Fe keeps a magnesium aluminosilicate melt/glass a defect semiconductor down to 800°C [Cook & Cooper, 2000]. Depending on composition, high-temperature melts can see ion species having a high-enough transport coefficient to allow decoupling, e.g., alkali cations in a basaltic melt [e.g., Pommier et al., 2010]. In this presentation, these ideas will be illustrated by examining redox dynamics in basaltic melts [e.g., Burgess et al., 2010; Cooper et al., 2010] and the reaction of magnesium aluminosilicate melts (transition-metal-ion-free and -doped) with liquid bronze (Cu-Sn alloy) [Pettersen et al., 2008], the latter demonstrating the importance of heterovalency in silicon [e.g., Borman et al., 1991] in effecting the reaction dynamics and resultant texture. Borman, V.D. et al. (1991) Phys. Rev. Lett. 67:2387-2390. Burgess, K. et al. (2010) Geochem. Geophys. Geosyst. 11:in press. Cook, G.B., and R.F. Cooper (2000) Am. Mineral. 85:397-406. Cooper, R.F. et al. (2010) Am. Mineral. 95:810-824. Pettersen, C., and R.F. Cooper (2008) J. Non-Crys. Solids 354:3194-3206. Pommier, A. et al. (2010) Geochim. Cosmochim. Acta 74:1653-1671.

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

Prabhakaran, Venkateshkumar; Johnson, Grant E.; Wang, Bingbing

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy.more » SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo12O403-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt40 ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newly developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. This capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

Chitosan-Acrylic Polymeric Nanoparticles with Dynamic Covalent Bonds. Synthesis and Stimuli Behavior.

PubMed

Palacio, Herman; Otálvaro, Felipe; Giraldo, Luis Fernando; Ponchel, Gilles; Segura-Sánchez, Freimar

2017-12-01

Drug delivery represents one of the most important research fields within the pharmaceutical industry. Different strategies are reported every day in a dynamic search for carriers with the ability to transport drugs across the body, avoiding or decreasing toxic issues and improving therapeutic activity. One of the most interesting strategies currently under research is the development of drug delivery systems sensitive to different stimuli, due to the high potential attributed to the selective delivery of the payload. In this work, a stimuli-sensitive nanocarrier was built with a bifunctional acrylic polymer, linked by imine and disulfide bonds to thiolate chitosan, the latter being a biopolymer widely known in the field of tissue engineering and drug delivery by its biodegradability and biocompatibility. These polymer nanoparticles were exposed to different changes in pH and redox potential, which are environments commonly found inside cancer cells. The results proof the ability of the nanoparticles to keep the original structure when either changes in pH or redox potential were applied individually. However, when both stimuli were applied simultaneously, a disassembly of the nanoparticles was evident. These special characteristics make these nanoparticles suitable nanocarriers with potential for the selective delivery of anticancer drugs.

Chemically grafted polymeric filters for chemical sensors: Hyperbranched poly(acrylic acid) films incorporating {Beta}-cyclodextrin receptors and amine-functionalized filter layers

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

Dermody, D.L.; Peez, R.F.; Bergbreiter, D.E.

1999-02-02

The authors report a new molecular-filter approach for enhancing the selectivity of chemical sensors. Specifically, they describe electrochemical sensors prepared from Au electrodes coated with {beta}-cyclodextrin-functionalized, hyperbranched poly(acrylic acid)(PAA) films capped with a chemically grafted, ultrathin polyamine layer. The hyperbranched PAA film is a highly functionalized framework for covalently binding the {beta}-cyclodextrin molecular receptors. The thin, grafted polyamine overlayer acts as a pH-sensitive molecular filter that selectively passes suitably charged analytes. Poly(amidoamine) dendrimers or poly-D-lysine is used as 10--15-nm-thick filter layers. The results show that at low pH, when the polyamines are fully protonated, positively charged redox probe molecules, suchmore » as benzyl viologen (BV), do not permeate the filter layer. However, at high pH, when the filter layer is uncharged, BV penetrates the filter layer and is reduced at the electrode. The opposite pH dependence is observed for negatively charged redox molecules such as anthraquinone-2-sulfonate (AQS). Both BV and AQS specifically interact with the {beta}-cyclodextrin receptors underlying the polyamine filter layers.« less

