Sample records for polymeric diazonium salt

  1. Direct peptide bioconjugation/PEGylation at tyrosine with linear and branched polymeric diazonium salts.

    PubMed

    Jones, Mathew W; Mantovani, Giuseppe; Blindauer, Claudia A; Ryan, Sinead M; Wang, Xuexuan; Brayden, David J; Haddleton, David M

    2012-05-02

    Direct polymer conjugation at peptide tyrosine residues is described. In this study Tyr residues of both leucine enkephalin and salmon calcitonin (sCT) were targeted using appropriate diazonium salt-terminated linear monomethoxy poly(ethylene glycol)s (mPEGs) and poly(mPEG) methacrylate prepared by atom transfer radical polymerization. Judicious choice of the reaction conditions-pH, stoichiometry, and chemical structure of diazonium salt-led to a high degree of site-specificity in the conjugation reaction, even in the presence of competitive peptide amino acid targets such as histidine, lysines, and N-terminal amine. In vitro studies showed that conjugation of mPEG(2000) to sCT did not affect the peptide's ability to increase intracellular cAMP induced in T47D human breast cancer cells bearing sCT receptors. Preliminary in vivo investigation showed preserved ability to reduce [Ca(2+)] plasma levels by mPEG(2000)-sCT conjugate in rat animal models. © 2012 American Chemical Society

  2. Photobleachable Diazonium Salt-Phenolic Resin Two-Layer Resist System

    NASA Astrophysics Data System (ADS)

    Uchino, Shou-ichi; Iwayanagi, Takao; Hashimoto, Michiaki

    1988-01-01

    This article describes a new negative two-layer photoresist system formed by a simple, successive spin-coating method. An aqueous acetic acid solution of diazonium salt and poly(N-vinylpyrrolidone) is deposited so as to contact a phenolic resin film spin-coated on a silicon wafer. The diazonium salt diffuses into the phenolic resin layer after standing for several minutes. The residual solution on the phenolic resin film doped with diazonium salt is spun to form the diazonium salt-poly(N-vinylpyrrolidone) top layer. This forms a uniform two-layer resist without phase separation or striation. Upon UV exposure, the diazonium salt in the top layer bleaches to act as a CEL dye, while the diazonium salt in the bottom layer decomposes to cause insolubilization. Half μm line-and-space patterns are obtained with an i-line stepper using 4-diazo-N,N-dimethylaniline chloride zinc chloride double salt as the diazonium salt and a cresol novolac resin for the bottom polymer layer. The resist formation processes, insolubilization mechanism, and the resolution capability of the new two-layer resist are discussed.

  3. Copper-promoted sandmeyer difluoromethylthiolation of aryl and heteroaryl diazonium salts.

    PubMed

    Wu, Jiang; Gu, Yang; Leng, Xuebing; Shen, Qilong

    2015-06-22

    An efficient copper-promoted difluoromethylthiolation of aryl and heteroaryl diazonium salts is described. The reaction is conducted under mild reaction conditions and various functional groups were compatible. In addition, reactions of heteroaryl diazonium salts such as pyridyl, quinolinyl, benzothiazolyl, thiophenyl, carbazolyl, and pyrazolyl diazonium salts occurred smoothly to afford the medicinally important difluoromethylthiolated heteroarenes. Furthermore, a more practical one-pot direct diazotization and difluoromethylthiolation protocol was developed, and it converts the aniline derivatives into difluoromethylthiolated arenes. The utility of the method is demonstrated by difluoromethylthiolation of a number of natural products and drug molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Aryl diazonium salts: a new class of coupling agents for bonding polymers, biomacromolecules and nanoparticles to surfaces.

    PubMed

    Mahouche-Chergui, Samia; Gam-Derouich, Sarra; Mangeney, Claire; Chehimi, Mohamed M

    2011-07-01

    This critical review summarizes existing knowledge on the use of diazonium salts as a new generation of surface modifiers and coupling agents for binding synthetic polymers, biomacromolecules, and nanoparticles to surfaces. Polymer grafts can be directly grown at surfaces through the so-called grafting from approaches based on several polymerization methods but can also be pre-formed in solution and then grafted to surfaces through grafting onto strategies including "click" reactions. Several routes are also described for binding biomacromolecules through aryl layers in view of developing biosensors and protein arrays, while the use of aryl diazonium coupling agents is extended to the attachment of nanoparticles. Patents and industrial applications of the surface chemistry of diazonium compounds are covered. This review stresses the paramount role of aryl diazonium coupling agents in adhesion, surface and materials sciences (114 references).

  5. Core/shell, protuberance-free multiwalled carbon nanotube/polyaniline nanocomposites via interfacial chemistry of aryl diazonium salts.

    PubMed

    Mekki, Ahmed; Samanta, Soumen; Singh, Ajay; Salmi, Zakaria; Mahmoud, Rachid; Chehimi, Mohamed M; Aswal, Dinesh K

    2014-03-15

    Highly uniform core-shell like multi-walled carbon nanotubes-polyaniline (MWCNT-PANI) nanocomposites were prepared in two steps (i) surface modification of MWCNTs with a 4-aminodiphenylamine group via in situ diazonium generation process; and (ii) polymerization of aniline onto surface modified MWCNTs. This functionalization helped to easily disperse the MWCNTs in acidic solutions; hence it is suitable for the chemical oxidative polymerization of aniline. It was found that MWCNT-PANI nano-composites with higher MWCNTs loading yield PANI chains with more quinoid units than the pure PANI, which results in significant improvement in the conductivity of the composites. This facile approach of synthesizing core-shell nanocomposites highlights the efficiency of the interfacial chemistry of aryl diazonium salts in generating conductive polymer/MWCNT nanocomposites with enhanced conductivity and high surface area. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. Diazonium salts as grafting agents and efficient radical-hydrosilylation initiators for freestanding photoluminescent silicon nanocrystals.

    PubMed

    Höhlein, Ignaz M D; Kehrle, Julian; Helbich, Tobias; Yang, Zhenyu; Veinot, Jonathan G C; Rieger, Bernhard

    2014-04-07

    The reactivity of diazonium salts towards freestanding, photoluminescent silicon nanocrystals (SiNCs) is reported. It was found that SiNCs can be functionalized with aryl groups by direct reductive grafting of the diazonium salts. Furthermore, diazonium salts are efficient radical initiators for SiNC hydrosilylation. For this purpose, novel electron-deficient diazonium salts, highly soluble in nonpolar solvents were synthesized. The SiNCs were functionalized with a variety of alkenes and alkynes at room temperature with short reaction times. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. On-off QD switch that memorizes past recovery from quenching by diazonium salts.

    PubMed

    Liras, Marta; González-Béjar, María; Scaiano, J C

    2010-09-07

    The understanding of the interaction of CdSe/ZnS semiconductor quantum dots (QD) with their chemical environment is fundamental, yet far from being fully understood. p-Methylphenyldiazonium tetrafluoroborate has been used to get some insight into the effect of diazonium salts on the spectroscopy of QD. Our study reveals that the surface of CdSe/ZnS quantum dots can be modified by diazonium salts (although not functionalized), showing and on-off fluorescence behaviour that memorizes past quenching recoveries. Facile modification of the surface confers protection against quenching by new molecules of diazonium salt and other known quenchers such as 4-amino-TEMPO. The reaction mechanism has been explored in detail by using different spectroscopic techniques. At the first time after addition of diazonium salt over QD the fluorescent is turned off with Stern-Volmer behaviour; the fluorescence recovers following irradiation. Subsequent additions of diazonium salts do not cause the same degree of quenching. We have noted that the third addition (following two cycles of addition and irradiation) is unable to quench the fluorescence. Monitoring the process using NMR techniques reveals the formation of p-difluoroborane toluene as a result of the irradiation of diazonium-treated QD; the treatment leads to the fluorination of the QD surface.

  8. Visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO.

    PubMed

    Pramanik, Mukund M D; Rastogi, Namrata

    2016-06-30

    The visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO is illustrated. This is the first example of DMSO being used as the source of the methylsulfinyl group. The procedure tolerates a wide range of functional groups on (het)aryl diazonium salts and provides aryl methyl sulfoxides in excellent yields under mild reaction conditions.

  9. Chemical modification of the cocoa shell surface using diazonium salts.

    PubMed

    Fioresi, Flavia; Vieillard, Julien; Bargougui, Radhouane; Bouazizi, Nabil; Fotsing, Patrick Nkuigue; Woumfo, Emmanuel Djoufac; Brun, Nicolas; Mofaddel, Nadine; Le Derf, Franck

    2017-05-15

    The outer portion of the cocoa bean, also known as cocoa husk or cocoa shell (CS), is an agrowaste material from the cocoa industry. Even though raw CS is used as food additive, garden mulch, and soil conditioner or even burnt for fuel, this biomass material has hardly ever been investigated for further modification. This article proposes a strategy of chemical modification of cocoa shell to add value to this natural material. The study investigates the grafting of aryl diazonium salt on cocoa shell. Different diazonium salts were grafted on the shell surface and characterized by infrared spectroscopy and scanning electronic microscopy imaging. Strategies were developed to demonstrate the spontaneous grafting of aryl diazonium salt on cocoa shell and to elucidate that lignin is mainly involved in immobilizing the phenyl layer. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Functionalized alkoxy arene diazonium salts from paracetamol.

    PubMed

    Schmidt, Bernd; Berger, René; Hölter, Frank

    2010-03-21

    Arene diazonium tetrafluoroborates can be synthesized from aromatic acetamides via a sequence of deacetylation, diazotation and precipitation, induced by anion exchange. The reaction is conducted as a convenient one-flask transformation with consecutive addition of the appropriate reagents. Exchange of solvents or removal of byproducts prior to isolation of the product is not required. The arene diazonium salts are isolated from the reaction mixture by simple filtration. Two complementary protocols are presented, and the utility of the reaction is exemplified for a synthesis of the diarylheptanoid natural product de-O-methyl centrolobine.

  11. Removal of amino groups from anilines through diazonium salt-based reactions.

    PubMed

    He, Linman; Qiu, Guanyinsheng; Gao, Yueqiu; Wu, Jie

    2014-09-28

    This minireview describes the applications of in situ generated diazonium salts from anilines in organic synthesis. In situ generation of diazonium salts from anilines represents an efficient and practical pathway, leading to a series of useful structures. In these transformations, the amino group of aniline formally acts as a leaving group. Two distinctive kinds of mechanisms, including transition metal (especially palladium)-catalyzed oxidative addition-reductive elimination and a radical process, are involved in the removal of amino groups from anilines, and both catalytic processes are described in this minireview.

  12. Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces.

    PubMed

    Mesnage, Alice; Lefèvre, Xavier; Jégou, Pascale; Deniau, Guy; Palacin, Serge

    2012-08-14

    The spontaneous reaction of diazonium salts on various substrates has been widely employed since it consists of a simple immersion of the substrate in the diazonium salt solution. As electrochemical processes involving the same diazonium salts, the spontaneous grafting is assumed to give covalently poly(phenylene)-like bonded films. Resistance to solvents and to ultrasonication is commonly accepted as indirect proof of the existence of a covalent bond. However, the most relevant attempts to demonstrate a metal-C interface bond have been obtained by an XPS investigation of spontaneously grafted films on copper. Similarly, our experiments give evidence of such a bond in spontaneously grafted films on nickel substrates in acetonitrile. In the case of gold substrates, the formation of a spontaneous film was unexpected but reported in the literature in parallel to our observations. Even if no interfacial bond was observed, formation of the films was explained by grafting of aryl cations or radicals on the surface arising from dediazoniation, the film growing later by azo coupling, radical addition, or cationic addition on the grafted phenyl layer. Nevertheless, none of these mechanisms fits our experimental results showing the presence of an Au-N bond. In this work, we present a fine spectroscopic analysis of the coatings obtained on gold and nickel substrates that allow us to propose a chemical structure of such films, in particular, their interface with the substrates. After testing the most probable mechanisms, we have concluded in favor of the involvement of two complementary mechanisms which are the direct reaction of diazonium salts with the gold surface that accounts for the observed Au-N interfacial bonds as well as the formation of aryl cations able to graft on the substrate through Au-C linkages.

  13. Metal-free, visible-light-mediated direct C-H arylation of heteroarenes with aryl diazonium salts.

    PubMed

    Hari, Durga Prasad; Schroll, Peter; König, Burkhard

    2012-02-15

    Visible light along with 1 mol % eosin Y catalyzes the direct C-H bond arylation of heteroarenes with aryl diazonium salts by a photoredox process. We have investigated the scope of the reaction for several aryl diazonium salts and heteroarenes. The general and easy procedure provides a transition-metal-free alternative for the formation of aryl-heteroaryl bonds.

  14. Synthesis of Quinolines through Three-Component Cascade Annulation of Aryl Diazonium Salts, Nitriles, and Alkynes.

    PubMed

    Wang, Hao; Xu, Qian; Shen, Sheng; Yu, Shouyun

    2017-01-06

    An efficient and rapid synthesis of multiply substituted quinolines is described. This method is enabled by a three-component cascade annulation of readily available aryl diazonium salts, nitriles, and alkynes. This reaction is catalyst- and additive-free. Various aryl diazonium salts, nitriles, and alkynes can participate in this transformation, and the yields are up to 83%.

  15. A general access to organogold(iii) complexes by oxidative addition of diazonium salts.

    PubMed

    Huang, Long; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

    2016-05-11

    At room temperature under mild photochemical conditions, namely irradiation with a simple blue light LED, gold(i) chloro complexes of both phosphane and carbene ligands in combination with aryldiazonium salts afford arylgold(iii) complexes. With chelating P,N-ligands cationic six- or five-membered chelate complexes were isolated in the form of salts with weakly coordinating counter anions that were brought in from the diazonium salt. With monodentate P ligands or N-heterocyclic carbene ligands and diazonium chlorides neutral arylgold(iii) dichloro complexes were obtained. The coordination geometry was determined by X-ray crystal structure analyses of representative compounds, a cis arrangement of the aryl and the phosphane ligand at the square planar gold(iii) center is observed.

  16. Facile synthesis of electrophilic vinyl boranes: reactions of alkynyl-borates and diazonium salts.

    PubMed

    Zhao, Xiaoxi; Liang, Liyuan; Stephan, Douglas W

    2012-10-21

    Reactions of alkynylborate salts, easily derived from reaction of frustrated Lewis pairs with terminal alkynes, with diazonium salts to induce 1,1-carboboration affording a facile and efficient route to substituted electrophilic vinyl boranes.

  17. Scope and limitations of the Heck-Matsuda-coupling of phenol diazonium salts and styrenes: a protecting-group economic synthesis of phenolic stilbenes.

    PubMed

    Schmidt, Bernd; Elizarov, Nelli; Berger, René; Hölter, Frank

    2013-06-14

    4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4'-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.

  18. Multicomponent, flow diazotization/Mizoroki-Heck coupling protocol: dispelling myths about working with diazonium salts.

    PubMed

    Nalivela, Kumara S; Tilley, Michael; McGuire, Michael A; Organ, Michael G

    2014-05-26

    A single pass flow diazotization/Mizoroki-Heck protocol has been developed for the production of cinnimoyl and styryl products. The factors that govern aryl diazonium salt stability have been examined in detail leading to the development of a MeOH/DMF co-solvent system in which the diazonium salts can be generated in the presence of all other reaction components and then coupled selectively to give the desired products. Finally the key role of the reaction quench for flow reactions has been demonstrated. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Controlled, Site-Specific Functionalization of Carbon Nanotubes with Diazonium Salts

    NASA Technical Reports Server (NTRS)

    Tour, James M.

    2013-01-01

    This work uses existing technologies to prepare a crossbar architecture of nano tubes, wherein one nanotube is fixed to a substrate, and a second nanotube is suspended a finite distance above. Both nano tubes can be individually addressed electrically. Application of opposite potentials to the two tubes causes the top tube to deform and to essentially come into contact with the lower tube. Contact here refers not to actual, physical contact, but rather within an infinitesimally small distance referred to as van der Walls contact, in which the entities may influence each other on a molecular and electronic scale. First, the top tube is physically deformed, leading to a potentially higher chemical reactivity at the point of deformation, based on current understanding of the effects of curvature strain on reactivity. This feature would allow selective functionalization at the junction via reaction with diazonium salts. Secondly, higher potential is achieved at the point of "cross" between the tubes. In a pending patent application, a method is claimed for directed self-assembly of molecular components onto the surface of metal or conductive materials by application of potential to the metal or conductive surface. In another pending patent application, a method is claimed for attaching molecules to the surface of nanotubes via the use of reactive diazonium salts. In the present invention, the directed functionalization of the crossed-nanotube junctions by applying a potential to the ends of the nanotubes in the presence of reactive diazonium slats, or other reactive molecular species is claimed. The diazonium salts are directed by the potential existing at the junction to react with the surface of the nanotube, thus placing functional molecular components at the junctions. The crossed nano tubes therefore provide a method of directly addressing the functionalized molecules, which have been shown to function as molecular switches, molecular wires, and in other

  20. Electrografted diazonium salt layers for antifouling on the surface of surface plasmon resonance biosensors.

    PubMed

    Zou, Qiongjing; Kegel, Laurel L; Booksh, Karl S

    2015-02-17

    Electrografted diazonium salt layers on the surface of surface plasmon resonance (SPR) sensors present potential for a significant improvement in antifouling coatings. A pulsed potential deposition profile was used in order to circumvent mass-transport limitations for layer deposition rate. The influence of number of pulses with respect to antifouling efficacy was evaluated by nonspecific adsorption surface coverage of crude bovine serum proteins. Instead of using empirical and rough estimated values, the penetration depth and sensitivity of the SPR instrument were experimentally determined for the calculation of nonspecific adsorption surface coverage. This provides a method to better examine antifouling surface coatings and compare crossing different coatings and experimental systems. Direct comparison of antifouling performance of different diazonium salts was facilitated by a tripad SPR sensor design. The electrografted 4-phenylalanine diazonium chloride (4-APhe) layers with zwitterionic characteristic demonstrate ultralow fouling.

  1. Maleimide-activated aryl diazonium salts for electrode surface functionalization with biological and redox-active molecules.

    PubMed

    Harper, Jason C; Polsky, Ronen; Wheeler, David R; Brozik, Susan M

    2008-03-04

    A versatile and simple method is introduced for formation of maleimide-functionalized surfaces using maleimide-activated aryl diazonium salts. We show for the first time electrodeposition of N-(4-diazophenyl)maleimide tetrafluoroborate on gold and carbon electrodes which was characterized via voltammetry, grazing angle FTIR, and ellipsometry. Electrodeposition conditions were used to control film thickness and yielded submonolayer-to-multilayer grafting. The resulting phenylmaleimide surfaces served as effective coupling agents for electrode functionalization with ferrocene and the redox-active protein cytochrome c. The utility of phenylmaleimide diazonium toward formation of a diazonium-activated conjugate, followed by direct electrodeposition of the diazonium-modified DNA onto the electrode surface, was also demonstrated. Effective electron transfer was obtained between immobilized molecules and the electrodes. This novel application of N-phenylmaleimide diazonium may facilitate the development of bioelectronic devices including biofuel cells, biosensors, and DNA and protein microarrays.

  2. Exploring Flow Procedures for Diazonium Formation.

    PubMed

    Hu, Te; Baxendale, Ian R; Baumann, Marcus

    2016-07-14

    The synthesis of diazonium salts is historically an important transformation extensively utilized in dye manufacture. However the highly reactive nature of the diazonium functionality has additionally led to the development of many new reactions including several carbon-carbon bond forming processes. It is therefore highly desirable to determine optimum conditions for the formation of diazonium compounds utilizing the latest processing tools such as flow chemistry to take advantage of the increased safety and continuous manufacturing capabilities. Herein we report a series of flow-based procedures to prepare diazonium salts for subsequent in-situ consumption.

  3. Reactions of aromatic diazonium salts with unsaturated compounds in the presence of nucleophiles

    NASA Astrophysics Data System (ADS)

    Grishchuk, B. D.; Gorbovoi, P. M.; Ganushchak, N. I.; Dombrovskii, A. V.

    1994-03-01

    The review surveys the reactions of aromatic diazonium salts with diene and monounsaturated compounds in the presence of nucleophiles. Certain further reactions of the reaction products and their application are considered. The bibliography includes 63 references.

  4. Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes.