Synthesis and properties of hydroxy acrylic resin with high solid content

NASA Astrophysics Data System (ADS)

Yu, Zhen; Hu, Mingguang; Cui, Han; Xiao, Jijun

2017-10-01

Manufacturers of automotive repair finishes are tending to reduce more and more the level of volatile organic compounds in their paints in order to comply with increasingly strict environmental legislation. A high solid hydroxy acrylic resin was synthesised using CARDURA E10 and a type of hydroxyacrylic acid resin, its' acid value, hydroxylvalue, viscosity, structure, morphology was measured and film-forming properties after curing were characterised. The results show that the addition of CARDURA E10 in the copolymer composition significantly reduced the viscosity of the polymer system, improved the solid content of the resin and the physical properties of the coating. The hydroxyl acrylate resin with solid content of 90% and excellent comprehensive performance were successfully prepared by controlling the initiator dosage, polymerization temperature and monomer ratio.

Multiscale Computational Modeling of the Nanostructure of Solid Dispersions of Hydroxypropyl Methylcellulose Acetate Succinate (HPMCAS) and Phenytoin.

PubMed

Huang, Wenjun; Mandal, Taraknath; Larson, Ronald G

2017-10-02

We recently developed coarse-grained (CG) force fields for hydroxypropyl methylcellulose acetate succinate (HPMCAS) polymers and the model drug molecule phenytoin, and a continuum transport model to study the polymer-drug nanostructures presented during a dissolution test after solvation of solid dispersion particles. We model the polymer-drug interactions that contribute to suppression of drug aggregation, release, and crystal growth during the dissolution process, and we take these as indicators of polymer effectiveness. We find that the size and the intermolecular interaction strength of the functional group and the drug loading concentration are the major factors that impact the effectiveness of the polymeric excipient. The hydroxypropyl acetyl group is the most effective functional group, followed by the acetyl group, while the deprotonated succinyl group is the least effective functional group, except that the deprotonated succinyl group at the 6-position is very effective in slowing down the phenytoin crystal growth. Our simulation results thus suggest HPMCAS with higher acetyl and lower succinyl content is more effective in promoting phenytoin solubility in dissolution media, and polymers become less effective when drug loading becomes high (i.e., 50% of the mass of the polymer/drug solid dispersion), agreeing with previous experimental studies. In addition, our transport model indicates that the drug release time from a solid dispersion particle of 2 μm diameter is less than 10 min, correlating well with the experimental time scale for a typical dissolution profile to reach maximum peak concentration. Our modeling effort, therefore, provides new avenues to understand the dissolution behavior of complex HPMCAS-phenytoin solid dispersions and offers a new design tool to optimize the formulation. Moreover, the systematic and robust approach used in our computational models can be extended to other polymeric excipients and drug candidates.

Trace metal cycling and 238U/235U in New Zealand's fjords: Implications for reconstructing global paleoredox conditions in organic-rich sediments

NASA Astrophysics Data System (ADS)

Hinojosa, Jessica L.; Stirling, Claudine H.; Reid, Malcolm R.; Moy, Christopher M.; Wilson, Gary S.