    PubMed

    Hilmer, Andrew J; McNicholas, Thomas P; Lin, Shangchao; Zhang, Jingqing; Wang, Qing Hua; Mendenhall, Jonathan D; Song, Changsik; Heller, Daniel A; Barone, Paul W; Blankschtein, Daniel; Strano, Michael S

    2012-01-17

    Because covalent chemistry can diminish the optical and electronic properties of single-walled carbon nanotubes (SWCNTs), there is significant interest in developing methods of controllably functionalizing the nanotube sidewall. To date, most attempts at obtaining such control have focused on reaction stoichiometry or strength of oxidative treatment. Here, we examine the role of surfactants in the chemical modification of single-walled carbon nanotubes with aryl diazonium salts. The adsorbed surfactant layer is shown to affect the diazonium derivatization of carbon nanotubes in several ways, including electrostatic attraction or repulsion, steric exclusion, and direct chemical modification of the diazonium reactant. Electrostatic effects are most pronounced in the cases of anionic sodium dodecyl sulfate and cationic cetyltrimethylammonium bromide, where differences in surfactant charge can significantly affect the ability of the diazonium ion to access the SWCNT surface. For bile salt surfactants, with the exception of sodium cholate, we find that the surfactant wraps tightly enough such that exclusion effects are dominant. Here, sodium taurocholate exhibits almost no reactivity under the explored reaction conditions, while for sodium deoxycholate and sodium taurodeoxycholate, we show that the greatest extent of reaction is observed among a small population of nanotube species, with diameters between 0.88 and 0.92 nm. The anomalous reaction of nanotubes in this diameter range seems to imply that the surfactant is less effective at coating these species, resulting in a reduced surface coverage on the nanotube. Contrary to the other bile salts studied, sodium cholate enables high selectivity toward metallic species and small band gap semiconductors, which is attributed to surfactant-diazonium coupling to form highly reactive diazoesters. Further, it is found that the rigidity of anionic surfactants can significantly influence the ability of the surfactant layer to

  5. Spectroscopic Identification of the Au-C Bond Formation upon Electroreduction of an Aryl Diazonium Salt on Gold.

    PubMed

    Guo, Limin; Ma, Lipo; Zhang, Yelong; Cheng, Xun; Xu, Ye; Wang, Jin; Wang, Erkang; Peng, Zhangquan

    2016-11-08

    Electroreduction of aryl diazonium salts on gold can produce organic films that are more robust than their analogous self-assembled monolayers formed from chemical adsorption of organic thiols on gold. However, whether the enhanced stability is due to the Au-C bond formation remains debated. In this work, we report the electroreduction of an aryl diazonium salt of 4,4'-disulfanediyldibenzenediazonium on gold forming a multilayer of Au-(Ar-S-S-Ar) n , which can be further degraded to a monolayer of Au-Ar-S - by electrochemical cleavage of the S-S moieties within the multilayer. By conducting an in situ surface-enhanced Raman spectroscopic study of both the multilayer formation/degradation and the monolayer reduction/oxidation processes, coupled to density functional theory calculations, we provide compelling evidence that an Au-C bond does form upon electroreduction of aryl diazonium salts on gold and that the enhanced stability of the electrografted organic films is due to the Au-C bond being intrinsically stronger than the Au-S bond for a given phenylthiolate compound by ca. 0.4 eV.

  6. Convenient and General Zinc‐Catalyzed Borylation of Aryl Diazonium Salts and Aryltriazenes under Mild Conditions

    PubMed Central

    Qi, Xinxin; Jiang, Li‐Bing; Zhou, Chao; Peng, Jin‐Bao

    2017-01-01

    Abstract A convenient and general zinc‐catalyzed borylation of aryl diazonium salts and aryltriazenes has been developed. With bis‐ (pinacolato)diboron as the borylation reagent, aryldiazonium tetrafluoroborate salts and aryltriazenes were transformed into the corresponding arylboronates in moderate to excellent yields under mild conditions. As a convenient and practical methodology, no additional ligands, base, or any other additives are required here. PMID:28638765

  7. Reactive Diazonium-Modified Silica Fillers for High-Performance Polymers.

    PubMed

    Sandomierski, Mariusz; Strzemiecka, Beata; Chehimi, Mohamed M; Voelkel, Adam

    2016-11-08

    We describe a simple way of modification of three silica-based fillers with in situ generated 4-hydroxymethylbenzenediazonium salt ( + N 2 -C 6 H 4 -CH 2 OH). The rationale for using a hydroxyl-functionalized diazonium salt is that it provides surface-functionalized fillers that can react with phenolic resins. The modification of silica by diazonium salts was assessed using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). FTIR spectroscopy permitted the tracking of benzene ring breathing and C-C. The absence of the characteristic N≡N stretching vibration in the 2200-2300 cm -1 range indicates the loss of the diazonium group. XPS results indicate a higher C/Si atomic ratio after the diazonium modification of fillers and the presence of π-π* C1s satellite peaks characteristic of the surface-tethered aromatic species. Adhesion of aryl layers to the silicas is excellent because they withstand harsh thermal and organic solvent treatments. Phenolic resins (used, for example, as binders in abrasive products) were filled with diazonium-modified silicas at 10-25 wt %. The reactivity of the fillers toward phenolic resins was evaluated by the determination of the flow distance. After annealing at 180 °C, the diazonium-modified silica/phenolic resin composites were mechanically tested using the three-point flexural method. The flexural strength was found to be up to 35% higher than that of the composites prepared without any diazonium salts. Diazonium-modified silica with surface-bound -CH 2 -OH groups is thus ideal reactive filler for phenolic resins. Such filler ensures interfacial chemical reactions with the matrix and imparts robust mechanical properties to the final composites. This specialty diazonium-modified silica will find potential application as fillers in the composites for the abrasive industry. More generally, aryl diazonium salts are a unique new series of compounds for tailoring the surface properties of fillers

  8. The photocatalyzed Meerwein arylation: classic reaction of aryl diazonium salts in a new light.

    PubMed

    Hari, Durga Prasad; König, Burkhard

    2013-04-26

    The use of diazonium salts for aryl radical generation and C-H arylation processes has been known since 1896 when Pschorr first used the reaction for intramolecular cyclizations. Meerwein developed it further in the early 1900s into a general arylation method. However, this reaction could not compete with the transition-metal-mediated formation of C(sp(2))-C(sp(2)) bonds. The replacement of the copper catalyst with iron and titanium compounds improved the situation, but the use of photocatalysis to induce the one-electron reduction and activation of the diazonium salts is even more advantageous. The first photocatalyzed Pschorr cyclization was published in 1984, and just last year a series of papers described applications of photocatalytic Meerwein arylations leading to aryl-alkene coupling products. In this Minireview we summarize the origins of this reaction and its scope and applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Integrated Affinity Biosensing Platforms on Screen-Printed Electrodes Electrografted with Diazonium Salts

    PubMed Central

    Yáñez-Sedeño, Paloma

    2018-01-01

    Adequate selection of the electrode surface and the strategies for its modification to enable subsequent immobilization of biomolecules and/or nanomaterials integration play a major role in the performance of electrochemical affinity biosensors. Because of the simplicity, rapidity and versatility, electrografting using diazonium salt reduction is among the most currently used functionalization methods to provide the attachment of an organic layer to a conductive substrate. This particular chemistry has demonstrated to be a powerful tool to covalently immobilize in a stable and reproducible way a wide range of biomolecules or nanomaterials onto different electrode surfaces. Considering the great progress and interesting features arisen in the last years, this paper outlines the potential of diazonium chemistry to prepare single or multianalyte electrochemical affinity biosensors on screen-printed electrodes (SPEs) and points out the existing challenges and future directions in this field. PMID:29495294

  10. Integrated Affinity Biosensing Platforms on Screen-Printed Electrodes Electrografted with Diazonium Salts.

    PubMed

    Yáñez-Sedeño, Paloma; Campuzano, Susana; Pingarrón, José M

    2018-02-24

    Adequate selection of the electrode surface and the strategies for its modification to enable subsequent immobilization of biomolecules and/or nanomaterials integration play a major role in the performance of electrochemical affinity biosensors. Because of the simplicity, rapidity and versatility, electrografting using diazonium salt reduction is among the most currently used functionalization methods to provide the attachment of an organic layer to a conductive substrate. This particular chemistry has demonstrated to be a powerful tool to covalently immobilize in a stable and reproducible way a wide range of biomolecules or nanomaterials onto different electrode surfaces. Considering the great progress and interesting features arisen in the last years, this paper outlines the potential of diazonium chemistry to prepare single or multianalyte electrochemical affinity biosensors on screen-printed electrodes (SPEs) and points out the existing challenges and future directions in this field.

  11. Acid-promoted Bicyclization of Diaryl Alkynes: Synthesis of 2H-Indazoles with in situ Generated Diazonium Salt as Nitrogen Source.

    PubMed

    Zhang, Cheng; Chang, Sailan; Dong, Shanliang; Qiu, Lihua; Xu, Xinfang

    2018-06-08

    An unprecedented transition-metal-free tandem bicyclization of diaryl alkynes has been disclosed, which provides a streamlined access to a range of polycyclic 2H-indazoles in high to excellent yields. The salient features of this reaction include readily available starting materials, good functional group compatibility, mild reaction conditions, no column chromatography, high bond-formation efficiency, and ease in further transformations. Notably, this is the first example for the synthesis of 2H-indazoles with in situ generated diazonium salt as the nitrogen source, and a mechanistic rationale involving an acid-promoted tandem diazonium salt formation/bicyclization process is discussed.

  12. Mesomeric Effects of Graphene Modified with Diazonium Salts: Substituent Type and Position Influence its Properties.

    PubMed

    Bouša, Daniel; Jankovský, Ondřej; Sedmidubský, David; Luxa, Jan; Šturala, Jiří; Pumera, Martin; Sofer, Zdeněk

    2015-12-01

    In the last decade, graphene and graphene derivatives have become some of the most intensively studied materials. Tuning of the electronic and electrochemical properties of graphene is of paramount importance. In this study, six diazonium-modified graphenes containing different functional groups according to the diazonium salt precursor were investigated. These diazonium moieties have a strong mesomeric (resonance) effect and act as either electron-donating or -withdrawing species. Different graphene precursors, such as thermally and chemically reduced graphenes were studied. All the products were characterized in detail by elemental combustion analysis, FTIR spectroscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. Resistivity and zeta potential measurements were consistent with theoretical (DFT) calculations. The results show that chemical modification of graphene by diazotation strongly influences its properties, creating a huge application potential in microelectronics, energy storage and conversion devices, and electrocatalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Amine-selective bioconjugation using arene diazonium salts.

    PubMed

    Diethelm, Stefan; Schafroth, Michael A; Carreira, Erick M

    2014-08-01

    A novel bioconjugation strategy is presented that relies on the coupling of diazonium terephthalates with amines in proteins. The diazonium captures the amine while the vicinal ester locks it through cyclization, ensuring no reversibility. The reaction is highly efficient and proceeds under mild conditions and short reaction times. Densely functionalized, complex natural products were directly coupled to proteins using low concentrations of coupling partners.

  14. Surface Patterning Using Diazonium Ink Filled Nanopipette.

    PubMed

    Zhou, Min; Yu, Yun; Blanchard, Pierre-Yves; Mirkin, Michael V

    2015-11-03

    Molecular grafting of diazonium is a widely employed surface modification technique. Local electrografting of this species is a promising approach to surface doping and related properties tailoring. The instability of diazonium cation complicates this process, so that this species was generated in situ in many reported studies. In this Article, we report the egress transfer of aryl diazonium cation across the liquid/liquid interface supported at the nanopipette tip that can be used for controlled delivery this species to the external aqueous phase for local substrate patterning. An aryl diazonium salt was prepared with weakly coordinating and lipophilic tetrakis(pentafluorophenyl)borate anion stable as a solid and soluble in low polarity media. The chemically stable solution of this salt in 1,2-dichloroethane can be used as "diazonium ink". The ink-filled nanopipette was employed as a tip in the scanning electrochemical microscope (SECM) for surface patterning with the spatial resolution controlled by the pipette orifice radius and a few nanometers film thickness. The submicrometer-size grafted spots produced on the HOPG surface were located and imaged with the atomic force microscope (AFM).

  15. Surface modified MXene Ti3C2 multilayers by aryl diazonium salts leading to large-scale delamination

    NASA Astrophysics Data System (ADS)

    Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Li, Gaiye; Zhang, Xin; Wang, Zhuyin

    2016-10-01

    Herein we report a simple and facile method to delaminate MXene Ti3C2 multilayers by the assistance of surface modification using aryl diazonium salts. The basic strategy involved the preparation of layered MAX Ti3AlC2 and the exfoliation of Ti3AlC2 into Ti3C2 multilayers, followed by Na+ intercalation and surface modification using sulfanilic acid diazonium salts. The resulting chemically grafted Ti3C2 flakes were characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. Ultraviolet-visible spectroscopy revealed that surface-modified MXene Ti3C2 sheets disperse well in water and the solutions obey Lambert-Beer's law. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to demonstrate the morphology and structure of delaminating MXene Ti3C2 flakes. The results indicated that chemical modification for MXene multilayers by aryl diazonium salts induced swelling that conversely weakened the bonds between MX layers, hence leading to large-scale delamination of multilayered MXene Ti3C2via mild sonication. Advantages of the present approach rely not only on the simplicity and efficiency of the delamination procedure but also on the grafting of aryl groups to MXene surfaces, highly suitable for further applications of the newly discovered two-dimensional materials.

  16. XPS study of ruthenium tris-bipyridine electrografted from diazonium salt derivative on microcrystalline boron doped diamond.

    PubMed

    Agnès, Charles; Arnault, Jean-Charles; Omnès, Franck; Jousselme, Bruno; Billon, Martial; Bidan, Gérard; Mailley, Pascal

    2009-12-28

    Boron doped diamond (BDD) functionalization has received an increasing interest during the last few years. Such an infatuation comes from the original properties of BDD, including chemical stability or an electrochemical window, that opens the way for the design of (bio)sensors or smart interfaces. In such a context, diazonium salts appear to be well suited for BDD functionalization as they enable covalent immobilization of functional entities such as enzymes or DNA. In this study we report microcrystalline BDD functionalization with a metallic complex, ruthenium tris(bipyridine), using the p-(tris(bipyridine)Ru(2+))phenyl diazonium salt. Electrografting using cyclic voltammetry (CV) allowed the formation of a ruthenium complex film that was finely characterized using electrochemistry and X-ray photoelectron spectroscopy (XPS). Moreover, we showed that chronopotentiometry (CP) is a convenient tool to monitor Ru complex film deposition through the control of the electrochemical pulse parameters (i.e. current density and pulse duration). Finally, such a control was demonstrated through the correlation between electrochemical and XPS characterizations.

  17. Fabrication of biomembrane-like films on carbon electrodes using alkanethiol and diazonium salt and their application for direct electrochemistry of myoglobin.

    PubMed

    Anjum, Saima; Qi, Wenjing; Gao, Wenyue; Zhao, Jianming; Hanif, Saima; Aziz-Ur-Rehman; Xu, Guobao

    2015-03-15

    Alkanethiols generally form self-assembled monolayers on gold electrodes and the electrochemical reduction of aromatic diazonium salts is a popular method for the covalent modification of carbon. Based on the reaction of alkanethiol with aldehyde groups covalently bound on carbon surface by the electrochemical reduction of aromatic diazonium salts, a new strategy for the modification of carbon electrodes with alkanethiols has been developed. The modification of carbon surface with aldehyde groups is achieved by the electrochemical reduction of aromatic diazonium salts in situ electrogenerated from a nitro precursor, p-nitrophenylaldehyde, in the presence of nitrous acid. By this way, in situ electrogenerated p-aminophenyl aldehyde from p-nitrophenylaldehyde immediately reacts with nitrous acid, effectively minimizing the side reaction of amine groups and aldehyde groups. The as-prepared alkanethiol-modified glassy carbon electrode was further used to make biomembrane-like films by casting didodecyldimethylammonium bromide on its surface. The biomembrane-like films enable the direct electrochemistry of immobilized myoglobin for the detection of hydrogen peroxide. The response is linear over the range of 1-600μM with a detection limit of 0.3μM. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Spontaneous modification of carbon surface with neutral red from its diazonium salts for bioelectrochemical systems.

    PubMed

    Guo, Kun; Chen, Xin; Freguia, Stefano; Donose, Bogdan C

    2013-09-15

    This study introduces a novel and simple method to covalently graft neutral red (NR) onto carbon surfaces based on spontaneous reduction of in situ generated NR diazonium salts. Immobilization of neutral red on carbon surface was achieved by immersing carbon electrodes in NR-NaNO2-HCl solution. The functionalized electrodes were characterized by cyclic voltammetry (CV), atomic force microscope (AFM), and X-ray photoelectron spectroscopy (XPS). Results demonstrated that NR attached in this way retains high electrochemical activity and proved that NR was covalently bound to the carbon surface via the pathway of reduction of aryl diazonium salts. The NR-modified electrodes showed a good stability when stored in PBS solution in the dark. The current output of an acetate-oxidising microbial bioanode made of NR-modified graphite felts were 3.63±0.36 times higher than the unmodified electrodes, which indicates that covalently bound NR can act as electron transfer mediator to facilitate electron transfer from bacteria to electrodes. Copyright © 2013 Elsevier B.V. All rights reserved.

  19. Using supramolecular binding motifs to provide precise control over the ratio and distribution of species in multiple component films grafted on surfaces: demonstration using electrochemical assembly from aryl diazonium salts.

    PubMed

    Gui, Alicia L; Yau, Hon Man; Thomas, Donald S; Chockalingam, Muthukumar; Harper, Jason B; Gooding, J Justin

    2013-04-16

    Supramolecular interactions between two surface modification species are explored to control the ratio and distribution of these species on the resultant surface. A binary mixture of aryl diazonium salts bearing oppositely charged para-substituents (either -SO3(-) or -N(+)(Me)3), which also reduce at different potentials, has been examined on glassy carbon surfaces using cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). Striking features were observed: (1) the two aryl diazonium salts in the mixed solution undergo reductive adsorption at the same potential which is distinctively less negative than the potential required for the reduction of either of the two aryl diazonium salts alone; (2) the surface ratio of the two phenyl derivatives is consistently 1:1 regardless of the ratio of the two aryl diazonium salts in the modification solutions. Homogeneous distribution of the two oppositely charged phenyl species on the modified surface has also been suggested by XPS survey spectra. Diffusion coefficient measurements by DOSY NMR and DFT based computation have indicated the association of the two aryl diazonium species in the solution, which has led to changes in the molecular orbital energies of the two species. This study highlights the potential of using intermolecular interactions to control the assembly of multicomponent thin layers.

  20. Pd-catalyzed arylation reactions with phenol diazonium salts: application in the synthesis of diarylheptanoids.

    PubMed

    Schmidt, Bernd; Hölter, Frank; Kelling, Alexandra; Schilde, Uwe

    2011-05-06

    The first total synthesis of the natural product (3S,7R)-5,6-dehydro-de-O-methyl centrolobine and various analogues is reported, using a highly regio- and diastereoselective Mizoroki-Heck reaction of phenol diazonium salts and enantiopure dihydropyrans. The assigned relative configuration was confirmed by single-crystal X-ray structure analysis, but a revision of the absolute configuration is proposed based on polarimetric measurement. © 2011 American Chemical Society

  1. Aromatic fluorine compounds. VI. Displacement of aryl fluorine in diazonium salts

    USGS Publications Warehouse

    Finger, G.C.; Oesterling, R.E.

    1956-01-01

    Several chlorofluorobenzenes have been isolated from the Schiemann synthesis of fluorobenzenes. These have been shown to be the products of two side reactions occurring during thermal decomposition of the dry benzenediazonium fluoborate salt containing coprecipitated sodium chloride, an unavoidable contaminant in large preparations involving the use of hydrochloric acid and sodium fluoborate. The major side reaction and its chloro product were unexpected; a unique displacement of fluorine ortho to the diazonium group was observed. Replacement of the diazo group with chlorine was the predicted side reaction which proved to be minor. Conditions causing the side reactions and the isolation and identification of the products are described.

  2. Preparation of water-soluble magnetic nanocrystals using aryl diazonium salt chemistry.

    PubMed

    Griffete, Nébéwia; Herbst, Frédéric; Pinson, Jean; Ammar, Souad; Mangeney, Claire

    2011-02-16

    A novel and facile methodology for the in situ surface functionalization of Fe(3)O(4) nanoparticles is proposed, based on the use of aryl diazonium salts chemistry. The grafting reaction involves the formation of diazoates in a basic medium. These species are unstable and dediazonize along a homolytic pathway to give aryl radicals which further react with the Fe(3)O(4) NPs during their formation and stop their growth. Advantages of the present approach rely not only on the simplicity, rapidity, and efficiency of the procedure but also on the formation of strong Fe(3)O(4)-aryl surface bonds, highly suitable for further applications.

  3. A one-pot radioiodination of aryl amines via stable diazonium salts: preparation of 125I-imaging agents.

    PubMed

    Sloan, Nikki L; Luthra, Sajinder K; McRobbie, Graeme; Pimlott, Sally L; Sutherland, Andrew

    2017-10-05

    An operationally simple, one-pot, two-step tandem procedure that allows the incorporation of radioactive iodine into aryl amines via stable diazonium salts is described. The mild conditions are tolerant of various functional groups and substitution patterns, allowing late-stage, rapid access to a wide range of 125 I-labelled aryl compounds and SPECT radiotracers.