2016-04-01

Reconstructing the history of ocean oxygenation provides insight into links between ocean anoxia, biogeochemical cycles, and climate. Certain redox-sensitive elements respond to changes in marine oxygen content through phase shifts and concomitant isotopic fractionation, providing new diagnostic proxies of past ocean hypoxia. Here we explore the behavior and inter-dependence of a suite of commonly utilized redox-sensitive trace metals (U, Mo, Fe, and Mn) and the emerging ;stable; isotope system of U (238U/235U, or δ238U) in New Zealand fjords. These semi-restricted basins have chemical conditions spanning the complete redox spectrum from fully oxygenated to suboxic to intermittently anoxic/euxinic. In the anoxic water column, U and Mo concentrations decrease, while Fe and Mn concentrations increase. Similarly, signals of past euxinic conditions can be found by U, Mo, Fe, and Mn enrichment in the underlying sediments. The expected U isotopic shift toward a lower δ238U in the anoxic water column due to U(VI)-U(IV) reduction is not observed; instead, water column δ238U profiles are consistent in fjords of all oxygen content, falling within previously reported ranges for open ocean seawater (δ238U = -0.42 ± 0.07‰). Additionally, surface sediment δ238U results show evidence for competing U isotope fractionation processes. One site indicates increased export of 238U from seawater to the underlying sediments (fractionation between aqueous seawater U and particulate sediment U, or ΔU(aq)-U(solid) = -0.25‰), consistent with redox-driven fractionation. Another site suggests potential U(VI) adsorption-driven fractionation, reflecting increased export of 235U from seawater to sediments (ΔU(aq)-U(solid) = 0.25‰). We discuss several potential factors that could alter δ238U in waters and sediments beyond redox-driven shifts, including adsorption to organic matter in waters of high primary productivity, reaction rates for competing processes of U adsorption and release, and isotopic constraints of U coming into the system from terrestrial environments. These potential complications should be understood and constrained through observations, experiments, and models before future application of δ238U as a global paleoredox tracer can achieve its full potential.

Microbial Preference for Soil Organic Carbon Changes Along Redox Gradients as a Function of the Energetic Cost of Respiration

NASA Astrophysics Data System (ADS)

Naughton, H.; Keiluweit, M.; Fendorf, S. E.; Farrant, D. N.

2016-12-01

Soil organic carbon (SOC) chemistry is known to impact carbon preservation via mineral associations and physical protection, which chemically or physically block SOC from microbial enzymatic access for decomposition. However, SOC decay models that include these processes do not reliably predict SOC dynamics. We propose that the energetics of respiration additionally regulate SOC cycling. Specifically, organic carbon will only be respired if the available electron acceptors yield enough energy for microbial growth when metabolically coupled to the SOC. To test this hypothesis, we constructed dual pore domain reactors in which water flows normal to a column of packed soil, allowing oxygen to diffuse from the upper channel through the soil and establish a redox gradient. With increasing depth into the soil column, the soil experiences a typical redox profile indicative of anaerobic respiration processes: after oxygen is consumed, nitrate, Mn, Fe, and sulfate serve as electron acceptors. We measure porewater and effluent for nitrate, sulfate, Fe(II) and Mn(II) and take microsensor profiles of dissolved oxygen and H2S to characterize the redox gradient and respiration pathways. To this we couple incubations of solid material at each depth post-experiment and quantify CO2 and CH4 production to assess respiration potential along the redox gradient. Porewater SOC chemistry is analyzed via spectroscopy and mass spectrometry to interpret SOC oxidation state and composition and thus test thermodynamic predictions on SOC stability given the available redox acceptors at a given depth in the reactor. Within 0.5 cm of the soil surface, oxygen concentrations drop below detection and signs of anaerobic respiration (Fe(II) production, loss of nitrate) initiate while respiration rates drops precipitously. More oxidized SOC is preferentially utilized with progression along the redox gradient, supporting thermodynamic predictions. This work highlights the potential of SOC chemistry within specific redox metabolic zones of soils and sediments to drive carbon utilization. An improved understanding on organic carbon utliization is critical to predict SOC dynamics under changing hydrology (e.g. saltwater intrusion, permafrost melting), temperature, and other factors impacting microbial respiration energetics.

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.