  4. Covalent electron transfer chemistry of graphene with diazonium salts.

    PubMed

    Paulus, Geraldine L C; Wang, Qing Hua; Strano, Michael S

    2013-01-15

    Graphene is an atomically thin, two-dimensional allotrope of carbon with exceptionally high carrier mobilities, thermal conductivity, and mechanical strength. From a chemist's perspective, graphene can be regarded as a large polycyclic aromatic molecule and as a surface without a bulk contribution. Consequently, chemistries typically performed on organic molecules and surfaces have been used as starting points for the chemical functionalization of graphene. The motivations for chemical modification of graphene include changing its doping level, opening an electronic band gap, charge storage, chemical and biological sensing, making new composite materials, and the scale-up of solution-processable graphene. In this Account, we focus on graphene functionalization via electron transfer chemistries, in particular via reactions with aryl diazonium salts. Because electron transfer chemistries depend on the Fermi energy of graphene and the density of states of the reagents, the resulting reaction rate depends on the number of graphene layers, edge states, defects, atomic structure, and the electrostatic environment. We limit our Account to focus on pristine graphene over graphene oxide, because free electrons in the latter are already bound to oxygen-containing functionalities and the resulting chemistries are dominated by localized reactivity and defects. We describe the reaction mechanism of diazonium functionalization of graphene and show that the reaction conditions determine the relative degrees of chemisorption and physisorption, which allows for controlled modulation of the electronic properties of graphene. Finally we discuss different applications for graphene modified by this chemistry, including as an additive in polymer matrices, as biosensors when coupled with cells and biomolecules, and as catalysts when combined with nanoparticles.

  5. Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts.

    PubMed

    Xia, Zhenyuan; Leonardi, Francesca; Gobbi, Marco; Liu, Yi; Bellani, Vittorio; Liscio, Andrea; Kovtun, Alessandro; Li, Rongjin; Feng, Xinliang; Orgiu, Emanuele; Samorì, Paolo; Treossi, Emanuele; Palermo, Vincenzo

    2016-07-26

    We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

  6. Synthesis of 3,3-disubstituted oxindoles by visible-light-mediated radical reactions of aryl diazonium salts with N-arylacrylamides.

    PubMed

    Fu, Weijun; Xu, Fengjuan; Fu, Yuqin; Zhu, Mei; Yu, Jiaqi; Xu, Chen; Zou, Dapeng

    2013-12-06

    A mild and efficient visible-light-mediated diarylation of N-arylacrylamides with aryl diazonium salts under mild conditions has been developed. This method provides convenient access to a variety of useful 3,3-disubstituted oxindoles by constructing two C-C bonds in one step.

  7. Grafting the sol-gel based sorbents by diazonium salts: a novel approach toward unbreakable capillary microextraction.

    PubMed

    Bagheri, Habib; Bayat, Parisa; Piri-Moghadam, Hamed

    2013-11-29

    The present work deals with a novel approach for grafting a sol-gel based sorbent, using diazonium salts for preparation of an unbreakable capillary microextraction (CME) device in on-line combination with high performance liquid chromatography (HPLC). The use of diazonium salts modifier allowed all types of metallic and non-metallic substrates to be used without any limitation. Substrates including copper, brass, stainless steel and polytetrafluoroethylene (PTFE) were chosen to be functionalized by chemical or electrochemical reduction of 4-amino phenyl acetic acid. Then, 3-(trimethoxysilyl)propylamine (3TMSPA) was selected as the precursor and the only reagent for preparation of the desired surface chemical bonded sorbent. The presence of chemical bond between substrate, diazonium salts and 3TMSPA is more probably responsible for thermal and solvent stability and long lifetime of the prepared sorbent. Characterization of the aryl group formation on the various substrates along with the prepared sorbents was thoroughly investigated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetry analysis (TGA). Typically, one of the prepared sorbents, deposited on the inner surface of the copper tube, was selected for assessing the developed method. The CME device was used for on-line extraction of atrazine, ametryn and terbutryn, as model compounds, from the aquatic media. After extraction, the HPLC mobile phase was used for on-line desorption and elution of the extracted analytes from the CME loop, containing the grafted sol-gel based sorbent, through the HPLC column. Figures of merit of the developed method were also obtained in which the linearity for the analytes was in the range of 30-1000μgL(-1). The value of LOD (S/N=3) for all analytes was 10μgL(-1) and the RSD% values (n=5) were all below 9.4% at the 500μgL(-1) level. Applicability of the developed method was examined by analyzing some real water samples in

  8. Optical excitation of carbon nanotubes drives stoichiometric reaction with diazonium salts

    NASA Astrophysics Data System (ADS)

    Powell, Lyndsey; Piao, Yanmei; Wang, Yuhuang; YuHuang Wang Research Group Team

    Covalent chemistry is known to lack the precision required to tailor the physical properties of carbon nanostructures. Here we show that, for the first time, light can be used to drive a typically inefficient reaction with single-walled carbon nanotubes in a more stoichiometric fashion. Specifically, our experimental results suggest that light can enhance the reaction rate of diazonium salt with carbon nanotubes by as much as 35-fold, making possible stoichiometric control of the covalent bonding of a functional group to the sp2 carbon lattice. This light-controlled reaction paves the way for the possibility of highly selective and precise chemistry on single-walled carbon nanotubes and other graphitic nanostructures.

  9. Diazonium cation-exchanged clay: an efficient, unfrequented route for making clay/polymer nanocomposites.

    PubMed

    Salmi, Zakaria; Benzarti, Karim; Chehimi, Mohamed M

    2013-11-05

    We describe a simple, off-the-beaten-path strategy for making clay/polymer nanocomposites through tandem diazonium salt interface chemistry and radical photopolymerization. Prior to photopolymerization, sodium montmorillonite (MMT) was ion exchanged with N,N'-dimethylbenzenediazonium cation (DMA) from the tetrafluoroborate salt precursor. DMA acts as a hydrogen donor for benzophenone in solution; this pair of co-initiators permits us to photopolymerize glycidyl methacrylate (GMA) between the lamellae of the diazonium-modified clay, therefore providing intercalated MMT-PGMA nanocomposites with an onset of exfoliation. This work conclusively provides a new approach for bridging reactive and functional polymers to layered nanomaterials via aryl diazonium salts in a simple, fast, efficient cation-exchange approach.

  10. Diazonium salt-mediated synthesis of new amino, hydroxy, propargyl, and maleinimido-containing superparamagnetic Fe@C nanoparticles as platforms for linking bio-entities or organocatalytic moieties

    NASA Astrophysics Data System (ADS)

    Bunge, Alexander; Magerusan, Lidia; Morjan, Ion; Turcu, Rodica; Borodi, Gheorghe; Liebscher, Jürgen

    2015-09-01

    New magnetic Fe@C nanoparticles in the size range of about 20-50 nm functionalized with amino, hydroxy, propargyl, or maleinimido groups were synthesized by reaction with aryl diazonium salts. Aryl diazonium salts wherein the functional groups are linked via a sulfonamide moiety turned out to be advantageous over those with direct linkage. The obtained Fe@C nanoparticles represent magnetic nanoplatforms for linking bio-entities and organocatalysts using amide formation, CuAAC, or thiol-ene click chemistry as exemplified by selected examples. The Fe@C nanoparticles obtained exhibit supramolecular behavior with high value of saturation magnetization rendering them attractive for practical applications in biomedicine and organocatalysis.

  11. The EPR of the triplet state of aryl cations in crystals of diazonium salts

    NASA Astrophysics Data System (ADS)

    Kondratenko, P. A.; Shrubovich, E. V.; Shulga, S. Z.

    The spectra of the electron paramagnetic resonance (EPR) of aryl cations possessing a principle triplet ground-state and orientated in a monocrystal of diazonium salts is studied. It is shown that two nonequivalent paramagnetic centers, which differ in orientation are formed within the crystal. A theoretic description of experimental results is possible only when allowing for the effect of low symmetry. This symmetry is invoked by the interactivity of the paramagnetic center of symmetry C(sub 2v) with the crystal field of symmetry C(sub i).

  12. Synthesis of radiolabelled aryl azides from diazonium salts: experimental and computational results permit the identification of the preferred mechanism.

    PubMed

    Joshi, Sameer M; de Cózar, Abel; Gómez-Vallejo, Vanessa; Koziorowski, Jacek; Llop, Jordi; Cossío, Fernando P

    2015-05-28

    Experimental and computational studies on the formation of aryl azides from the corresponding diazonium salts support a stepwise mechanism via acyclic zwitterionic intermediates. The low energy barriers associated with both transition structures are compatible with very fast and efficient processes, thus making this method suitable for the chemical synthesis of radiolabelled aryl azides.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

  14. Fabrication of superhydrophobic surface on zinc substrate by 3-trifluoromethylbenzene diazonium tetrafluoroborate salts

    NASA Astrophysics Data System (ADS)

    Li, Hong; Huang, Chengya; Zhang, Long; Lou, Wanqiu

    2014-09-01

    In this study we report a new and efficient method of fabricating superhydrophobic surface on zinc plate modified with 3-trifluoromethylbenzene diazonium tetrafluoroborate salts (CF3BD), which shows a water contact angle of 160° for a 4 μl water droplet and a low sliding angle of about 1°. The morphology and chemical composition of as-prepared superhydrophobic zinc surfaces are investigated by means of scanning electron microscopy (SEM), electron probe microanalyzer (EPMA) and FT-IR spectrum. The results show that the organic layers formed on zinc plate surface are provided with the special hierarchical porous microstructure and the low surface energy, which lead to the superhydrophobicity surface on the modified zinc.

  15. Controlled Zn-mediated grafting of thin layers of bipodal diazonium salt on gold and carbon substrates.

    PubMed

    Torréns, Mabel; Ortiz, Mayreli; Turner, Anthony P F; Beni, Valerio; O'Sullivan, Ciara K

    2015-01-07

    A controlled, rapid, and potentiostat-free method has been developed for grafting the diazonium salt (3,5-bis(4-diazophenoxy)benzoic acid tetrafluoroborate (DCOOH)) on gold and carbon substrates, based on a Zn-mediated chemical dediazonation. The highly stable thin layer organic platforms obtained were characterized by cyclic voltammetry, AFM, impedance, XP, and Raman spectroscopies. A dediazonation mechanism based on radical formation is proposed. Finally, DCOOH was proved as a linker to an aminated electroactive probe. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Polymeric salt bridges for conducting electric current in microfluidic devices

    DOEpatents

    Shepodd, Timothy J [Livermore, CA; Tichenor, Mark S [San Diego, CA; Artau, Alexander [Humacao, PR

    2009-11-17

    A "cast-in-place" monolithic microporous polymer salt bridge for conducting electrical current in microfluidic devices, and methods for manufacture thereof is disclosed. Polymeric salt bridges are formed in place in capillaries or microchannels. Formulations are prepared with monomer, suitable cross-linkers, solvent, and a thermal or radiation responsive initiator. The formulation is placed in a desired location and then suitable radiation such as UV light is used to polymerize the salt bridge within a desired structural location. Embodiments are provided wherein the polymeric salt bridges have sufficient porosity to allow ionic migration without bulk flow of solvents therethrough. The salt bridges form barriers that seal against fluid pressures in excess of 5000 pounds per square inch. The salt bridges can be formulated for carriage of suitable amperage at a desired voltage, and thus microfluidic devices using such salt bridges can be specifically constructed to meet selected analytical requirements.

  17. Clay/Polyaniline Hybrid through Diazonium Chemistry: Conductive Nanofiller with Unusual Effects on Interfacial Properties of Epoxy Nanocomposites.

    PubMed

    Jlassi, Khouloud; Chandran, Sarath; Poothanari, Mohammed A; Benna-Zayani, Mémia; Thomas, Sabu; Chehimi, Mohamed M

    2016-04-12

    The concept of conductive network structure in thermoset matrix without sacrificing the inherent mechanical properties of thermoset polymer (e.g., epoxy) is investigated here using "hairy" bentonite fillers. The latter were prepared through the in situ polymerization of aniline in the presence of 4-diphenylamine diazonium (DPA)-modified bentonite (B-DPA) resulting in a highly exfoliated bentonite-DPA/polyaniline (B-DPA/PANI). The nanocomposite filler was mixed with diglycidyl ether of bisphenol A (DGEBA), and the curing agent (4,4'-diaminodiphenylsulfone) (DDS) at high temperature in order to obtain nanocomposites through the conventional melt mixing technique. The role of B-DPA in the modification of the interface between epoxy and B-DPA/polyaniline (B-DPA/PANI) is investigated and compared with the filler B/PANI prepared without any diazonium modification of the bentonite. Synergistic improvement in dielectric properties and mechanical properties points to the fact that the DPA aryl groups from the diazonium precursor significantly modify the interface by acting as an efficient stress transfer medium. In DPA-containing nanocomposites, unique fibril formation was observed on the fracture surface. Moreover, dramatic improvement (210-220%) in fracture toughness of epoxy composite was obtained with B-DPA/PANI filler as compared to the weak improvement of 20-30% noted in the case of the B/PANI filler. This work shows that the DPA diazonium salt has an important effect on the improvement of the interfacial properties and adhesion of DGEBA and clay/PANI nanofillers.

  18. Antimicrobial Polymeric Materials with Quaternary Ammonium and Phosphonium Salts

    PubMed Central

    Xue, Yan; Xiao, Huining; Zhang, Yi

    2015-01-01

    Polymeric materials containing quaternary ammonium and/or phosphonium salts have been extensively studied and applied to a variety of antimicrobial-relevant areas. With various architectures, polymeric quaternary ammonium/phosphonium salts were prepared using different approaches, exhibiting different antimicrobial activities and potential applications. This review focuses on the state of the art of antimicrobial polymers with quaternary ammonium/phosphonium salts. In particular, it discusses the structure and synthesis method, mechanisms of antimicrobial action, and the comparison of antimicrobial performance between these two kinds of polymers. PMID:25667977

  19. A simple approach to patterned protein immobilization on silicon via electrografting from diazonium salt solutions.

    PubMed

    Flavel, Benjamin S; Gross, Andrew J; Garrett, David J; Nock, Volker; Downard, Alison J

    2010-04-01

    A highly versatile method utilizing diazonium salt chemistry has been developed for the fabrication of protein arrays. Conventional ultraviolet mask lithography was used to pattern micrometer sized regions into a commercial photoresist on a highly doped p-type silicon (100) substrate. These patterned regions were used as a template for the electrochemical grafting of the in situ generated p-aminobenzenediazonium cation to form patterns of aminophenyl film on silicon. Immobilization of biomolecules was demonstrated by coupling biotin to the aminophenyl regions followed by reaction with fluorescently labeled avidin and visualization with fluorescence microscopy. This simple patterning strategy is promising for future application in biosensor devices.

  20. Tunable Cascade Reaction of Aryl Diazonium Salts and Trialkylamine: Synthesis of Monofluorinated Arylhydrazones and gem-Difluorinated Azo Compounds.

    PubMed

    Guo, Rui; Zhang, Zhengjuan; Shi, Feng; Tang, Pingping

    2016-03-04

    The first example of a mild and tunable cascade reaction of aryl diazonium salts and trialkylamine in the presence of Selectfluor to prepare monofluorinated arylhydrazones and gem-difluorinated azo compounds without metal has been explored. In the presence of H2O, the monofluorinated arylhydrazones were observed in moderate to good yield. In the absence of H2O, the gem-difluorinated azo compounds were obtained. The fluorinated arylhydrazones were utilized to synthesize fluorinated pyrazoles and other nitrogen-containing compounds.

  1. Formation of mixed organic layers by stepwise electrochemical reduction of diazonium compounds.

    PubMed

    Santos, Luis; Ghilane, Jalal; Lacroix, Jean Christophe

    2012-03-28

    This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

  2. Chameleonic reactivity of vicinal diazonium salt of acetylenyl-9,10-anthraquinones: synthetic application toward two heterocyclic targets.

    PubMed

    Stepanov, A A; Gornostaev, L M; Vasilevsky, S F; Arnold, E V; Mamatyuk, V I; Fadeev, D S; Gold, B; Alabugin, I V

    2011-11-04

    The nature of products in the diazotization of 1-amino-2-acetylenyl-9,10-anthraquinones strongly depends on the nature of substituents at both the alkyne and at the anthraquinone core. Donor substitution (NHAr, OH) at the fourth position stabilizes the diazonium salt at C1, decelerating electrophilic cyclization at the arylethynyl substituent at C2. This effect allows the replacement of the diazonium with azide group and subsequent closure into isoxazole ring with preservation of the alkyne. In contrast, electrophilic 5-exo-dig cyclizations to condensed pyrazoles is observed for the combination of donor substituents at the aryl alkyne moiety and an OAc substituent at C4. The latter process provides a new synthetic route to 3-ethynyl-[1,9-cd]isoxazol-6-ones that are difficult to access otherwise. DFT calculations suggest that donor substituents have only a minor effect on alkyne and diazonium polarization in the reactant but provide specific transition state stabilization by stabilizing the incipient vinyl cation. This analysis provides the first computational data on electrophilic 5-exo-dig cyclization in its parent form and the nucleophile-promoted version. This cyclization is a relatively fast but endothermic process that is rendered thermodynamically feasible by the enol-keto tautomerization with concomitant aromatization in the five-membered heteroaromatic ring. Computations suggest that the importance of nucleophilic assistance in the transition state for a relatively weak nucleophile such as water is minor because the energy gain due to the Lewis base coordination to the carbocationic center is more than compensated for by the unfavorable entropic term for the bimolecular proces.

  3. Functionalization of magnetic nanocrystals by oligo (ethylene oxide) chains carrying diazonium and iniferter end groups.

    PubMed

    Ahmad, Randa; Griffete, Nébéwia; Lamouri, Aazdine; Mangeney, Claire

    2013-10-01

    The water stability of iron oxide nanoparticles (NPs) is a major issue for biomedical and biological applications. This paper presents a versatile approach for preparing water-soluble iron oxide nanoparticles coated by bifunctional oligo(ethylene oxide) (OEO) chains, carrying on the one side a diazonium end group for covalent grafting at the NP surface and on the other side an iniferter group (diethyl dithiocarbamate) for initiating the growing of poly(methacrylic acid). The nanoparticles were synthesized by coprecipitation in basic media and functionalized in situ by adding the diazonium salt directly in the synthesis medium. Oligo(ethylene oxide) with various chain lengths (from one to three monomer units) was grafted at the NP surface using this approach. The length of the OEO spacer between the NP surface and the iniferter end group was found to be a critical parameter for controlling the colloidal stability of the hybrid NPs. The polymerization time was also shown to strongly influence their colloidal stability, emphasizing the interest to control the interfacial properties of the hybrids for obtaining stable dispersions in water. Copyright © 2013 Elsevier Inc. All rights reserved.

  4. SiGe derivatization by spontaneous reduction of aryl diazonium salts

    NASA Astrophysics Data System (ADS)

    Girard, A.; Geneste, F.; Coulon, N.; Cardinaud, C.; Mohammed-Brahim, T.

    2013-10-01

    Germanium semiconductors have interesting properties for FET-based biosensor applications since they possess high surface roughness allowing the immobilization of a high amount of receptors on a small surface area. Since SiGe combined low cost of Si and intrinsic properties of Ge with high mobility carriers, we focused the study on this particularly interesting material. The comparison of the efficiency of a functionalization process involving the spontaneous reduction of diazonium salts is studied on Si(1 0 0), SiGe and Ge semiconductors. XPS analysis of the functionalized surfaces reveals the presence of a covalent grafted layer on all the substrates that was confirmed by AFM. Interestingly, the modified Ge derivatives have still higher surface roughness after derivatization. To support the estimated thickness by XPS, a step measurement of the organic layers is done by AFM or by profilometer technique after a O2 plasma etching of the functionalized layer. This original method is well-adapted to measure the thickness of thin organic films on rough substrates such as germanium. The analyses show a higher chemical grafting on SiGe substrates compared with Si and Ge semiconductors.

  5. Base free aryl coupling of diazonium compounds and boronic esters: self-activation allowing an overall highly practical process.

    PubMed

    Bonin, Hélène; Delbrayelle, Dominique; Demonchaux, Patrice; Gras, Emmanuel

    2010-04-21

    Boronic esters have long been considered as poor partners in cross-coupling reactions with arene diazoniums. Here is reported an unprecedented application of self-activated boronic esters in a base-free cross-coupling reaction with diazonium salts under mild and user friendly conditions.

  6. Synergistic effect in carbon coated LiFePO4 for high yield spontaneous grafting of diazonium salt. Structural examination at the grain agglomerate scale.

    PubMed

    Madec, Lénaïc; Robert, Donatien; Moreau, Philippe; Bayle-Guillemaud, Pascale; Guyomard, Dominique; Gaubicher, Joël

    2013-08-07

    Molecular grafting of p-nitrobenzene diazonium salt at the surface of (Li)FePO4-based materials was thoroughly investigated. The grafting yields obtained by FTIR, XPS, and elemental analysis for core shell LiFePO4-C are found to be much higher than the sum of those associated with either the LiFePO4 core or the carbon shell alone, thereby revealing a synergistic effect. Electrochemical, XRD, and EELS experiments demonstrate that this effect stems from the strong participation of the LiFePO4 core that delivers large amounts of electrons to the carbon substrate at a constant energy, above the Fermi level of the diazonium salt. Correspondingly large multilayer anisotropic structures that are associated with outstanding grafting yields could be observed from TEM experiments. Results therefore constitute strong evidence of a grafting mechanism where homolytic cleavage of the N2(+) species occurs together with the formation and grafting of radical nitro-aryl intermediates. Although the oxidation and concomitant Li deintercalation of LiFePO4 grains constitute the main driving force of the functionalization reaction, EFTEM EELS mapping shows a striking lack of spatial correlation between grafted grains and oxidized ones.

  7. One-step formation of bifunctionnal aryl/alkyl grafted films on conducting surfaces by the reduction of diazonium salts in the presence of alkyl iodides.

    PubMed

    Hetemi, Dardan; Hazimeh, Hassan; Decorse, Philippe; Galtayries, Anouk; Combellas, Catherine; Kanoufi, Frédéric; Pinson, Jean; Podvorica, Fetah I

    2015-05-19

    The formation of partial perfluoroalkyl or alkyl radicals from partial perfluoroalkyl or alkyl iodides (ICH2CH2C6F13 and IC6H13) and their reaction with surfaces takes place at low driving force (∼-0.5 V/SCE) when the electrochemical reaction is performed in acetonitrile in the presence of diazonium salts (ArN2(+)), at a potential where the latter is reduced. By comparison to the direct grafting of ICH2CH2C6F13, this corresponds to a gain of ∼2.1 V in the case of 4-nitrobenzenediazonium. Such electrochemical reaction permits the modification of gold surfaces (and also carbon, iron, and copper) with mixed aryl-alkyl groups (Ar = 3-CH3-C6H4, 4-NO2-C6H4, and 4-Br-C6H4, R = C6H13 or (CH2)2-C6F13). These strongly bonded mixed layers are characterized by IRRAS, XPS, ToF-SIMS, ellipsometry, water contact angles, and cyclic voltammetry. The relative proportions of grafted aryl and alkyl groups can be varied along with the relative concentrations of diazonium and iodide components in the grafting solution. The formation of the films is assigned to the reaction of aryl and alkyl radicals on the surface and on the first grafted layer. The former is obtained from the electrochemical reduction of the diazonium salt; the latter results from the abstraction of an iodine atom by the aryl radical. The mechanism involved in the growth of the film provides an example of complex surface radical chemistry.

  8. Bulk functionalization of graphene using diazonium compounds and amide reaction

    NASA Astrophysics Data System (ADS)

    Peng, Chang; Xiong, Yuzi; Liu, Zhibo; Zhang, Fan; Ou, Encai; Qian, Jiangtao; Xiong, Yuanqin; Xu, Weijian

    2013-09-01

    An efficient and convenient method is applied to introduce varieties of simple functionalities onto the graphene surface for the bulk preparation, which begins with pristine graphite that does not require initial oxidative damage of the graphene basal planes. Diazonium compounds functionalized reaction is demonstrated and it successfully prevented the aggregation of graphene for which providing solubility in high polar organic media or even in volatile solvents such as ethanol and acetone. This approach is complemented by the phenyl carboxylic diazonium salt functionalized graphene (PCFG) attachment of a symmetrically substituted zinc phthalocyanine (PCFG-Pc) using the amide reaction, which is used for the covalent introduction of a complex phthalocyanine molecule.

  9. Process for derivatizing carbon nanotubes with diazonium species

    NASA Technical Reports Server (NTRS)

    Tour, James M. (Inventor); Bahr, Jeffrey L. (Inventor); Yang, Jiping (Inventor)

    2007-01-01

    The invention incorporates new processes for the chemical modification of carbon nanotubes. Such processes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications and sensor devices. The methods of derivatization include electrochemical induced reactions thermally induced reactions (via in-situ generation of diazonium compounds or pre-formed diazonium compounds), and photochemically induced reactions. The derivatization causes significant changes in the spectroscopic properties of the nanotubes. The estimated degree of functionality is ca. 1 out of every 20 to 30 carbons in a nanotube bearing a functionality moiety. Such electrochemical reduction processes can be adapted to apply site-selective chemical functionalization of nanotubes. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes ##STR00001##.

  10. Electrochemical Grafting of Graphene Nano Platelets with Aryl Diazonium Salts.

    PubMed

    Qiu, Zhipeng; Yu, Jun; Yan, Peng; Wang, Zhijie; Wan, Qijin; Yang, Nianjun

    2016-10-26

    To vary interfacial properties, electrochemical grafting of graphene nano platelets (GNP) with 3,5-dichlorophenyl diazonium tetrafluoroborate (aryl-Cl) and 4-nitrobenzene diazonium tetrafluoroborate (aryl-NO 2 ) was realized in a potentiodynamic mode. The covalently bonded aryl layers on GNP were characterized using atomic force microscopy and X-ray photoelectron spectroscopy. Electrochemical conversion of aryl-NO 2 into aryl-NH 2 was conducted. The voltammetric and impedance behavior of negatively and positively charged redox probes (Fe(CN) 6 3-/4- and Ru(NH 3 ) 6 2+/3+ ) on three kinds of aryl layers grafted on GNP reveal that their interfacial properties are determined by the charge states of redox probes and reactive terminal groups (-Cl, -NO 2 , -NH 2 ) in aryl layers. On aryl-Cl and aryl-NH 2 garted GNP, selective and sensitive monitoring of positively charged lead ions as well as negatively charged nitrite and sulfite ions was achieved, respectively. Such a grafting procedure is thus a perfect way to design and control interfacial properties of graphene.

  11. Electrodeposited Organic Layers Formed from Aryl Diazonium Salts for Inhibition of Copper Corrosion

    PubMed Central

    Chira, Ana; Bucur, Bogdan; Radu, Gabriel-Lucian

    2017-01-01

    Copper substrates deposed on a gold screen-printed electrode were covered with different aryl diazonium salts by electrodeposition at 0.25 mA for 30 or 300 s. Seven compounds were investigated: 4-aminophenylacetic acid, 4-aminophenethyl alcohol, 4-fluoroaniline, 4-(heptadecafluorooctyl)aniline, 4-aminoantipyrine, 4-(4-aminophenyl)butyric acid and 3,4,5-trimethoxyaniline. Quantitative monitoring of the electrodeposition process was carried out by electrogravimetry using quartz crystal microbalance (QCM). The electrodeposited mass varies between 26 ng/cm2 for 4-fluoroaniline formed during 30 s to 442 ng/cm2 for 4-phenylbutyric acid formed during 300 s. The corrosion inhibition properties of aryl-modified layers have been studied in buffer citrate with pH = 3 or 3.5% NaCl solutions using electrochemical noise (ECN) and Tafel potentiodynamic polarization measurements. A corrosion inhibiting efficiency up to 90% was found. The highest corrosion inhibition was obtained for 4-(4-aminophenyl)butyric acid and the lowest for 4-fluoroaniline. A relation between the inhibition efficiency and the chemical nature of the substituents in the protective layer was found. PMID:28772600

  12. Electrodeposited Organic Layers Formed from Aryl Diazonium Salts for Inhibition of Copper Corrosion.

    PubMed

    Chira, Ana; Bucur, Bogdan; Radu, Gabriel-Lucian

    2017-02-28

    Copper substrates deposed on a gold screen-printed electrode were covered with different aryl diazonium salts by electrodeposition at 0.25 mA for 30 or 300 s. Seven compounds were investigated: 4-aminophenylacetic acid, 4-aminophenethyl alcohol, 4-fluoroaniline, 4-(heptadecafluorooctyl)aniline, 4-aminoantipyrine, 4-(4-aminophenyl)butyric acid and 3,4,5-trimethoxyaniline. Quantitative monitoring of the electrodeposition process was carried out by electrogravimetry using quartz crystal microbalance (QCM). The electrodeposited mass varies between 26 ng/cm² for 4-fluoroaniline formed during 30 s to 442 ng/cm² for 4-phenylbutyric acid formed during 300 s. The corrosion inhibition properties of aryl-modified layers have been studied in buffer citrate with pH = 3 or 3.5% NaCl solutions using electrochemical noise (ECN) and Tafel potentiodynamic polarization measurements. A corrosion inhibiting efficiency up to 90% was found. The highest corrosion inhibition was obtained for 4-(4-aminophenyl)butyric acid and the lowest for 4-fluoroaniline. A relation between the inhibition efficiency and the chemical nature of the substituents in the protective layer was found.

  13. Diazonium-derived aryl films on gold nanoparticles: evidence for a carbon-gold covalent bond.

    PubMed

    Laurentius, Lars; Stoyanov, Stanislav R; Gusarov, Sergey; Kovalenko, Andriy; Du, Rongbing; Lopinski, Gregory P; McDermott, Mark T

    2011-05-24

    Tailoring the surface chemistry of metallic nanoparticles is generally a key step for their use in a wide range of applications. There are few examples of organic films covalently bound to metal nanoparticles. We demonstrate here that aryl films are formed on gold nanoparticles from the spontaneous reduction of diazonium salts. The structure and the bonding of the film is probed with surface-enhanced Raman scattering (SERS). Extinction spectroscopy and SERS show that a nitrobenzene film forms on gold nanoparticles from the corresponding diazonium salt. Comparison of the SERS spectrum with spectra computed from density functional theory models reveals a band characteristic of a Au-C stretch. The observation of this stretch is direct evidence of a covalent bond. A similar band is observed in high-resolution electron energy loss spectra of nitrobenzene layers on planar gold. The bonding of these types of films through a covalent interaction on gold is consistent with their enhanced stability observed in other studies. These findings provide motivation for the use of diazonium-derived films on gold and other metals in applications where high stability and/or strong adsorbate-substrate coupling are required.

  14. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

    PubMed

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

    2016-03-14

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

  15. Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

    PubMed Central

    Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T.; Evoy, Stephane

    2016-01-01

    Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors. PMID:26985910

  16. Electrografting of alkyl films at low driving force by diverting the reactivity of aryl radicals derived from diazonium salts.

    PubMed

    Hetemi, Dardan; Kanoufi, Frédéric; Combellas, Catherine; Pinson, Jean; Podvorica, Fetah I

    2014-11-25

    Alkyl and partial perfluoroalkyl groups are strongly attached to carbon surfaces through (i) the abstraction of the iodine atom from an iodoalkane by the sterically hindered 2,6-dimethylphenyl radical and (ii) the reaction of the ensuing alkyl radical with the carbon surface. Since the 2,6-dimethylphenyl radical is obtained at -0.25 V/Ag/AgCl by reducing the corresponding diazonium salt, the electrografting reaction is facilitated by ∼1.7 V by comparison with the direct electrografting of the iodo compounds. Layers of various thicknesses, including monolayers, are obtained by controlling the time duration of the electrolysis. The grafted films are characterized by electrochemistry, IR, XPS, ellipsometry, and water contact angles.

  17. Effect of doping on the modification of polycrystalline silicon by spontaneous reduction of diazonium salts

    NASA Astrophysics Data System (ADS)

    Girard, A.; Coulon, N.; Cardinaud, C.; Mohammed-Brahim, T.; Geneste, F.

    2014-09-01

    The chemical modification of doped polycrystalline silicon materials (N+, N++ and P++) and silicon (1 0 0) and (1 1 1) used as references is investigated by spontaneous reduction of diazonium salts. The effectiveness of the grafting process on all polySi surfaces is shown by AFM and XPS analyses. The effect of substrate doping on the efficiency of the electrografting process is compared by using the thicknesses of the deposited organic films. For a better accuracy, two methods are used to estimate the thicknesses: XPS and the coupling of a O2 plasma etching with AFM measurement. Structural characteristics of the poly-Si films were investigated by Scanning Electron Microscopy and X-ray diffraction to find a correlation between the structure of the material and its reactivity. Different parameters that could have an impact on the efficiency of the grafting procedure are discussed. The observed differences between differently doped silicon surfaces is rather limited, this is in agreement with the radical character of the reacting species.

  18. Enhanced chemiluminescence-based detection on gold substrate after electrografting of diazonium precursor-coated gold nanoparticles.

    PubMed

    Houmed Adabo, Ali; Zeggari, Rabah; Mohamed Saïd, Nasser; Bazzi, Rana; Elie-Caille, Céline; Marquette, Christophe; Martini, Matteo; Tillement, Olivier; Perriat, Pascal; Chaix, Carole; Boireau, Wilfrid; Roux, Stéphane

    2016-04-01

    Since it was demonstrated that nanostructured surfaces are more efficient for the detection based on the specific capture of analytes, there is a real need to develop strategies for grafting nanoparticles onto flat surfaces. Among the different routes for the functionalization of a surface, the reduction of diazonium salts appears very attractive for the covalent immobilization of nanoparticles because this method does not require a pre-treatment of the surface. For achieving this goal, gold nanoparticles coated by precursor of diazonium salts were synthesized by reduction of gold salt in presence of mercaptoaniline. These mercaptoaniline-coated gold nanoparticles (Au@MA) were successfully immobilized onto various conducting substrates (indium tin oxide (ITO), glassy carbon (GC) and gold electrodes with flat terraces) after addition of sodium nitrite at fixed potential. When applied onto the gold electrodes, such a grafting strategy led to an obvious enhancement of the luminescence of luminol used for the biodetection. Copyright © 2016 Elsevier Inc. All rights reserved.

  19. Protein resistance of surfaces modified with oligo(ethylene glycol) aryl diazonium derivatives.

    PubMed

    Fairman, Callie; Ginges, Joshua Z; Lowe, Stuart B; Gooding, J Justin

    2013-07-22

    Anti-fouling surfaces are of great importance for reducing background interference in biosensor signals. Oligo(ethylene glycol) (OEG) moieties are commonly used to confer protein resistance on gold, silicon and carbon surfaces. Herein, we report the modification of surfaces using electrochemical deposition of OEG aryl diazonium salts. Using electrochemical and contact angle measurements, the ligand packing density is found to be loose, which supports the findings of the fluorescent protein labelling that aryl diazonium OEGs confer resistance to nonspecific adsorption of proteins albeit lower than alkane thiol-terminated OEGs. In addition to protein resistance, aryl diazonium attachment chemistry results in stable modification. In common with OEG species on gold electrodes, OEGs with distal hydroxyl moieties do confer superior protein resistance to those with a distal methoxy group. This is especially the case for longer derivatives where superior coiling of the OEG chains is possible. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Formylbenzene diazonium hexafluorophosphate reagent for tyrosine-selective modification of proteins and the introduction of a bioorthogonal aldehyde.

    PubMed

    Gavrilyuk, Julia; Ban, Hitoshi; Nagano, Masanobu; Hakamata, Wataru; Barbas, Carlos F

    2012-12-19

    4-Formylbenzene diazonium hexafluorophosphate (FBDP) is a novel bench-stable crystalline diazonium salt that reacts selectively with tyrosine to install a bioorthogonal aldehyde functionality. Model studies with N-acyl-tyrosine methylamide allowed us to identify conditions optimal for tyrosine ligation reactions with small peptides and proteins. FBDP-based conjugation was used for the facile introduction of small molecule tags, poly(ethylene glycol) chains (PEGylation), and functional small molecules onto model proteins and to label the surface of living cells.

  1. Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays

    PubMed Central

    Zheng, Wei; Du, Rongbing; Cao, Yong; Mohammad, Mohammad A.; Dew, Steven K.; McDermott, Mark T.; Evoy, Stephane

    2015-01-01

    Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings. PMID:26263989

  2. Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays.

    PubMed

    Zheng, Wei; Du, Rongbing; Cao, Yong; Mohammad, Mohammad A; Dew, Steven K; McDermott, Mark T; Evoy, Stephane

    2015-07-30

    Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings.

  3. Formylbenzene diazonium hexafluorophosphate reagent for tyrosine-selective modification of proteins and the introduction of a bioorthogonal aldehyde

    PubMed Central

    Gavrilyuk, Julia; Ban, Hitoshi; Nagano, Masanobu; Hakamata, Wataru; Barbas, Carlos F.

    2012-01-01

    4-Formylbenzene diazonium hexafluorophosphate (FBDP) is a novel bench-stable crystalline diazonium salt that reacts selectively with tyrosine to install a bioorthogonal aldehyde functionality. Model studies with N-acyl-tyrosine methylamide allowed us to identify conditions optimal for tyrosine ligation reactions with small peptides and proteins. FBDP-based conjugation was used for the facile introduction of small molecule tags, poly(ethylene) glycol chains (PEGylation), and functional small molecules onto model proteins and to label the surface of living cells. PMID:23181702

  4. Carbon nanotube-poly(methyl methacrylate) hybrid films: preparation using diazonium salt chemistry and mechanical properties.

    PubMed

    Mammeri, Fayna; Teyssandier, Joan; Darche-Dugaret, Clément; Debacker, Sabine; Le Bourhis, Eric; Chehimi, Mohamed Mehdi

    2014-11-01

    The poor miscibility of carbon nanotubes (CNTs) in common organic solvents and organic monomers requires their modification by suitable functional (reactive or not) groups prior to their incorporation in thermoplastic polymers. Dispersion behavior of carbon nanotubes and mechanical properties of various CNT-poly(methylmethacrylate) (PMMA) nanocomposites were investigated. We studied the influence of the surface chemistry through the use of diazonium salts as an elegant and environmentally friendly platform to provide a suitable sidewall functionalization by methyl methacrylate functions. We used either a molecular size functional group through the grafting of methacryloxypropyltrimethoxysilane or a macromolecular size one, consisting in PMMA brushes grown by SI-ATRP in order to study the influence of the length of methacrylate function on the dispersion of CNT in PMMA. The hardness and the elastic indentation modulus of all hybrid films were obtained through nanoindentation measurements and found to increase, using ATRP-modified CNTs, suggesting a better dispersion of CNTs in PMMA due to optimal inorganic-organic interactions promoted by the short chains of PMMA. Copyright © 2014 Elsevier Inc. All rights reserved.

  5. Molecular perspective on diazonium adsorption for controllable functionalization of single-walled carbon nanotubes in aqueous surfactant solutions.

    PubMed

    Lin, Shangchao; Hilmer, Andrew J; Mendenhall, Jonathan D; Strano, Michael S; Blankschtein, Daniel

    2012-05-16

    Functionalization of single-walled carbon nanotubes (SWCNTs) using diazonium salts allows modification of their optical and electronic properties for a variety of applications, ranging from drug-delivery vehicles to molecular sensors. However, control of the functionalization process remains a challenge, requiring molecular-level understanding of the adsorption of diazonium ions onto heterogeneous, charge-mobile SWCNT surfaces, which are typically decorated with surfactants. In this paper, we combine molecular dynamics (MD) simulations, experiments, and equilibrium reaction modeling to understand and model the extent of diazonium functionalization of SWCNTs coated with various surfactants (sodium cholate, sodium dodecyl sulfate, and cetyl trimethylammonium bromide). We show that the free energy of diazonium adsorption, determined using simulations, can be used to rank surfactants in terms of the extent of functionalization attained following their adsorption on the nanotube surface. The difference in binding affinities between linear and rigid surfactants is attributed to the synergistic binding of the diazonium ion to the local "hot/cold spots" formed by the charged surfactant heads. A combined simulation-modeling framework is developed to provide guidance for controlling the various sensitive experimental conditions needed to achieve the desired extent of SWCNT functionalization.

  6. Hydroxynaphthoquinone ultrathin films obtained by diazonium electroreduction: toward design of biosensitive electroactive interfaces.

    PubMed

    March, Gregory; Reisberg, Steeve; Piro, Benoit; Pham, Minh-Chau; Fave, Claire; Noel, Vincent

    2010-05-01

    Electroactive 2-(phenylsulfanyl)-8-hydroxy-1,4-naphthoquinone has been electrodeposited via the reduction of the corresponding diazonium salt on Au electrodes. Surface characterizations by X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IRRAS) reveal that the mechanism of film deposition follows an aryl radical formation and its immobilization on the electrode surface. Electrochemical study shows that the surface coverage can be finely tuned (thickness between one and four layers) by adjusting the potential and the deposition time. By managing the potential applied when reducing diazonium in potentiostatic mode, the formed layer could mediate or not charge transfer. This is the first time that the films obtained by diazonium process are demonstrated to act as mediators in the growth process. Hence, with potentials higher than the formal potential of quinone group, very thin and homogeneous layers are obtained, whereas thicker films are formed when more cathodic potentials than that of quinone are applied. The possibility to manage the charge-transfer kinetics, the thickness, and the homogeneity of electroactive deposits is interesting in the scope of designing electrochemical transducers.

  7. A transition-metal-free synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides.

    PubMed

    Xia, Zhonghua; Zhu, Qiang

    2013-08-16

    A transition-metal-free carboxyamidation process, using aryl diazonium tetrafluoroborates and isocyanides under mild conditions, has been developed. This novel conversion was initiated by a base and solvent induced aryl radical, followed by radical addition to isocyanide and single electron transfer (SET) oxidation, affording the corresponding arylcarboxyamide upon hydration of the nitrilium intermediate.