Nanoionic devices: Interface nanoarchitechtonics for physical property tuning and enhancement

NASA Astrophysics Data System (ADS)

Tsuchiya, Takashi; Terabe, Kazuya; Yang, Rui; Aono, Masakazu

2016-11-01

Nanoionic devices have been developed to generate novel functions overcoming limitations of conventional materials synthesis and semiconductor technology. Various physical properties can be tuned and enhanced by local ion transport near the solid/solid interface. Two electronic carrier doping methods can be used to achieve extremely high-density electronic carriers: one is electrostatic carrier doping using an electric double layer (EDL); the other is electrochemical carrier doping using a redox reaction. Atomistic restructuring near the solid/solid interface driven by a DC voltage, namely, interface nanoarchitechtonics, has huge potential. For instance, the use of EDL enables high-density carrier doping in potential superconductors, which can hardly accept chemical doping, in order to achieve room-temperature superconductivity. Optical bandgap and photoluminescence can be controlled for various applications including smart windows and biosensors. In situ tuning of magnetic properties is promising for low-power-consumption spintronics. Synaptic plasticity in the human brain is achieved in neuromorphic devices.

Water-Free Proton-Conducting Membranes for Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram; Yen, Shiao-Pin

2007-01-01

Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a white granular solid. In another synthesis, nanoparticles of silica rich with surface hydroxyl groups were added to P4VP in methanol solution, which was then reacted with excess sulfuric acid to precipitate granules of a composite that most probably had the composition (P4VPBS)-SiO2-SiO(HSO4)2. The granular P4VPBS produced in the first-mentioned synthesis was dissolved in water to make a glue-like, turbid solution; the granular P4VPBS/silica composite produced in the second-mentioned synthesis was mixed with water to make a turbid, glue-like suspension. The proportions of polymer salt to water in such preparations can be varied; it was found that approximately equal parts of water and polymer salt yield a solution or suspension amenable to further processing.

Preparation of clenbuterol imprinted monolithic polymer with hydrophilic outer layers by reversible addition-fragmentation chain transfer radical polymerization and its application in the clenbuterol determination from human serum by on-line solid-phase extraction/HPLC analysis.

PubMed

Li, Xiaobing; Zhou, Man; Turson, Mamat; Lin, Shen; Jiang, Ping; Dong, Xiangchao

2013-05-21

A novel imprinted monolithic material with the ability of protein exclusion was developed for the selective extraction of clenbuterol (CLE) from biological samples by direct injection in the HPLC analysis. The material has an imprinted inner structure and hydrophilic outer layer. The reversible addition-fragmentation chain transfer (RAFT) polymerization was employed in the material preparation by a two-step procedure. In the first step, clenbuterol imprinted monolithic polymer was synthesized by combining the molecular imprinting and the RAFT polymerization techniques. The resulting monolithic polymer has a RAFT chain transfer agent (trithioester groups) in its structure, which was used to graft poly(glycerol mono-methacrylate) [pGMMA] in the second step by post-RAFT polymerization. The hydrophilic pGMMA layers grafted on the surface of the imprinted monolith created barriers for protein diffusion. More than 90% of bovine serum albumin can be excluded from the pGMMA coated monolithic column. Meanwhile the clenbuterol was retained selectively with a large retention factor. The result indicated that the column, denoted as RA-MIM, has both the merits of a molecularly imprinted polymer and restricted access material. By using RA-MIM as the solid-phase extraction pre-column, an on-line column-switching HPLC method for the determination of clenbuterol in human serum has been established and validated. The recoveries of clenbuterol from the serum were 87.3-96.9% in the spiked level 2-1000 ng mL(-1). Both good linearity (R = 0.999) and acceptable reproducibility (RSD < 7.0%) were obtained. The limit of detection and the limit of quantitation were 0.7 ng mL(-1) and 2.0 ng mL(-1) respectively, which is sensitive in terms of UV detection. The results have demonstrated that the RAFT polymerization can be used to synthesize bi-functional monolithic columns by using its living reaction property. The resulting RA-MIM in this research can be used for efficient clenbuterol determination by HPLC from biological samples.