  8. Triggering the Electrolyte-Gated Organic Field-Effect Transistor output characteristics through gate functionalization using diazonium chemistry: Application to biodetection of 2,4-dichlorophenoxyacetic acid.

    PubMed

    Nguyen, T T K; Nguyen, T N; Anquetin, G; Reisberg, S; Noël, V; Mattana, G; Touzeau, J; Barbault, F; Pham, M C; Piro, B

    2018-08-15

    We investigated an Electrolyte-Gated Organic Field-Effect transistor based on poly(N-alkyldiketopyrrolo-pyrrole dithienylthieno[3,2-b]thiophene) as organic semiconductor whose gate electrode was functionalized by electrografting a functional diazonium salt capable to bind an antibody specific to 2,4-dichlorophenoxyacetic acid (2,4-D), an herbicide well-known to be a soil and water pollutant. Molecular docking computations were performed to design the functional diazonium salt to rationalize the antibody capture on the gate surface. Sensing of 2,4-D was performed through a displacement immunoassay. The limit of detection was estimated at around 2.5 fM. Copyright © 2018 Elsevier B.V. All rights reserved.

  9. New Method for Super Hydrophobic Treatment of Gas Diffusion Layers for Proton Exchange Membrane Fuel Cells Using Electrochemical Reduction of Diazonium Salts.

    PubMed

    Thomas, Yohann R J; Benayad, Anass; Schroder, Maxime; Morin, Arnaud; Pauchet, Joël

    2015-07-15

    The purpose of this article is to report a new method for the surface functionalization of commercially available gas diffusion layers (GDLs) by the electrochemical reduction of diazonium salt containing hydrophobic functional groups. The method results in superhydrophobic GDLs, over a large area, without pore blocking. An X-ray photoelectron spectroscopy study based on core level spectra and chemical mapping has demonstrated the successful grafting route, resulting in a homogeneous distribution of the covalently bonded hydrophobic molecules on the surface of the GDL fibers. The result was corroborated by contact angle measurement, showing similar hydrophobicity between the grafted and PTFE-modified GDLs. The electrochemically modified GDLs were tested in proton exchange membrane fuel cells under automotive, wet, and dry conditions and demonstrated improved performance over traditional GDLs.

  10. 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.

  11. Induction heating to trigger the nickel surface modification by in situ generated 4-carboxybenzene diazonium

    NASA Astrophysics Data System (ADS)

    Arrotin, Bastien; Jacques, Amory; Devillers, Sébastien; Delhalle, Joseph; Mekhalif, Zineb

    2016-05-01

    Nickel is commonly used in numerous applications and is one of the few materials that present strong ferromagnetic properties. These make it a suitable material for induction heating which can be used to activate the grafting of organic species such as diazonium salts onto the material. Diazonium compounds are often used for the modification of metals and alloys thanks to their easy chemical reduction onto the substrates and the possibility to apply a one-step in situ generation process of the diazonium species. This work focuses on the grafting of 4-aminocarboxybenzene on nickel substrates in the context of a spontaneous grafting conducted either at room temperature or by thermal assistance through conventional heating and induction heating. These modifications are also carried out with the goal of maintaining the oxides layer as much as possible unaffected. The benefits of using induction heating with respect to conventional heating are an increase of the grafting rate, a better control of the reaction and a slighter impact on the oxides layer.

  12. Electrochemical immunosensor for ethinylestradiol using diazonium salt grafting onto silver nanoparticles-silica-graphene oxide hybrids.

    PubMed

    Cincotto, Fernando H; Martínez-García, Gonzalo; Yáñez-Sedeño, Paloma; Canevari, Thiago C; Machado, S A S; Pingarrón, José M

    2016-01-15

    This work describes the preparation of an electrochemical immunosensor for ethinylestradiol (EE2) based on grafting of diazonium salt of 4-aminobenzoic acid onto a glassy carbon electrode modified with silver nanoparticles/SiO2/graphene oxide hybrid followed by covalent binding of anti-ethinylestradiol (anti-EE2) to activated carboxyl groups. A competitive immunoassay was developed for the determination of the hormone using peroxidase-labeled ethinylestradiol (HRP-EE2) and measurement of the amperometric response at -200mV in the presence of hydroquinone (HQ) as redox mediator. The calibration curve for EE2 exhibited a linear range between 0.1 and 50ng/mL (r(2)=0.996), with a detection limit of 65pg/mL. Interference studies with other hormones related with EE2 revealed the practical specificity of the developed method for the analyte. A good reproducibility, with RSD=4.5% (n=10) was also observed. The operating stability of a single bioelectrode modified with anti-EE2 was maintained at least for 15 days when it was stored at 4°C under humid conditions between measurements. The developed immunosensor was applied to the analysis of spiked urine with good results. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Metal-composite adhesion based on diazonium chemistry.

    PubMed

    Oweis, Yara; Alageel, Omar; Kozak, Paige; Abdallah, Mohamed-Nur; Retrouvey, Jean-Marc; Cerruti, Marta; Tamimi, Faleh

    2017-11-01

    Composite resins do not adhere well to dental alloys. This weak bond can result in failure at the composite-metal interface in fixed dental prostheses and orthodontic brackets. The aim of this study was to develop a new adhesive, based on diazonium chemistry, to facilitate chemical bonding between dental alloys and composite resin. Samples of two types of dental alloys, stainless steel and cobalt chromium were primed with a diazonium layer in order to create a surface coating favorable for composite adhesion. Untreated metal samples served as controls. The surface chemical composition of the treated and untreated samples was analyzed by X-ray photoelectron spectroscopy (XPS) and the tensile strength of the bond with composite resin was measured. The diazonium adhesive was also tested for shear bond strength between stainless steel orthodontic brackets and teeth. XPS confirmed the presence of a diazonium coating on the treated metals. The coating significantly increased the tensile and shear bond strengths by three and four folds respectively between the treated alloys and composite resin. diazonium chemistry can be used to develop composite adhesives for dental alloys. Diazonium adhesion can effectively achieve a strong chemical bond between dental alloys and composite resin. This technology can be used for composite repair of fractured crowns, for crown cementation with resin based cements, and for bracket bonding. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  14. Electrografting of conductive oligomers and polymers using diazonium electroreduction

    NASA Astrophysics Data System (ADS)

    Lacroix, Jean Christophe; Trippe-Allard, Gaelle; Ghilane, Jalal; Martin, Pascal

    2014-03-01

    This paper describes the attachment of conjugated oligomers onto electrode surface through the reduction of diazonium compounds. In this connection some properties of conjugated oligomers and of layers grafted through diazonium electroreduction will first be briefly presented. The electrochemical behavior of conjugated oligomers grafted on a surface using diazonium electroreduction will then be discussed.

  15. Gold Redox Catalysis through Base-Initiated Diazonium Decomposition toward Alkene, Alkyne, and Allene Activation.

    PubMed

    Dong, Boliang; Peng, Haihui; Motika, Stephen E; Shi, Xiaodong

    2017-08-16

    The discovery of photoassisted diazonium activation toward gold(I) oxidation greatly extended the scope of gold redox catalysis by avoiding the use of a strong oxidant. Some practical issues that limit the application of this new type of chemistry are the relative low efficiency (long reaction time and low conversion) and the strict reaction condition control that is necessary (degassing and inert reaction environment). Herein, an alternative photofree condition has been developed through Lewis base induced diazonium activation. With this method, an unreactive Au I catalyst was used in combination with Na 2 CO 3 and diazonium salts to produce a Au III intermediate. The efficient activation of various substrates, including alkyne, alkene and allene was achieved, followed by rapid Au III reductive elimination, which yielded the C-C coupling products with good to excellent yields. Relative to the previously reported photoactivation method, our approach offered greater efficiency and versatility through faster reaction rates and broader reaction scope. Challenging substrates such as electron rich/neutral allenes, which could not be activated under the photoinitiation conditions (<5 % yield), could be activated to subsequently yield the desired coupling products in good to excellent yield. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Grafting of a peptide probe for Prostate-Specific Antigen detection using diazonium electroreduction and click chemistry.

    PubMed

    Strzemińska, I; Sainte Rose Fanchine, S; Anquetin, G; Reisberg, S; Noël, V; Pham, M C; Piro, B

    2016-07-15

    The main objective of this work was to validate a label-free electrochemical method of protein detection using peptides as capture probes. As a proof-of-concept, we used a 7 amino acids sequence (HSSKLQL) specific for Prostate Specific Antigen. We investigated various electrografting conditions of two anilines (2-[(4-aminophenyl)sulfanyl]-8-hydroxy-1,4-naphthoquinone and 4-azidoaniline) further converted in situ into their corresponding diazonium salts on glassy carbon electrodes. It was demonstrated that the best method to obtain a mixed layer is the simultaneous electroreduction of the two diazonium salts. 4-azidoaniline was used to covalently immobilize the ethynyl-functionalized peptide probe by click coupling, and the hydroxynaphthoquinone derivative plays the role of electrochemical transducer of the peptide-protein recognition. The proteolytic activity of PSA towards a small peptide substrate carrying streptavidin at its distal end was also investigated to design an original sensing architecture leading to a reagentless, label free, and "signal-on" PSA sensor. Without optimization, the limit of quantification can be estimated in the nM to pM range. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers.

    PubMed

    Kim, Moon Suk; Lee, Sang Bong

    2014-07-31

    In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF₆). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO > GME > GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

  18. Graphite anode surface modification with controlled reduction of specific aryl diazonium salts for improved microbial fuel cells power output.

    PubMed

    Picot, Matthieu; Lapinsonnière, Laure; Rothballer, Michael; Barrière, Frédéric

    2011-10-15

    Graphite electrodes were modified with reduction of aryl diazonium salts and implemented as anodes in microbial fuel cells. First, reduction of 4-aminophenyl diazonium is considered using increased coulombic charge density from 16.5 to 200 mC/cm(2). This procedure introduced aryl amine functionalities at the surface which are neutral at neutral pH. These electrodes were implemented as anodes in "H" type microbial fuel cells inoculated with waste water, acetate as the substrate and using ferricyanide reduction at the cathode and a 1000 Ω external resistance. When the microbial anode had developed, the performances of the microbial fuel cells were measured under acetate saturation conditions and compared with those of control microbial fuel cells having an unmodified graphite anode. We found that the maximum power density of microbial fuel cell first increased as a function of the extent of modification, reaching an optimum after which it decreased for higher degree of surface modification, becoming even less performing than the control microbial fuel cell. Then, the effect of the introduction of charged groups at the surface was investigated at a low degree of surface modification. It was found that negatively charged groups at the surface (carboxylate) decreased microbial fuel cell power output while the introduction of positively charged groups doubled the power output. Scanning electron microscopy revealed that the microbial anode modified with positively charged groups was covered by a dense and homogeneous biofilm. Fluorescence in situ hybridization analyses showed that this biofilm consisted to a large extent of bacteria from the known electroactive Geobacter genus. In summary, the extent of modification of the anode was found to be critical for the microbial fuel cell performance. The nature of the chemical group introduced at the electrode surface was also found to significantly affect the performance of the microbial fuel cells. The method used for

  19. Trace lead analysis based on carbon-screen-printed-electrodes modified via 4-carboxy-phenyl diazonium salt electroreduction.

    PubMed

    Bouden, Sarra; Chaussé, Annie; Dorbes, Stephane; El Tall, Omar; Bellakhal, Nizar; Dachraoui, Mohamed; Vautrin-Ul, Christine

    2013-03-15

    This paper describes the use of 4-carboxyphenyl-grafted screen-printed carbon electrodes (4-CP-SPEs) for trace lead analysis. These novel and simple use of electrodes were easily prepared by the electrochemical reduction of the corresponding diazonium salt. Pb detection was then performed by a three-steps method in order to avoid oxygen interference: (i) immersion of the grafted screen-printed electrode (SPE) in the sample and adsorption of Pb(II), (ii) reduction of adsorbed Pb(II) by chronoamperometry (CA), and (iii) oxidation of Pb by Anodic Square Wave Voltammetry (SWV). The reoxidation response was exploited for lead detection and quantification. In order to optimize the analytical responses, the influence of the adsorption medium pH and the adsorption time were investigated. Moreover, an interference study was carried out with Cu(II), Hg(II), Al(III), Mn(II), Zn(II), Cd(II) and no major interference can be expected to quantify Pb(II). The described method provided a limit of detection and a limit of quantification of 1.2 × 10(-9)M and 4.1 × 10(-9)M, respectively. These performances indicate that the 4-CP-SPE could be considered as an efficient tool for environmental analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

    PubMed Central

    Kim, Moon Suk; Lee, Sang Bong

    2014-01-01

    In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively. PMID:28788147

  1. Transparent Metal-Salt-Filled Polymeric Radiation Shields

    NASA Technical Reports Server (NTRS)

    Edwards, David; Lennhoff, John; Harris, George

    2003-01-01

    "COR-RA" (colorless atomic oxygen resistant -- radiation shield) is the name of a transparent polymeric material filled with x-ray-absorbing salts of lead, bismuth, cesium, and thorium. COR-RA is suitable for use in shielding personnel against bremsstrahlung radiation from electron-beam welding and industrial and medical x-ray equipment. In comparison with lead-foil and leaded-glass shields that give equivalent protection against x-rays (see table), COR-RA shields are mechanically more durable. COR-RA absorbs not only x-rays but also neutrons and rays without adverse effects on optical or mechanical performance. The formulation of COR-RA with the most favorable mechanical-durability and optical properties contains 22 weight percent of bismuth to absorb x-rays, plus 45 atomic percent hydrogen for shielding against neutrons.

  2. Electrochemical impedance immunosensor based on gold nanoparticles and aryl diazonium salt functionalized gold electrodes for the detection of antibody.

    PubMed

    Liu, Guozhen; Liu, Jingquan; Davis, Thomas P; Gooding, J Justin

    2011-04-15

    Electrodes modified with passivating organic layers have been shown to, here and previously, to exhibit good Faradaic electrochemistry upon attachment of gold nanoparticles (AuNP). Due to their low background capacitances these constructs have good potential in electrochemical sensing. Herein is reported the application of these electrode constructs for impedance based immunosensing. The immunosensor was constructed by modifying a gold electrode with 4-thiophenol (4-TP) passivating layers by diazonium salt chemistry. Subsequently, the attachment of AuNP and then a biotin derivative as a model epitope to detect anti-biotin IgG were carried out. The interfacial properties of the modified electrodes were evaluated in the presence of Fe(CN)(6)(4-/3-) redox couple as a probe by cyclic voltammetry and electrochemical impedance spectroscopy. The impedance change, due to the specific immuno-interaction at the immunosensor surface was utilized to detect anti-biotin IgG. The increase in charge-transfer resistance (R(ct)) was linearly proportional to the concentration of anti-biotin IgG in the range of 5-500 ng mL(-1), with a detection limit of 5 ng mL(-1). Copyright © 2011 Elsevier B.V. All rights reserved.

  3. In situ diazonium-modified flexible ITO-coated PEN substrates for the deposition of adherent silver-polypyrrole nanocomposite films.

    PubMed

    Samanta, Soumen; Bakas, Idriss; Singh, Ajay; Aswal, Dinesh K; Chehimi, Mohamed M

    2014-08-12

    In this paper, we report a simple and versatile process of electrografting the aryl multilayers onto indium tin oxide (ITO)-coated flexible poly(ethylene naphthalate) (PEN) substrates using a diazonium salt (4-pyrrolylphenyldiazonium) solution, which was generated in situ from a reaction between the 4-(1H-pyrrol-1-yl)aniline precursor and sodium nitrite in an acidic medium. The first aryl layer bonds with the ITO surface through In-O-C and Sn-O-C bonds which facilitate the formation of a uniform aryl multilayer that is ∼8 nm thick. The presence of the aryl multilayer has been confirmed by impedance spectroscopy as well as by electron-transfer blocking measurements. These in situ diazonium-modified ITO-coated PEN substrates may find applications in flexible organic electronics and sensor industries. Here we demonstrate the application of diazonium-modified flexible substrates for the growth of adherent silver/polpyrrole nanocomposite films using surface-confined UV photopolymerization. These nanocomposite films have platelet morphology owing to the template effect of the pyrrole-terminated aryl multilayers. In addition, the films are highly doped (32%). This work opens new areas in the design of flexible ITO-conductive polymer hybrids.

  4. Direct functionalization of pristine single-walled carbon nanotubes by diazonium-based method with various five-membered S- or N- heteroaromatic amines

    NASA Astrophysics Data System (ADS)

    Leinonen, Heli; Lajunen, Marja

    2012-09-01

    Reactivity of five-membered, variously substituted, heteroaromatic diazonium salts was studied toward pristine single-walled carbon nanotubes (SWCNTs), prepared by high-pressure CO conversion (HiPCO) method. Average size range of individual HiPCO SWCNTs was 0.8-1.2 nm (diameter) and 100-1,000 nm (length). Functionalizations were performed by a one-pot diazotization-dediazotization method with methyl-2-aminothiophene-3-carboxylate, 2-aminothiophene-3-carbonitrile, 2-aminoimidazole sulfate, or 3-aminopyrazole in acetic acid using sodium nitrite at room temperature or by heating. According to Raman and Fourier transform infrared spectroscopy, all used heterocyclic diazonium salts formed a covalent bond with SWCNTs and yielded new kinds of five-membered heterocycle-functionalized SWCNTs. Methyl-2-thiophenyl-3-carboxylate-functionalized SWCNTs formed a highly soluble, stable dispersion in tetrahydrofuran (THF), 3-pyrazoyl-functionalized SWCNTs in ethanol, and 2-imidazoyl- or 2-thiophenyl-3-carbonitrile-functionalized SWCNTs in ethanol and THF. The thermogravimetric analysis as well as energy-filtered transmission electron microscopy imaging of the products confirmed the successful functionalization of SWCNTs.

  5. Electrochemiluminescent DNA sensor based on controlled Zn-mediated grafting of diazonium precursors.

    PubMed

    Torréns, Mabel; Ortiz, Mayreli; Bejarano-Nosas, Diego; O'Sullivan, Ciara K

    2015-07-01

    Controlled Zn-mediated grafting of a thin layer of a diazonium salt was used to functionalise a carbon electrode with ruthenium(II)-tris-bipyridine (Ru)-labelled DNA for use as a capture probe in an electrochemiluminescent genosensor. A secondary reporter probe was labelled with a ferrocene (Fc) molecule, and in the presence of the single-stranded DNA target a genocomplex formed, where the Fc-label effectively quenched the electrochemiluminescence of the signal emitted from the Ru-label. The spacing of the labels for maximum sensitivity and minimum detection limit was optimised, and the signal reproducibility and stability of the method was established.

  6. Fast dye salts provide fast access to azidoarene synthons in multi-step one-pot tandem click transformations

    PubMed Central

    Fletcher, James T.; Reilly, Jacquelline E.

    2012-01-01

    This study examined whether commercially available diazonium salts could be used as efficient aromatic azide precursors in one-pot multi-step click transformations. Seven different diazonium salts, including Fast Red RC, Fast Blue B, Fast Corinth V and Variamine Blue B were surveyed under aqueous click reaction conditions of CuSO4/Na ascorbate catalyst with 1:1 t-BuOH:H2O solvent. Two-step tandem reactions with terminal alkyne and diyne co-reactants led to 1,2,3-triazole products in 66%-88% yields, while three-step tandem reactions with trimethylsilyl-protected alkyne and diyne co-reactants led to 1,2,3-triazole products in 61%-78% yields. PMID:22368306

  7. Tuneable enhancement of the salt and thermal stability of polymeric micelles by cyclized amphiphiles

    PubMed Central

    Honda, Satoshi; Yamamoto, Takuya; Tezuka, Yasuyuki

    2013-01-01

    Cyclic molecules provide better stability for their aggregates. Typically in nature, the unique cyclic cell membrane lipids allow thermophilic archaea to inhabit extreme conditions. By mimicking the biological design, the robustness of self-assembled synthetic nanostructures is expected to be improved. Here we report topology effects by cyclized polymeric amphiphiles against their linear counterparts, demonstrating a drastic enhancement in the thermal, as well as salt stability of self-assembled micelles. Furthermore, through coassembly of the linear and cyclic amphiphiles, the stability was successfully tuned for a wide range of temperatures and salt concentrations. The enhanced thermal/salt stability was exploited in a halogen exchange reaction to stimulate the catalytic activity. The mechanism for the enhancement was also investigated. These topology effects by the cyclic amphiphiles offer unprecedented opportunities in polymer materials design unattainable by traditional means. PMID:23481382

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

    PubMed

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

    2014-05-13

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

  9. Spatial and temporal control of the diazonium modification of sp2 carbon surfaces.

    PubMed

    Kirkman, Paul M; Güell, Aleix G; Cuharuc, Anatolii S; Unwin, Patrick R

    2014-01-08

    Interest in the controlled chemical functionalization of sp(2) carbon materials using diazonium compounds has been recently reignited, particularly as a means to generate a band gap in graphene. We demonstrate local diazonium modification of pristine sp(2) carbon surfaces, with high control, at the micrometer scale through the use of scanning electrochemical cell microscopy (SECCM). Electrochemically driven diazonium patterning is investigated at a range of driving forces, coupled with surface analysis using atomic force microscopy (AFM) and Raman spectroscopy. We highlight how the film density, level of sp(2)/sp(3) rehybridization and the extent of multilayer formation can be controlled, paving the way for the use of localized electrochemistry as a route to controlled diazonium modification.

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

    PubMed

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

    2016-08-01

    A highly efficient methodology for preparing a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on the surface of poly(ether ether ketone) (PEEK) was examined by photoinduced and self-initiated graft polymerization. To enhance the polymerization rate, we demonstrated the effects of inorganic salt additives in the feed monomer solution on thickness of grafted PMPC layer. Photoinduced polymerization occurred and the PMPC graft layer was successfully formed on the PEEK surface, regardless of inorganic salt additives. Moreover, it was clearly observed that the addition of inorganic salt enhanced the grafting thickness of PMPC layer on the surface even when the photoirradiation time was shortened. The addition of inorganic salt additives in the feed monomer solution enhanced the polymerization rate of MPC and resulted in thicker PMPC layers. In particular, we evaluated the effect of NaCl concentration and how this affected the polymerization rate and layer thickness. We considered that this phenomenon was due to the hydration of ions in the feed monomer solution and subsequent apparent increase in the MPC concentration. A PMPC layer with over 100-nm-thick, which was prepared by 5-min photoirradiation in 2.5mol/L inorganic salt aqueous solution, showed good wettability and protein adsorption resistance compared to that of untreated PEEK. Hence, we concluded that the addition of NaCl into the MPC feed solution would be a convenient and efficient method for preparing a graft layer on PEEK. Photoinduced and self-initiated graft polymerization on the PEEK surface is one of the several methodologies available for functionalization. However, in comparison with free-radical polymerization, the efficiency of polymerization at the solid-liquid interface is limited. Enhancement of the polymerization rate for grafting could solve the problem. In this study, we observed the acceleration of the polymerization rate of MPC in an aqueous solution by the addition of inorganic

  11. Process for derivatizing carbon nanotubes with diazonium species and compositions thereof

    NASA Technical Reports Server (NTRS)

    Bahr, Jeffrey L. (Inventor); Tour, James M. (Inventor); Yang, Jiping (Inventor)

    2011-01-01

    Methods for the chemical modification of carbon nanotubes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications, and sensor devices. The methods of derivatization include electrochemical induced reactions, thermally induced reactions, and photochemically induced reactions. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes.

  12. Electrophoretic Approach for the Simultaneous Deposition and Functionalization of Reduced Graphene Oxide Nanosheets with Diazonium Compounds: Application for Lysozyme Sensing in Serum.

    PubMed

    Wang, Qian; Vasilescu, Alina; Wang, Qi; Coffinier, Yannick; Li, Musen; Boukherroub, Rabah; Szunerits, Sabine

    2017-04-12

    Electrophoretic deposition (EPD) of reduced graphene oxide nanosheets (rGO) offers several advantages over other surface coating approaches, including process simplicity, uniformity of the deposited films, and good control of the film thickness. The EPD conditions might also be of interest for the reduction of diazonium salts, which upon the release of N 2 molecules and generation of radicals, can form covalent bonds with the sp 2 hybridized carbon lattice atoms of rGO films. In this work, we report on the coating of gold electrodes in one step with rGO/polyethylenimine (PEI) thin films and their simultaneous modification using different phenyl (Ph) diazonium salt precursors bearing various functionalities such as -B(OH) 2 , -COOH, and -C≡CH. We show further the interest of such interfaces for designing highly sensitive sensing platforms. Azide-terminated lysozyme aptamers were clicked onto the rGO/PEI/Ph-alkynyl matrix and used for the sensing of lysozyme levels in patients suffering from inflammatory bowel disease (IBD), where lysozyme levels are up-regulated. The approach attained the required demand for the determination of lysozyme level in patients suffering from IBD with a 200 fM detection limit and a linear range up to 20 pM without signal amplification.

  13. The Hydractinia echinata test-system. III: Structure-toxicity relationship study of some azo-, azo-anilide, and diazonium salt derivatives.

    PubMed

    Chicu, Sergiu Adrian; Munteanu, Melania; Cîtu, Ioana; Soica, Codruta; Dehelean, Cristina; Trandafirescu, Cristina; Funar-Timofei, Simona; Ionescu, Daniela; Simu, Georgeta Maria

    2014-07-08

    Structure-toxicity relationships for a series of 75 azo and azo-anilide dyes and five diazonium salts were developed using Hydractinia echinata (H. echinata) as model species. In addition, based on these relationships, predictions for 58 other azo-dyes were made. The experimental results showed that the measured effectiveness Mlog(1/MRC50) does not depend on the number of azo groups or the ones corresponding to metobolites, but it is influenced by the number of anilide groups, as well as by the substituents' positions within molecules. The conformational analysis pointed out the intramolecular hydrogen bonds, especially the simple tautomerization of quinoidic (STOH) or aminoidic (STNH2) type. The effectiveness is strongly influenced by the "push-pull" electronic effect, specific to two hydroxy or amino groups separated by an azo moiety (double alternate tautomery, (DAT), to the -COOH or -SO3H groups which are located in ortho or para position with respect to the azo group. The levels of the lipophylic/hydrophilic, electronic and steric equilibriums, pointed out by the Mlog(1/MRC50) values, enabled the calculation of their average values Clog(1/MRC50) ("Köln model"), characteristic to one derivative class (class isotoxicity). The azo group reduction and the hydrolysis of the amido/peptidic group are two concurrent enzymatic reactions, which occur with different reaction rates and mechanisms. The products of the partial biodegradation are aromatic amines. No additive or synergic effects are noticed among them.

  14. Surface modification of GC and HOPG with diazonium, amine, azide, and olefin derivatives.

    PubMed

    Tanaka, Mutsuo; Sawaguchi, Takahiro; Sato, Yukari; Yoshioka, Kyoko; Niwa, Osamu

    2011-01-04

    Surface modification of glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) was carried out with diazonium, amine, azide, and olefin derivatives bearing ferrocene as an electroactive moiety. Features of the modified surfaces were evaluated by surface concentrations of immobilized molecule, blocking effect of the modified surface against redox reaction, and surface observation using cyclic voltammetry and electrochemical scanning tunneling microscope (EC-STM). The measurement of surface concentrations of immobilized molecule revealed the following three aspects: (i) Diazonium and olefin derivatives could modify substrates with the dense-monolayer concentration. (ii) The surface concentration of immobilized amine derivative did not reach to the dense-monolayer concentration reflecting their low reactivity. (iii) The surface modification with the dense-monolayer concentration was also possible with azide derivative, but the modified surface contained some oligomers produced by the photoreaction of azides. Besides, the blocking effect against redox reaction was observed for GC modified with diazonium derivative and for HOPG modified with diazonium and azide derivatives, suggesting fabrication of a densely modified surface. Finally, the surface observation for HOPG modified with diazonium derivative by EC-STM showed a typical monolayer structure, in which the ferrocene moieties were packed densely at random. On the basis of those results, it was demonstrated that surface modification of carbon substrates with diazonium could afford a dense monolayer similar to the self-assembled monolayer (SAM) formation.

  15. Antibacterial Drug Releasing Materials by Post-Polymerization Surface Modification

    NASA Astrophysics Data System (ADS)

    Chng, Shuyun; Moloney, Mark G.; Wu, Linda Y. L.

    Functional materials are available by the post-polymerization surface modification of diverse polymers in a three-step process mediated, firstly, by carbene insertion chemistry, secondly, by diazonium coupling, and thirdly by modification with a remotely tethered spiropyran unit, and these materials may be used for the reversible binding and release of Penicillin V. Surface loading densities of up to 0.19mmol/g polymer are achievable, leading to materials with higher loading densities and release behavior relative to unmodified controls, and observable antibacterial biocidal activity.

  16. Simple diazonium chemistry to develop specific gene sensing platforms.

    PubMed

    Revenga-Parra, M; García-Mendiola, T; González-Costas, J; González-Romero, E; Marín, A García; Pau, J L; Pariente, F; Lorenzo, E

    2014-02-27

    A simple strategy for covalent immobilizing DNA sequences, based on the formation of stable diazonized conducting platforms, is described. The electrochemical reduction of 4-nitrobenzenediazonium salt onto screen-printed carbon electrodes (SPCE) in aqueous media gives rise to terminal grafted amino groups. The presence of primary aromatic amines allows the formation of diazonium cations capable to react with the amines present at the DNA capture probe. As a comparison a second strategy based on the binding of aminated DNA capture probes to the developed diazonized conducting platforms through a crosslinking agent was also employed. The resulting DNA sensing platforms were characterized by cyclic voltammetry, electrochemical impedance spectroscopy and spectroscopic ellipsometry. The hybridization event with the complementary sequence was detected using hexaamineruthenium (III) chloride as electrochemical indicator. Finally, they were applied to the analysis of a 145-bp sequence from the human gene MRP3, reaching a detection limit of 210 pg μL(-1). Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Electronic structure and optical spectra of semiconducting carbon nanotubes functionalized by diazonium salts

    NASA Astrophysics Data System (ADS)

    Ramirez, Jessica; Mayo, Michael L.; Kilina, Svetlana; Tretiak, Sergei

    2013-02-01

    We report density functional (DFT) calculations on finite-length semiconducting carbon nanotubes covalently and non-covalently functionalized by aryl diazonium moieties and their chlorinated derivatives. For these systems, we investigate (i) an accuracy of different functionals and basis sets, (ii) a solvent effect, and (iii) the impact of the chemical functionalization on optical properties of nanotubes. In contrast to B3LYP, only long-range-corrected functionals, such as CAM-B3LYP and wB97XD, properly describe the ground and excited state properties of physisorbed molecules. We found that physisorbed cation insignificantly perturbs the optical spectra of nanotubes. In contrast, covalently bound complexes demonstrate strong redshifts and brightening of the lowest exciton that is optically dark in pristine nanotubes. However, the energy and oscillator strength of the lowest state are dictated by the position of the molecule on the nanotube. Thus, if controllable and selective chemical functionalization is realized, the PL of nanotubes could be improved.

  18. Gas anti-solvent precipitation assisted salt leaching for generation of micro- and nano-porous wall in bio-polymeric 3D scaffolds.

    PubMed

    Flaibani, Marina; Elvassore, Nicola

    2012-08-01

    The mass transport through biocompatible and biodegradable polymeric 3D porous scaffolds may be depleted by non-porous impermeable internal walls. As consequence the concentration of metabolites and growth factors within the scaffold may be heterogeneous leading to different cell fate depending on spatial cell location, and in some cases it may compromise cell survival. In this work, we fabricated polymeric scaffolds with micro- and nano-scale porosity by developing a new technique that couples two conventional scaffold production methods: solvent casting-salt leaching and gas antisolvent precipitation. 10-15 w/w solutions of a hyaluronic benzyl esters (HYAFF11) and poly-(lactic acid) (PLA) were used to fill packed beds of 0.177-0.425 mm NaCl crystals. The polymer precipitation in micro and nano-porous structures between the salt crystals was induced by high-pressure gas, then its flushing extracted the residual solvent. The salt was removed by water-wash. Morphological analysis by scanning electron microscopy showed a uniform porosity (~70%) and a high interconnectivity between porous. The polymeric walls were porous themselves counting for 30% of the total porosity. This wall porosity did not lead to a remarkable change in compressive modulus, deformation, and rupture pressure. Scaffold biocompatibility was tested with murine muscle cell line C2C12 for 4 and 7 days. Viability analysis and histology showed that micro- and nano-porous scaffolds are biocompatible and suitable for 3D cell culture promoting cell adhesion on the polymeric wall and allowing their proliferation in layers. Micro- and nano-scale porosities enhance cell migration and growth in the inner part of the scaffold. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Cu-Click Compatible Triazabutadienes To Expand the Scope of Aryl Diazonium Ion Chemistry.

    PubMed

    Cornali, Brandon M; Kimani, Flora W; Jewett, John C

    2016-10-07

    Triazabutadienes can be used to readily generate reactive aryl diazonium ions under mild, physiologically relevant conditions. These conditions are compatible with a range of functionalities that do not tolerate traditional aryl diazonium ion generation. To increase the utility of this aryl diazonium ion releasing chemistry an alkyne-containing triazabutadiene was synthesized. The copper-catalyzed azide-alkyne cycloaddition ("Cu-click") reaction was utilized to modify the alkyne-containing triazabutadiene and shown to be compatible with the nitrogen-rich triazabutadiene. One of the triazole products was tethered to a fluorophore, thus enabling the direct fluorescent labeling of a model protein.

  20. Diazonium-protein adducts for graphite electrode microarrays modification: direct and addressed electrochemical immobilization.

    PubMed

    Corgier, Benjamin P; Marquette, Christophe A; Blum, Loïc J

    2005-12-28

    Diazonium cation electrodeposition was investigated for the direct and electro-addressed immobilization of proteins. For the first time, this reaction was triggered directly onto diazonium-modified proteins. Screen-printed (SP) graphite electrode microarrays were studied as active support for this immobilization. A 10-microelectrode (eight working electrodes, 0.2 mm2 each; one reference; and one auxiliary) setup was used to study the addressing possibilities of the method. These electrode microarrays were shown to be able to covalently graft diazonium cations through electrochemical reduction. Cyclic voltammetry and X-ray photoelectron spectroscopy were used to characterize the electrochemical grafting onto our SP graphite surface and suggested that a diazonium monolayer was deposited. Rabbit and human immunoglobulins (IgGs) were then chemically coupled to an aniline derivative (4-carboxymethylaniline), followed by diazotation to form an aryl diazonium function available for the electrodeposition. These modified proteins were both successfully electro-addressed at the surface of the graphite electrodes without cross-talk or interference. The immuno-biochip obtained using this novel approach enabled the specific detection of anti-rabbit IgG antibodies with a detection limit of 50 fmol of protein. A promising strategy to immobilize markedly different biological entities was then presented, providing an excellent spatial specificity of the electro-addressing.

  1. Isolation of a Moderately Stable but Sensitive Zwitterionic Diazonium Tetrazolyl-1,2,3-triazolate.

    PubMed

    Klapötke, Thomas M; Krumm, Burkhard; Pflüger, Carolin

    2016-07-15

    An unexpected formation of a diazonium compound was observed by nitration of an amino substituted triazolyl tetrazole with mixed acid. The crystal structure determination revealed a zwitterionic diazonium tetrazolyl-1,2,3-triazolate, whose constitution was supported by NMR and vibrational spectroscopic analysis. The thermal stability and sensitivity toward impact and friction were determined. In contrast, diazotriazoles are rather unstable and are mainly handled in solution and/or low temperatures, which is not the case for this diazonium tetrazolyl-1,2,3-triazolate, being stable at ambient temperature.

  2. Flexible strategy for immobilizing redox-active compounds using in situ generation of diazonium salts. Investigations of the blocking and catalytic properties of the layers.

    PubMed

    Noël, Jean-Marc; Sjöberg, Béatrice; Marsac, Rémi; Zigah, Dodzi; Bergamini, Jean-François; Wang, Aifang; Rigaut, Stéphane; Hapiot, Philippe; Lagrost, Corinne

    2009-11-03

    A versatile two-step method is developed to covalently immobilize redox-active molecules onto carbon surfaces. First, a robust anchoring platform is grafted onto surfaces by electrochemical reduction of aryl diazonium salts in situ generated. Depending on the nature of the layer termini, -COOH or -NH(2), a further chemical coupling involving ferrocenemethylamine or ferrocene carboxylic acid derivatives leads to the covalent binding of ferrocene centers. The chemical strategy using acyl chloride activation is efficient and flexible, since it can be applied either to surface-reactive end groups or to reactive species in solution. Cyclic voltammetry analyses point to the covalent binding of ferrocene units restricted to the upper layers of the underlying aryl films, while AFM measurements show a lost of compactness of the layers after the chemical attachment of ferrocene centers. The preparation conditions of the anchoring layers were found to determine the interfacial properties of the resulted ferrocenyl-modified electrodes. The ferrocene units promoted effective redox mediation providing that the free redox probes are adequately chosen (i.e., vs size/formal potential) and the underlying layers exhibit strong blocking properties. For anchoring films with weaker blocking effect, the coexistence of two distinct phenomena, redox mediation and ET at pinholes could be evidenced.

  3. Protein-functionalized hairy diamond nanoparticles.

    PubMed

    Dahoumane, Si Amar; Nguyen, Minh Ngoc; Thorel, Alain; Boudou, Jean-Paul; Chehimi, Mohamed M; Mangeney, Claire

    2009-09-01

    Diazonium salt chemistry and atom transfer radical polymerization (ATRP) were combined in view of preparing new bioactive hairy diamond nanoparticles containing, or potentially containing, nitrogen-vacancy (NV) fluorescent centers (fluorescent nanodiamonds, or fNDs). fNDs were modified by ATRP initiators using the electroless reduction of the diazonium salt BF(4)(-),(+)N(2)-C(6)H(4)-CH(CH(3))-Br. The strongly bound aryl groups -C(6)H(4)-CH(CH(3))-Br efficiently initiated the ATRP of tert-butyl methacrylate (tBMA) at the surface of the nanodiamonds, which resulted in obtaining ND-PtBMA hybrids. The grafted chain thickness, estimated from X-ray photoelectron spectroscopy (XPS), was found to increase linearly with respect to time before reaching a plateau value of ca. 2 nm. These nanoobjects were further hydrolyzed into ND-PMAA (where PMAA is the poly(methacrylic acid) graft) and further decorated by bovine serum albumin through the 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling procedure.

  4. Enhanced interfacial properties of carbon fiber composites via aryl diazonium reaction “on water”

    NASA Astrophysics Data System (ADS)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Ma, Lichun; Qi, Meiwei; Yu, Jiali; Huang, Yudong

    2014-10-01

    Polyacrylonitrile-based carbon fibers were functionalized with phenyl amine group via aryl diazonium reaction "on water" to improve their interfacial bonding with resin matrix. Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize ordered degree, functional groups, chemical states and morphology of carbon fiber surface, respectively. The results showed that phenyl amine groups were grafted on the fiber surface successfully. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 73%, while the tensile strength was down very slightly. Hence aryl diazonium reaction "on water" could be a facile green platform to functionalize carbon fibers for many interesting applications.

  5. Modification of Ti6Al4V surface by diazonium compounds

    NASA Astrophysics Data System (ADS)

    Sandomierski, Mariusz; Buchwald, Tomasz; Strzemiecka, Beata; Voelkel, Adam

    2018-02-01

    Ti6Al4V alloy is the most commonly used in orthopedic industry as an endoprosthesis. Ti6Al4V exhibits good mechanical properties, except the abrasion resistance. Surface modification of Ti6Al4V in order to obtain organic layer, and then the attachment of the polymer, can allow for overcoming this problem. The aim of the work was the modification of Ti6Al4V surface by diazonium compounds: salt or cation generated in situ and examine the influence of the reducing agent - ascorbic acid, and the temperature of reaction on modification process. Moreover, the simulated body fluid was used for the assessment of the organic layer stability on Ti6Al4V surface. The evaluation of the modification was carried out using the following methods: Raman microspectroscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Higher temperature of modification by 4-hydroxymethylbenzenediazonium cation, provides the largest amount of organic layer on the Ti6Al4V alloy. In the case of the Ti6Al4V modified by Variamine Blue B salt, the amount of organic layer is not dependent on the reaction condition. Moreover, the ascorbic acid and the presence of TiO2 does not effect on the modification. The modified surface is completely coated with the organic layer which is stable in simulated body fluid.