Novel indirect Z-scheme photocatalyst of Ag nanoparticles and polymer polypyrrole co-modified BiOBr for photocatalytic decomposition of organic pollutants

NASA Astrophysics Data System (ADS)

Liu, Xingqi; Cai, Li

2018-07-01

Mimicking the natural photosynthesis, artificial Z-scheme photocatalysis enables more efficient utilization of solar energy for degradation of organic pollutants. Herein, an indirect Z-scheme photocatalyst of Ag nanoparticles and polymer polypyrrole (PPy) co-modified BiOBr was rationally designed and successfully synthesized via a combination of hydrothermal technique, in-situ photo-reduction and oxidative polymerization method. Dramatically, BiOBr-Ag-PPy system showed superior photocatalytic performance and excellent stability in degradation of both the typical triphenylmethane dye (malachite green) and colorless organic compound (phenol). Especially for BAP-0.4, its degradation conversion of malachite green was 6.4, 2.4 and 1.6 times of those of pure BiOBr, BiOBr-Ag and BiOBr-PPy, respectively, and can still maintain more than 91% even after fifth cycle experiment. The trapping experiments of reactive species and electron spin resonance (ESR) tests confirmed that the radO2- and h+ were main active species in photocatalytic degradation. Through experimental investigations and theoretical analyses, the possible charge carriers transfer process over BiOBr-Ag-PPy ternary Z-scheme photocatalyst was proposed. In the indirect all-solid-state Z-scheme BiOBr-Ag-PPy heterojunction structure, by quenching the photo-generated electrons and holes with weaker redox ability in metal Ag nanoparticles, the electrons in the lowest unoccupied molecular orbital (LUMO) of PPy and holes in the valence band (VB) of BiOBr can survive and then have the opportunity to participate in the surface reaction, thus showing an increased photocatalytic activity.

Determination of Cr(III) solids formed by reduction of Cr(VI) in a contaminated fractured bedrock aquifer: evidence for natural attenuation of Cr(VI)

EPA Science Inventory

Hexavalent chromium Cr(VI) is toxic and can be highly mobile in many aquifer systems. Redox reactions with naturally occurring minerals and organic compounds can reduce Cr(VI) to Cr(III), forming labile Cr(III) oxyhydroxide precipitates, which is a natural attenuation process. In...

Elucidating the Charge Transfer Mechanism in Radical Polymer Thin Films

NASA Astrophysics Data System (ADS)

Mukherjee, Sanjoy; Boudouris, Bryan

The active role of polymers in organic electronics has attracted significant attention in recent decades. Beyond conventional conjugated polymers, recently radical polymers have received a great deal of consideration by the community. Radical polymers are redox-active macromolecules with non-conjugated backbones functionalized with persistent radical sites. Because of their nascent nature, many open questions regarding the physics of their solid-state charge transfer mechanism still exist. In order to address these questions, well-defined radical polymers were synthesized and blended in a manner such that there was tight control over the radical density within the conducting thin films. We demonstrate that the systematic manipulation of the radical-to-radical spacing in open-shell macromolecules leads to exponential changes in the macroscopic electrical conductivity, and temperature-independent charge transport behaviour. Thus, a clear picture emerges that charge transfer in radical polymers is dictated by a tunnelling mechanism between proximal sites. This behavior is consistent with a distinct mechanism similar to redox reactions in biological media, but is unique relative to transport in common conjugated polymers. These results constitute the first experimental insight into the mechanism of solid-state electrical conduction in radical polymers.

Catalytic oxidation of soot on mesoporous ceria-based mixed oxides with cetyltrimethyl ammonium bromide (CTAB)-assisted synthesis.

PubMed

Zhu, Hongjian; Xu, Jing; Yichuan, Yuge; Wang, Zhongpeng; Gao, Yibo; Liu, Wei; Yin, Henan

2017-12-15

Mesoporous ceria and transition metal-doped ceria (M 0.1 Ce 0.9 O 2 (M=Mn, Fe, Co, Cu)) catalysts were synthesized via CTAB-assisted method. The physicochemical properties of the prepared catalysts were characterized by XRD, DLS analysis, SEM, BET, Raman, H 2 -TPR and in situ DRIFT techniques. The catalytic activity tests for soot oxidation were performed under tight contact of soot/catalyst mixtures in the presence of O 2 and NO+O 2 , respectively. The obtained results show that mesoporous ceria-based solid solutions can be formed with large surface areas and small crystallite size. Transition metals doping enhances the oxygen vacancies and improves redox properties of the solids, resulting in the increased NO oxidation capacity and NO x adsorption capacity. The soot oxidation activity in the presence of O 2 is enhanced by doping transition metal, which may be related to their high surface area, increased oxygen vacancies and improved redox properties. The soot combustion is accelerated by the NO 2 -assisted mechanism under NO+O 2 atmosphere, facilitating an intimate contact between the soot and the catalyst. Copyright © 2017 Elsevier Inc. All rights reserved.

Monitoring local redox processes in LiNi0.5Mn1.5O4 battery cathode material by in operando EPR spectroscopy.

PubMed

Niemöller, Arvid; Jakes, Peter; Eurich, Svitlana; Paulus, Anja; Kungl, Hans; Eichel, Rüdiger-A; Granwehr, Josef

2018-01-07

Despite the multitude of analytical methods available to characterize battery cathode materials, identifying the factors responsible for material aging is still challenging. We present the first investigation of transient redox processes in a spinel cathode during electrochemical cycling of a lithium ion battery by in operando electron paramagnetic resonance (EPR). The battery contains a LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode, which is a material whose magnetic interactions are well understood. The evolution of the EPR signal in combination with electrochemical measurements shows the impact of Mn 3+ on the Li + motion inside the spinel. Moreover, state of charge dependent linewidth variations confirm the formation of a solid solution for slow cycling, which is taken over by mixed models of solid solution and two-phase formation for fast cycling due to kinetic restrictions and overpotentials. Long-term measurements for 480 h showed the stability of the investigated LNMO, but also small amounts of cathode degradation products became visible. The results point out how local, exchange mediated magnetic interactions in cathode materials are linked with battery performance and can be used for material characterization.

Intensive Study on the Catalytical Behavior of N-Methylphenothiazine as a Soluble Mediator to Oxidize the Li2O2 Cathode of the Li-O2 Battery.

PubMed

Feng, Ningning; Mu, Xiaowei; Zhang, Xueping; He, Ping; Zhou, Haoshen

2017-02-01

Aprotic Li-O 2 batteries have attracted worldwide interest owing to their ultrahigh theoretical energy density. However, the practical Li-O 2 batteries still suffer from high charge overpotential and low energy efficiency resulting from the sluggish kinetics in electrochemically oxidizing the insulating lithium peroxide (Li 2 O 2 ). Recently, dissolved redox mediators in the electrolyte have enabled the effective catalytic oxidation of Li 2 O 2 at the liquid-solid interface. Here, we report that the incorporation of N-methylphenothiazine (MPT), as a redox shuttle in Li-O 2 batteries, provides a dramatic reduction in charge overpotential to 0.67 V and an improved round-trip efficiency close to 76%. Moreover, the efficacy of MPT in Li-O 2 cells was further investigated by various characterizations. On charging, MPT + cations are first generated electrochemically at the cathode surface and subsequently oxidize the solid discharge products Li 2 O 2 through a chemical reaction. Furthermore, the presence of MPT has been demonstrated to improve the cycling stability of the cells and suppress side reactions arising from carbon and electrolytes at high potentials.