  6. Osteoinductive activity of insulin-functionalized cell culture surfaces obtained using diazonium chemistry

    NASA Astrophysics Data System (ADS)

    Mikulska, Anna; Filipowska, Joanna; Osyczka, Anna; Nowakowska, Maria; Szczubiałka, Krzysztof

    2014-12-01

    Polymeric surfaces suitable for cell culture (DR/Pec) were constructed from diazoresin (DR) and pectin (Pec) in a form of ultrathin films using the layer-by-layer (LbL) technique. The surfaces were functionalized with insulin using diazonium chemistry. Such functionalized surfaces were used to culture human mesenchymal stem cells (hMSCs) to assess their suitability for bone tissue engineering and regeneration. The activity of insulin immobilized on the surfaces (DR/Pec/Ins) was compared to that of insulin dissolved in the culture medium. Human MSC grown on insulin-immobilized DR/Pec surfaces displayed increased proliferation and higher osteogenic activity. The latter was determined by means of alkaline phosphatase (ALP) activity, which increases at early stages of osteoblasts differentiation. Insulin dissolved in the culture medium did not stimulate cell proliferation and its osteogenic activity was significantly lower. Addition of recombinant human bone morphogenetic protein 2 (rhBMP-2) to the culture medium further increased ALP activity in hMSCs indicating additive osteogenic action of immobilized insulin and rhBMP-2

  7. Osteoinductive activity of insulin-functionalized cell culture surfaces obtained using diazonium chemistry

    PubMed Central

    Mikulska, Anna; Filipowska, Joanna; Osyczka, Anna M.; Nowakowska, Maria; Szczubiałka, Krzysztof

    2015-01-01

    Polymeric surfaces suitable for cell culture (DR/Pec) were constructed from diazoresin (DR) and pectin (Pec) in a form of ultrathin films using the layer-by-layer (LbL) technique. The surfaces were functionalized with insulin using diazonium chemistry. Such functionalized surfaces were used to culture human mesenchymal stem cells (hMSCs) to assess their suitability for bone tissue engineering and regeneration. The activity of insulin immobilized on the surfaces (DR/Pec/Ins) was compared to that of insulin dissolved in the culture medium. Human MSC grown on insulin-immobilized DR/Pec surfaces displayed increased proliferation and higher osteogenic activity. The latter was determined by means of alkaline phosphatase (ALP) activity, which increases at early stages of osteoblasts differentiation. Insulin dissolved in the culture medium did not stimulate cell proliferation and its osteogenic activity was significantly lower. Addition of recombinant human bone morphogenetic protein 2 (rhBMP-2) to the culture medium further increased ALP activity in hMSCs indicating additive osteogenic action of immobilized insulin and rhBMP-2. PMID:25629028

  8. A highly efficient dual-diazonium reagent for protein crosslinking and construction of a virus-based gel.

    PubMed

    Ma, Dejun; Zhang, Jie; Zhang, Changyu; Men, Yuwen; Sun, Hongyan; Li, Lu-Yuan; Yi, Long; Xi, Zhen

    2018-05-09

    A new bench-stable reagent with double diazonium sites was designed and synthesized for protein crosslinking. Based on the highly efficient diazonium-Tyr coupling reaction, a direct mixture of the reagent and tobacco mosaic virus led to the formation of a new hydrogel, which could be degraded by chemicals and could be used to encapsulate small molecules for sustained release. Because plant viruses exhibit many chemical characteristics like protein labelling and nucleic acid packaging, the virus-based hydrogel will have large chemical space for further functionalization. Besides, this dual-diazonium reagent should be a generally useful crosslinker for chemical biology and biomaterials.

  9. Diazonium functionalized graphene: microstructure, electric, and magnetic properties.

    PubMed

    Huang, Ping; Jing, Long; Zhu, Huarui; Gao, Xueyun

    2013-01-15

    The unique honeycomb lattice structure of graphene gives rise to its outstanding electronic properties such as ultrahigh carrier mobility, ballistic transport, and more. However, a crucial obstacle to its use in the electronics industry is its lack of an energy bandgap. A covalent chemistry strategy could overcome this problem, and would have the benefits of being highly controllable and stable in the ambient environment. One possible approach is aryl diazonium functionalization. In this Account, we investigate the micromolecular/lattice structure, electronic structure, and electron-transport properties of nitrophenyl-diazonium-functionalized graphene. We find that nitrophenyl groups mainly adopt random and inhomogeneous configurations on the graphene basal plane, and that their bonding with graphene carbon atoms leads to slight elongation of the graphene lattice spacing. By contrast, hydrogenated graphene has a compressed lattice. Low levels of functionalization suppressed the electric conductivity of the resulting functionalized graphene, while highly functionalized graphene showed the opposite effect. This difference arises from the competition between the charge transfer effect and the scattering enhancement effect introduced by nitrophenyl groups bonding with graphene carbon atoms. Detailed electron transport measurements revealed that the nitrophenyl diazonium functionalization locally breaks the symmetry of graphene lattice, which leads to an increase in the density of state near the Fermi level, thus increasing the carrier density. On the other hand, the bonded nitrophenyl groups act as scattering centers, lowering the mean free path of the charge carriers and suppressing the carrier mobility. In rare cases, we observed ordered configurations of nitrophenyl groups in local domains on graphene flakes due to fluctuations in the reaction processes. We describe one example of such a superlattice, with a lattice constant nearly twice of that of pristine graphene

  10. Taming hazardous chemistry in flow: the continuous processing of diazo and diazonium compounds.

    PubMed

    Deadman, Benjamin J; Collins, Stuart G; Maguire, Anita R

    2015-02-02

    The synthetic utilities of the diazo and diazonium groups are matched only by their reputation for explosive decomposition. Continuous processing technology offers new opportunities to make and use these versatile intermediates at a range of scales with improved safety over traditional batch processes. In this minireview, the state of the art in the continuous flow processing of reactive diazo and diazonium species is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Diazonium-functionalized horseradish peroxidase immobilized via addressable electrodeposition: direct electron transfer and electrochemical detection.

    PubMed

    Polsky, Ronen; Harper, Jason C; Dirk, Shawn M; Arango, Dulce C; Wheeler, David R; Brozik, Susan M

    2007-01-16

    A simple one-step procedure is introduced for the preparation of diazonium-enzyme adducts. The direct electrically addressable deposition of diazonium-modified enzymes is examined for electrochemical sensor applications. The deposition of diazonium-horseradish peroxidase leads to the direct electron transfer between the enzyme and electrode exhibiting a heterogeneous rate constant, ks, of 10.3 +/- 0.7 s-1 and a DeltaEp of 8 mV (v = 150 mV/s). The large ks and low DeltaEp are attributed to the intimate contact between enzyme and electrode attached by one to three phenyl molecules. Such an electrode shows high nonmediated catalytic activity toward H2O2 reduction. Future generations of arrayed electrochemical sensors and studies of direct electron transfer of enzymes can benefit from protein electrodes prepared by this method.

  12. Reporter-free potentiometric sensing of boronic acids and their reactions by using quaternary ammonium salt-functionalized polymeric liquid membranes.

    PubMed

    Wang, Xuewei; Yue, Dengfeng; Lv, Enguang; Wu, Lei; Qin, Wei

    2014-02-18

    The tremendous applications of boronic acids (BAs) in chemical sensing, medical chemistry, molecular assembly, and organic synthesis lead to an urgent demand for developing effective sensing methods for BAs. This paper reports a facile and sensitive potentiometric sensor scheme for heterogeneous detection of BAs based on their unexpected potential responses on quaternary ammonium salt-doped polymeric liquid membranes. (11)B NMR data reveal that a quaternary ammonium chloride can trigger the hydrolysis of an electrically neutral BA in an aprotic solvent. Using the quaternary ammonium salt as the receptor, the BA molecules can be extracted from the sample solution into the polymeric membrane phase and undergo the concomitant hydrolysis. Such salt-triggered hydrolysis generates H(+) ions, which can be coejected into the aqueous phase with the counterions (e.g., Cl(-)) owing to their high hydrophilicities. The perturbation on the ionic partition at the sample-membrane interface changes the phase boundary potential and thus enables the potentiometric sensing of BAs. In contrast to other transduction methods for BAs, for which labeled or separate reporters are exclusively required, the present heterogeneous sensing scheme allows the direct detection of BAs without using any reporter molecules. This technique shows superior detection limits for BAs (e.g., 1.0 × 10(-6) M for phenylboronic acid) as compared to previously reported methods based on colorimetry, fluorimetry, and mass spectrometry. The proposed sensing strategy has also been successfully applied to potentiometric indication of the BA reactions with hydrogen peroxide and saccharides, which allows indirect and sensitive detection of these important species.

  13. Modification of Ti6Al4V surface by diazonium compounds.

    PubMed

    Sandomierski, Mariusz; Buchwald, Tomasz; Strzemiecka, Beata; Voelkel, Adam

    2018-02-15

    Ti6Al4V alloy is the most commonly used in orthopedic industry as an endoprosthesis. Ti6Al4V exhibits good mechanical properties, except the abrasion resistance. Surface modification of Ti6Al4V in order to obtain organic layer, and then the attachment of the polymer, can allow for overcoming this problem. The aim of the work was the modification of Ti6Al4V surface by diazonium compounds: salt or cation generated in situ and examine the influence of the reducing agent - ascorbic acid, and the temperature of reaction on modification process. Moreover, the simulated body fluid was used for the assessment of the organic layer stability on Ti6Al4V surface. The evaluation of the modification was carried out using the following methods: Raman microspectroscopy, scanning electron microscopy and energy-dispersive X-ray spectroscopy. Higher temperature of modification by 4-hydroxymethylbenzenediazonium cation, provides the largest amount of organic layer on the Ti6Al4V alloy. In the case of the Ti6Al4V modified by Variamine Blue B salt, the amount of organic layer is not dependent on the reaction condition. Moreover, the ascorbic acid and the presence of TiO 2 does not effect on the modification. The modified surface is completely coated with the organic layer which is stable in simulated body fluid. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Impregnated metal-polymeric functional beads

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

  15. Impregnated metal-polymeric functional beads

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

  16. Water-soluble triazabutadienes that release diazonium species upon protonation under physiologically relevant conditions.

    PubMed

    Kimani, Flora W; Jewett, John C

    2015-03-23

    Triazabutadienes are an understudied structural motif that have remarkable reactivity once rendered water-soluble. It is shown that these molecules readily release diazonium species in a pH-dependent manner in a series of buffer solutions with pH ranges similar to those found in cells. Upon further development, we expect that this process will be well suited to cargo-release strategies and organelle-specific bioconjugation reactions. These compounds offer one of the mildest ways of generating diazonium species in aqueous solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis of stilbene derivatives via visible-light-induced cross-coupling of aryl diazonium salts with nitroalkenes using -NO2 as a leaving group.

    PubMed

    Zhang, Na; Quan, Zheng-Jun; Zhang, Zhang; Da, Yu-Xia; Wang, Xi-Cun

    2016-12-06

    The straightforward visible-light-induced synthesis of stilbene compounds via the cross-coupling of nitroalkenes and diazonium tetrafluoroborates under transition-metal-free conditions is described. The protocol uses green LEDs as light sources and eosin Y as an organophotoredox catalyst. Broad substrate scope and exclusive selectivity for the (E)-configuration of stilbenes are observed. This protocol proceeds via a radical pathway, with nitroalkenes serving as the radical acceptor, and the nitro group is cleaved during the process.

  18. Aryl diazonium for biomolecules immobilization onto SPRi chips.

    PubMed

    Mandon, Céline A; Blum, Loïc J; Marquette, Christophe A

    2009-12-21

    A method for the immobilization of proteins at the surface of surface plasmon resonance imaging (SPRi) chips is presented. The technology, based on the electro-deposition of a 4-carboxymethyl aryl diazonium (CMA) monolayer is compared to a classical thioctic acid self-assembled monolayer. SPRi live recording experiments followed by the quantification of the diazonium surface coverage demonstrate the presence of a monolayer of electro-deposited molecules (11*10(12) molecules mm(-2)). This monolayer, when activated through a classical carbodiimide route, generates a surface suitable for the protein immobilization. In the present study, protein A and BSA are immobilized as specific and control spots (150 microm id), respectively. The AFM characterization of the spots deposited onto CMA or thioctic acid modified chips prove the presence of 4.7 nm protein monolayers. Finally, the SPRi detection capabilities of the two surface chemistries are compared according to specific signal, non-specific interaction and regeneration possibilities. Advantages are given to the CMA surface modification since no measurable non-specific signal is obtained while reaching a higher specific signal.

  19. Stability of SG1 nitroxide towards unprotected sugar and lithium salts: a preamble to cellulose modification by nitroxide-mediated graft polymerization

    PubMed Central

    Moreira, Guillaume; Charles, Laurence; Major, Mohamed; Vacandio, Florence; Guillaneuf, Yohann

    2013-01-01

    Summary The range of applications of cellulose, a glucose-based polysaccharide, is limited by its inherently poor mechanical properties. The grafting of synthetic polymer chains by, for example, a “grafting from” process may provide the means to broaden the range of applications. The nitroxide-mediated polymerization (NMP) method is a technique of choice to control the length, the composition and the architecture of the grafted copolymers. Nevertheless, cellulose is difficult to solubilize in organic media because of inter- and intramolecular hydrogen bonds. One possibility to circumvent this limitation is to solubilize cellulose in N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA) with 5 to 10 wt % of lithium salts (LiCl or LiBr), and carry out grafted polymerization in this medium. The stability of nitroxides such as SG1 has not been studied under these conditions yet, even though these parameters are of crucial importance to perform the graft modification of polysaccharide by NMP. The aim of this work is to offer a model study of the stability of the SG1 nitroxide in organic media in the presence of unprotected glucose or cellobiose (used as a model of cellulose) and in the presence of lithium salts (LiBr or LiCl) in DMF or DMA. Contrary to TEMPO, SG1 proved to be stable in the presence of unprotected sugar, even with an excess of 100 molar equivalents of glucose. On the other hand, lithium salts in DMF or DMA clearly degrade SG1 nitroxide as proven by electron-spin resonance measurements. The instability of SG1 in these lithium-containing solvents may be explained by the acidification of the medium by the hydrolysis of DMA in the presence of LiCl. This, in turn, enables the disproportionation of the SG1 nitroxide into an unstable hydroxylamine and an oxoammonium ion. Once the conditions to perform an SG1-based nitroxide-mediated graft polymerization from cellobiose have been established, the next stage of this work will be the modification of

  20. Surface functionalization of cyclic olefin copolymer with aryldiazonium salts: A covalent grafting method

    NASA Astrophysics Data System (ADS)

    Brisset, Florian; Vieillard, Julien; Berton, Benjamin; Morin-Grognet, Sandrine; Duclairoir-Poc, Cécile; Le Derf, Franck

    2015-02-01

    Covalent immobilization of biomolecules on the surface of cyclic olefin copolymer (COC) is still a tough challenge. We developed a robust method for COC surface grafting through reaction with aryldiazonium. Chemical diazonium reduction generated an aryl radical and the formation of a grafted film layer on the organic surface. We also demonstrated that the chemical reduction of diazonium salt was not sufficient to form a film on the COC surface. UV illumination had to be combined with chemical reduction to graft an aryl layer onto the COC surface. We optimized organic film deposition by using different chemical reducers, different reaction times and reagent proportions. We characterized surface modifications by fluorescence microscopy and contact angle measurements, infrared spectroscopy, X-ray photoemission spectroscopy and Raman spectroscopy, and assessed the topography of the aryl film by atomic force microscopy. This original strategy allowed us to evidence various organic functions to graft biomolecules onto COC surfaces with a fast and efficient technique.

  1. Graft polymerization of acrylic acid and methacrylic acid onto poly(vinylidene fluoride) powder in presence of metallic salt and sulfuric acid

    NASA Astrophysics Data System (ADS)

    Deng, Bo; Yu, Yang; Zhang, Bowu; Yang, Xuanxuan; Li, Linfan; Yu, Ming; Li, Jingye

    2011-02-01

    Poly(vinylidene fluoride) (PVDF) powder was grafted with acrylic acid (AAc) or methacrylic acid (MAA) by the pre-irradiation induced graft polymerization technique. The presence of graft chains was proven by FT-IR spectroscopy. The degree of grafting (DG) was calculated by the acid-base back titration method. The synergistic effect of acid and Mohr's salt on the grafting kinetics was examined. The results indicated that adding sulfuric acid and Mohr's salt simultaneously in AAc or MAA solutions led to a strong enhancement in the degree of grafting. The grafted PVDF powder was cast into microfiltration (MF) membranes using the phase inversion method and some properties of the obtained MF membranes were characterized.

  2. Spontaneous Aryldiazonium Film Formation on 440C Stainless Steel in Nonaqueous Environments

    DOE PAGES

    Small, Leo J.; Hibbs, Michael R.; Wheeler, David R.

    2014-11-07

    The ability of three aryldiazonium salts to spontaneously assemble onto the surface of type 440C stainless steel is investigated in acetonitrile and the model hydraulic fluids tributyl phosphate and hexamethyldisiloxane. Competition between native oxide growth and organic film growth at different diazonium salt concentrations is monitored by electrochemical impedance spectroscopy. At 1 mM diazonium salt, 70% of total assembly is complete within 10 minutes, though total surface coverage by organics is limited to ≈ 0.15 monolayers. X-ray photoelectron spectroscopy confirms preferential bonding of organic molecules to iron over chromium, and adsorption of BF - 4 onto the surface. Secondary ionmore » mass spectroscopy reveals the ability of these films to self-heal when mechanically removed or damaged. Aging the diazonium salts in these nonaqueous environments demonstrates that up to 90% of the original diazonium salt concentration remains after 21 days at room temperature, while increasing the temperature beyond 50 °C results complete decomposition within 24 hours, regardless of solvent-salt combination.« less

  3. An electrochemical immunosensor for brain natriuretic peptide prepared with screen-printed carbon electrodes nanostructured with gold nanoparticles grafted through aryl diazonium salt chemistry.

    PubMed

    Serafín, V; Torrente-Rodríguez, R M; González-Cortés, A; García de Frutos, P; Sabaté, M; Campuzano, S; Yáñez-Sedeño, P; Pingarrón, J M

    2018-03-01

    A sensitive amperometric immunosensor has been prepared by immobilization of capture antibodies onto gold nanoparticles (AuNPs) grafted on a screen-printed carbon electrode (SPCE) through aryl diazonium salt chemistry using 4-aminothiophenol (AuNPs-S-Phe-SPCE). The immunosensor was designed for the accurate determination of clinically relevant levels of B-type natriuretic peptide (BNP) in human serum samples. The nanostructured electrochemical platform resulted in an ordered layer of AuNPs onto SPCEs which combined the advantages of high conductivity and improved stability of immobilized biomolecules. The resulting disposable immunosensor used a sandwich type immunoassay involving a peroxidase-labeled detector antibody. The amperometric transduction was carried out at -0.20V (vs the Ag pseudo-reference electrode) upon the addition of hydroquinone (HQ) as electron transfer mediator and H 2 O 2 as the enzyme substrate. The nanostructured immunosensors show a storage stability of at least 25 days, a linear range between 0.014 and 15ngmL -1 , and a LOD of 4pgmL -1 , which is 100 times lower than the established cut-off value for heart failure (HF) diagnosis. The performance of the immunosensor is advantageously compared with that provided with immunosensors prepared by grafting SPCE with p-phenylendiamine (H 2 N-Phe-SPCE) and attaching AuNPs by immersion into an AuNPs suspension or by electrochemical deposition, as well as with immunosensors constructed using commercial AuNPs-modified SPCEs. The developed immunosensor was applied to the successful analysis of human serum from heart failure (HF) patients upon just a 10-times dilution as sample treatment. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Mechanism of the coupling of diazonium to single-walled carbon nanotubes and its consequences.

    PubMed

    Schmidt, Grégory; Gallon, Salomé; Esnouf, Stéphane; Bourgoin, Jean-Philippe; Chenevier, Pascale

    2009-01-01

    On the tube: The coupling of diazonium ions onto single-walled carbon nanotubes is shown to proceed through a radical chain reaction by kinetic analysis of the absorption peak drop (see picture). Radical species are also revealed by ESR. Metallic (m) nanotubes play a special catalytic role in the functionalization of semiconducting (sc) nanotubes.Due to its simplicity and versatility, diazonium coupling is the most widely used method for carbon nanotube (CNT) functionalization to increase CNT processability and add new functionalities. Yet, its mechanism is so far mostly unknown. Herein, we use kinetic analysis to shed light on this complex mechanism. A free-radical chain reaction is revealed by absorption spectroscopy and ESR. Metallic CNTs are shown to play an unexpected catalytic role. The step determining the selectivity towards metallic CNTs is identified by a Hammett correlation. A mechanistic model is proposed that predicts reactivity and selectivity as a function of diazonium electrophilicity and metallic-to-semiconducting CNT ratio, thus opening perspectives of controlled high-yield functionalization and purification.

  5. Protein-diazonium adduct direct electrografting onto SPRi-biochip.

    PubMed

    Corgier, Benjamin P; Bellon, Sophie; Anger-Leroy, Marielle; Blum, Loïc J; Marquette, Christophe A

    2009-08-18

    A direct protein immobilization method for surface plasmon resonance imaging (SPRi) gold chip arraying is exposed. The biomolecule electroaddressing strategy, previously demonstrated by our team on carbon surfaces, is here valuably involved and adapted to create a straightforward and efficient protein immobilization process onto SPRi-biochips. The proteins, modified with an aryl-diazonium adduct, are addressed to the SPRi chip surface through the electroreduction of the aryl-diazonium. The biomolecule deposition was followed through SPRi live measurements during the electrografting process. A specially designed setup enabled us to directly observe the mass increasing at the sensor surface while the proteins were electrografted. A pin electrospotting method, allowing the achievement of distinct sensing layers on gold SPRi-biochips, was used to generate microarray biochips. The integrity of the immobilized proteins and the specificity of the detection, based on antigen/antibody interactions, were demonstrated for the detection of specific antibodies and ovalbumin. The SPRi detection limit of ovalbumin using the electroaddressing of anti-ovalbumin IgG was compared with two other immobilization procedures, cystamine-glutaraldehyde self-assembled monolayer and pyrrole, and was found to be a decade lower than these ones (100 ng/mL, i.e., 2 nM).

  6. Bimetallic complexes and polymerization catalysts therefrom

    DOEpatents

    Patton, Jasson T.; Marks, Tobin J.; Li, Liting

    2000-11-28

    Group 3-6 or Lanthanide metal complexes possessing two metal centers, catalysts derived therefrom by combining the same with strong Lewis acids, Bronsted acid salts, salts containing a cationic oxidizing agent or subjected to bulk electrolysis in the presence of compatible, inert non-coordinating anions and the use of such catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers are disclosed.

  7. Unprecedented Self-Organized Monolayer of a Ru(II) Complex by Diazonium Electroreduction.

    PubMed

    Nguyen, Van Quynh; Sun, Xiaonan; Lafolet, Frédéric; Audibert, Jean-Frédéric; Miomandre, Fabien; Lemercier, Gilles; Loiseau, Frédérique; Lacroix, Jean-Christophe

    2016-08-03

    A new heteroleptic polypyridyle Ru(II) complex was synthesized and deposited on surface by the diazonium electroreduction process. It yields to the covalent grafting of a monolayer. The functionalized surface was characterized by XPS, electrochemistry, AFM, and STM. A precise organization of the molecules within the monolayer is observed with parallel linear stripes separated by a distance of 3.8 nm corresponding to the lateral size of the molecule. Such organization suggests a strong cooperative process in the deposition process. This strategy is an original way to obtain well-controlled and stable functionalized surfaces for potential applications related to the photophysical properties of the grafted chromophore. As an exciting result, it is the first example of a self-organized monolayer (SOM) obtained using diazonium electroreduction.

  8. Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry.

    PubMed

    Ryder, Christopher R; Wood, Joshua D; Wells, Spencer A; Yang, Yang; Jariwala, Deep; Marks, Tobin J; Schatz, George C; Hersam, Mark C

    2016-06-01

    Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)-a layered two-dimensional semiconductor-exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

  9. Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.

    PubMed

    Simula, Alexandre; Anastasaki, Athina; Haddleton, David M

    2016-02-01

    The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475) (DPn = 10-80, Mn ≈ 10,000-40 000 g mol(-1)) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1)) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. One-pot in situ mixed film formation by azo coupling and diazonium salt electrografting.

    PubMed

    Esnault, Charles; Delorme, Nicolas; Louarn, Guy; Pilard, Jean-François

    2013-06-24

    So simple: The in situ synthesis of an aryldiazonium salt and an azo-aryldiazonium salt by azo coupling from sulfanilic acid and aniline is reported. Formation of a mixed organic layer is monitored by cyclic voltammetry and atomic force microscopy. A compact mixed layer is obtained with a global roughness of 0.4 nm and 10-15 % vertical extension in the range 1.5-6 nm. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry

    NASA Astrophysics Data System (ADS)

    Ryder, Christopher R.; Wood, Joshua D.; Wells, Spencer A.; Yang, Yang; Jariwala, Deep; Marks, Tobin J.; Schatz, George C.; Hersam, Mark C.

    2016-06-01

    Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)—a layered two-dimensional semiconductor—exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

  12. Reaction of the antitumor antibiotic olivomycin I with aryl diazonium salts. Synthesis, cytotoxic and antiretroviral potency of 5-aryldiazenyl-6-O-deglycosyl derivatives of olivomycin I.

    PubMed

    Tevyashova, Anna N; Olsufyeva, Eugenia N; Turchin, Konstantin F; Balzarini, Jan; Bykov, Eugenyi E; Dezhenkova, Lyubov G; Shtil, Alexander A; Preobrazhenskaya, Maria N

    2009-07-15

    The azo coupling of the antibiotic olivomycin I (1) with aryl diazonium tetrafluoroborates produced 5-aryldiazenyl-6-O-deglycosyl derivatives of 1. The structures of new compounds were confirmed by (1)H NMR and mass spectrometry analysis. A quantum-chemical study was performed to analyze the possible directions of electrophilic substitution of 1 and the easiness of 6-O-disaccharide hydrolysis in the course of azo coupling. The antiproliferative and anti-retroviral activities of novel derivatives were studied.

  13. A simple, enaminone-based approach to some bicyclic pyridazinium tetrafluoroborates

    PubMed Central

    Josefík, František; Svobodová, Markéta; Bertolasi, Valerio

    2013-01-01

    Summary Easily obtainable cyclic enaminones (piperidin-2-ylidenealkanones) can be transformed into substituted bicyclic pyridazinium tetrafluoroborates upon treatment with corresponding diazonium salts. The transformation can be performed either in a one-pot way or in a two-step process with the isolation of single azo-coupled enaminone as the intermediate. The former method is superior. Under the optimized conditions, a number of pyridazinium salts substituted with both electron-donating and electron-withdrawing substituents was easily synthesized. A mechanism of the formation of the pyridazinium salts is suggested. A partial drawback is the possibility of the formation of a mixture of products when using a different diazonium salt in each step due to a reversibility of the azo coupling. This can be suppressed by using a more reactive diazonium salt before a less reactive one. PMID:23946844

  14. Electrolytic orthoborate salts for lithium batteries

    DOEpatents

    Angell, Charles Austen [Mesa, AZ; Xu, Wu [Tempe, AZ

    2008-01-01

    Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.

  15. Electrolytic orthoborate salts for lithium batteries

    DOEpatents

    Angell, Charles Austen [Mesa, AZ; Xu, Wu [Tempe, AZ

    2009-05-05

    Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.

  16. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

  17. Synthesis and immobilization of Ag(0) nanoparticles on diazonium modified electrodes: SECM and cyclic voltammetry studies of the modified interfaces.

    PubMed

    Noël, Jean-Marc; Zigah, Dodzi; Simonet, Jacques; Hapiot, Philippe

    2010-05-18

    A versatile method was used to prepare modified surfaces on which metallic silver nanoparticles are immobilized on an organic layer. The preparation method takes advantage, on one hand, of the activated reactivity of some alkyl halides with Ag-Pd alloys to produce metallic silver nanoparticles and, on the other hand, of the facile production of an anchoring polyphenyl acetate layer by the electrografting of substituted diazonium salts on carbon surfaces. Transport properties inside such modified layers were investigated by cyclic voltammetry, scanning electrochemical microscopy (SECM) in feedback mode, and conducting AFM imaging for characterizing the presence and nature of the conducting pathways. The modification of the blocking properties of the surface (or its conductivity) was found to vary to a large extent on the solvents used for surface examination (H(2)O, CH(2)Cl(2), and DMF).

  18. Surface modification of poly(D,L-lactic acid) scaffolds for orthopedic applications: a biocompatible, nondestructive route via diazonium chemistry.

    PubMed

    Mahjoubi, Hesameddin; Kinsella, Joseph M; Murshed, Monzur; Cerruti, Marta

    2014-07-09

    Scaffolds made with synthetic polymers such as polyesters are commonly used in bone tissue engineering. However, their hydrophobicity and the lack of specific functionalities make their surface not ideal for cell adhesion and growth. Surface modification of these materials is thus crucial to enhance the scaffold's integration in the body. Different surface modification techniques have been developed to improve scaffold biocompatibility. Here we show that diazonium chemistry can be used to modify the outer and inner surfaces of three-dimensional poly(D,L-lactic acid) (PDLLA) scaffolds with phosphonate groups, using a simple two-step method. By changing reaction time and impregnation procedure, we were able to tune the concentration of phosphonate groups present on the scaffolds, without degrading the PDLLA matrix. To test the effectiveness of this modification, we immersed the scaffolds in simulated body fluid, and characterized them with scanning electron microscopy, X-ray photoelectron spectroscopy, Raman, and infrared spectroscopy. Our results showed that a layer of hydroxyapatite particles was formed on all scaffolds after 2 and 4 weeks of immersion; however, the precipitation was faster and in larger amounts on the phosphonate-modified than on the bare PDLLA scaffolds. Both osteogenic MC3T3-E1 and chondrogenic ATDC5 cell lines showed increased cell viability/metabolic activity when grown on a phosphonated PDLLA surface in comparison to a control PDLLA surface. Also, more calcium-containing minerals were deposited by cultures grown on phosphonated PDLLA, thus showing the pro-mineralization properties of the proposed modification. This work introduces diazonium chemistry as a simple and biocompatible technique to modify scaffold surfaces, allowing to covalently and homogeneously bind a number of functional groups without degrading the scaffold's polymeric matrix.

  19. Chemically functionalized two-dimensional titanium carbide MXene by in situ grafting-intercalating with diazonium ions to enhance supercapacitive performance

    NASA Astrophysics Data System (ADS)

    Wang, Hongbing; Zhang, Jianfeng; Wu, Yuping; Huang, Huajie; Jiang, Quanguo

    2018-04-01

    Two-dimensional Ti3C2 MXene nanosheets were functionalized with phenylsulfonic groups derived from in situ generated diazonium ions by the corresponding amine. During the functionalization process, the aryl groups were attached onto the MXene surfaces in the form of strong MXene-aryl (Tisbnd Osbnd C) linkages. Simultaneously, the intercalation of diazonium ions enabled Ti3C2 multi-layers to be delaminated into separate few-layer nanosheets via weak sonication with low energy. As a result of chemical functionalization for MXene Ti3C2, the dispersibility was greatly improved and the specific surface area increased significantly. The grafted functional groups are still stable up to at least 200 °C upon thermogravimetric analysis measurements. With diazonium ions intercalating and electroactive groups grafting between-in MXene layers, the chemically functionalized Ti3C2 electrodes exhibited an enhanced supercapacitive performance, which acquired a specific capacitance more than double that of pristine Ti3C2 samples and excellent cycling stability (91% capacity retention after 10,000 cycles at 3 A g-1). This feasible modification scheme can be also extended to functionalize other types of MXenes materials with this or other aryl diazonium ions as surface modifiers and intercalants, thus offering scope for full potential applications of the new 2D materials.

  20. Ab initio and density functional force field studies on the IR spectra and structure of diazonium dicyanomethylide (diazodicyanomethane)

    NASA Astrophysics Data System (ADS)

    Georgieva, Miglena K.

    2004-03-01

    The structure of diazonium dicyanomethylide (diazodicyanomethane) +N 2-C(CN) 2-↔N 2C(CN) 2 has been studied on the basis of ab initio HF, MP2 and DFT BLYP force field calculations, as well as of literature IR spectra and X-ray diffraction structural data. The results have been compared with those obtained for a series of chemical relatives of the title compound, i.e. molecules, push-pull molecules, anions and zwitterions, containing α-dicyano or diazo fragments, and especially substituted ammonium dicyanomethylides and diazomethane +N 2-CH 2-↔N 2CH 2. It has been found on the basis of spectral, bond length, bond order and electric charge analyses that the diazonium (or carbanionic, left) canonical form is much more important for the title zwitterion, than the corresponding one for diazomethane. So, the title compound can be named (and considered as) both diazonium dicyanomethylide and dicyanodiazomethane.

  1. Immobilised histidine tagged β2-adrenoceptor oriented by a diazonium salt reaction and its application in exploring drug-protein interaction using ephedrine and pseudoephedrine as probes.

    PubMed

    Li, Qian; Bian, Liujiao; Zhao, Xinfeng; Gao, Xiaokang; Zheng, Jianbin; Li, Zijian; Zhang, Youyi; Jiang, Ru; Zheng, Xiaohui

    2014-01-01

    A new oriented method using a diazonium salt reaction was developed for linking β2-adrenoceptor (β2-AR) on the surface of macroporous silica gel. Stationary phase containing the immobilised receptor was used to investigate the interaction between β2-AR and ephedrine plus pseudoephedrine by zonal elution. The isotherms of the two drugs best fit the Langmuir model. Only one type of binding site was found for ephedrine and pseudoephedrine targeting β2-AR. At 37 °C, the association constants during the binding were (5.94±0.05)×103/M for ephedrine and (3.80±0.02) ×103/M for pseudoephedrine, with the binding sites of (8.92±0.06) ×10-4 M. Thermodynamic studies showed that the binding of the two compounds to β2-AR was a spontaneous reaction with exothermal processes. The ΔGθ, ΔHθ and ΔSθ for the interaction between ephedrine and β2-AR were -(22.33±0.04) kJ/mol, -(6.51±0.69) kJ/mol and 50.94±0.31 J/mol·K, respectively. For the binding of pseudoephedrine to the receptor, these values were -(21.17±0.02) kJ/mol, -(7.48±0.56) kJ/mol and 44.13±0.01 J/mol·K. Electrostatic interaction proved to be the driving force during the binding of the two drugs to β2-AR. The proposed immobilised method will have great potential for attaching protein to solid substrates and realizing the interactions between proteins and drugs.

  2. Immobilised Histidine Tagged β 2-Adrenoceptor Oriented by a Diazonium Salt Reaction and Its Application in Exploring Drug-Protein Interaction Using Ephedrine and Pseudoephedrine as Probes

    PubMed Central

    Li, Qian; Bian, Liujiao; Zhao, Xinfeng; Gao, Xiaokang; Zheng, Jianbin; Li, Zijian; Zhang, Youyi; Jiang, Ru; Zheng, Xiaohui

    2014-01-01

    A new oriented method using a diazonium salt reaction was developed for linking β 2-adrenoceptor (β 2-AR) on the surface of macroporous silica gel. Stationary phase containing the immobilised receptor was used to investigate the interaction between β 2-AR and ephedrine plus pseudoephedrine by zonal elution. The isotherms of the two drugs best fit the Langmuir model. Only one type of binding site was found for ephedrine and pseudoephedrine targeting β 2-AR. At 37 °C, the association constants during the binding were (5.94±0.05)×103/M for ephedrine and (3.80±0.02) ×103/M for pseudoephedrine, with the binding sites of (8.92±0.06) ×10−4 M. Thermodynamic studies showed that the binding of the two compounds to β 2-AR was a spontaneous reaction with exothermal processes. The ΔGθ, ΔHθ and ΔSθ for the interaction between ephedrine and β 2-AR were −(22.33±0.04) kJ/mol, −(6.51±0.69) kJ/mol and 50.94±0.31 J/mol·K, respectively. For the binding of pseudoephedrine to the receptor, these values were −(21.17±0.02) kJ/mol, −(7.48±0.56) kJ/mol and 44.13±0.01 J/mol·K. Electrostatic interaction proved to be the driving force during the binding of the two drugs to β 2-AR. The proposed immobilised method will have great potential for attaching protein to solid substrates and realizing the interactions between proteins and drugs. PMID:24747442

  3. Interactions of p-Nitrobenzene Diazonium Fluoroborate and Analogs with the Active Sites of Acetylcholine-Receptor and -Esterase*

    PubMed Central

    Mautner, Henry G.; Bartels, Eva

    1970-01-01

    p-Nitrobenzene diazonium fluoroborate (NDF) is a potent inhibitor of the carbamylcholine-induced depolarization of the electroplax and of acetylcholinesterase. It probably forms covalent bonds with the acetylcholine-receptor and -esterase at the active site of the proteins. Its inhibitory strength is at least the same as that of trimethylammonium diazonium fluoroborate (TDF). The p-acetoxy analog, with its weaker electron-withdrawing group, is about ten times weaker as an inhibitor than the trimethylammonium or p-nitro analogs, both of which have strong electron-withdrawing groups. After treatment of the electroplax preparation with dithiothreitol, NDF remains an irreversible receptor-inhibitor, while TDF becomes a potent reversible receptor-activator. TDF is self-inhibitory: applied before reduction, it no longer depolarizes. Although the first observations on TDF suggested that the compound labels both proteins by virtue of the steric complementary of its trimethylammonium group to a negative subsite in the proteins, the present study indicates that it is the positively charged diazonium group that reacts with the active sites of the proteins to form a covalent bond with an appropriate amino-acid residue. PMID:5272331

  4. Diazotisation of Weakly Basic Aromatic and Heterocyclic Amines in Strongly Acid Media

    NASA Astrophysics Data System (ADS)

    Godovikova, Tamara I.; Rakitin, Oleg A.; Khmel'nitskii, Lenor I.

    1983-05-01

    The review is devoted to the diazotisation of weakly basic aromatic amines. The methods of synthesis of diazonium salts based on these amines by non-traditional methods are examined. Data on the mechanism of the diazotisation reaction in strongly acid media are surveyed. Reactions of diazonium salts leading to the synthesis of new compounds are presented. The bibliography includes 75 references.

  5. Alkali and alkaline earth metal salts of tetrazolone: structurally interesting and excellently thermostable.

    PubMed

    He, Piao; Wu, Le; Wu, Jin-Ting; Yin, Xin; Gozin, Michael; Zhang, Jian-Guo

    2017-07-04

    Tetrazolone (5-oxotetrazole) was synthesized by a moderate strategy through three steps (addition, cyclization and catalytic hydrogenation) avoiding the unstable intermediate diazonium, as reported during the previous preparation. Alkali and alkaline earth metal salts with lithium (1), sodium (2), potassium (3), rubidium (4) caesium (5), magnesium (6), calcium (7), strontium (8) and barium (9) were prepared and fully characterized using elemental analysis, IR and NMR spectroscopy, DSC and TG analysis. All metal salts were characterized via single-crystal X-ray diffraction. They crystallize in common space groups with high densities ranging from 1.479 (1) to 3.060 g cm -3 (5). Furthermore, the crystal structures of 7, 8 and 9 reveal interesting porous energetic coordination polymers with strong hydrogen bond interactions. All new salts have good thermal stabilities with decomposition temperature between 215.0 °C (4) and 328.2 °C (7), significantly higher than that of the reported nitrogen-rich salt neutral tetrazolone. The sensitivities towards impact and friction were tested using standard methods, and all the tetrazolone-based compounds investigated can be classified into insensitive. The flame test of these metal salts supports their potential use as perchlorate-free pyrotechnics or eco-friendly insensitive energetic materials.

  6. Charge transfer from TiO2 into adsorbed benzene diazonium compounds

    NASA Astrophysics Data System (ADS)

    Merson, A.; Dittrich, Th.; Zidon, Y.; Rappich, J.; Shapira, Yoram

    2004-08-01

    Electron transfer from sol-gel-prepared TiO2 into adsorbed benzene diazonium compounds has been investigated using cyclic voltammetry, x-ray photoelectron spectroscopy, contact potential difference, and surface photovoltage spectroscopy. The results show that the potential of maximum electron transfer depends strongly on the dipole moment of the benzene compound. Two reactive surface sites at which electron transfer occurs have been identified.

  7. 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.

  8. A Novel, Diazonium-Phenolic Resin Two-Layer Resist System Utilizing Photoinduced Interfacial Insolubilization

    NASA Astrophysics Data System (ADS)

    Uchino, Shou-ichi; Iwayanagi, Takao; Ueno, Takumi; Hashimoto, Michiaki; Nonogaki, Saburo

    1987-08-01

    This paper deals with a negative two-layer photoresist system utilizing a photoinduced insolubilization process at the interface. The bottom layer is a phenolic resin either with or without aromatic azide and the top layer is a photosensitive layer comprised of an aromatic diazonium compound and a water soluble polymer. Upon exposure to light, the diazo compound decomposes to cause insolubilization at the interface between the two layers. The system exhibits high contrast due to the combination of interfacial insolubilization and contrast enhancement by photobleaching of the diazonium compound. Patterns of 0.5 um lines and spaces are obtained using an i-line stepper and a resist system containing 4-diazo-N,N-dimethylaniline chloride zinc chloride in the top layer and 3-(4-azidostyry1)- 5,5-dimethyl- 2-cyclohexen-1-one in the bottom layer. Resists with varying spectral responses from mid-UV to g-line can be designed by selecting the kind of diazo compound used in the top layer.

  9. 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.

  10. 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.

  11. Electrografting of diazonium-functionalized polyoxometalates: synthesis, immobilisation and electron-transfer characterisation from glassy carbon.

    PubMed

    Rinfray, Corentin; Izzet, Guillaume; Pinson, Jean; Gam Derouich, Sarra; Ganem, Jean-Jacques; Combellas, Catherine; Kanoufi, Frédéric; Proust, Anna

    2013-10-04

    Polyoxometalates (POMs) are attractive candidates for the rational design of multi-level charge-storage materials because they display reversible multi-step reduction processes in a narrow range of potentials. The functionalization of POMs allows for their integration in hybrid complementary metal oxide semiconductor (CMOS)/molecular devices, provided that fine control of their immobilisation on various substrates can be achieved. Owing to the wide applicability of the diazonium route to surface modification, a functionalized Keggin-type POM [PW11 O39 {Ge(p-C6 H4 -CC-C6 H4 -${{\\rm N}{{+\\hfill \\atop 2\\hfill}}}$)}](3-) bearing a pending diazonium group was prepared and subsequently covalently anchored onto a glassy carbon electrode. Electron transfer with the immobilised POM was thoroughly investigated and compared to that of the free POM in solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Functionalization of multilayer fullerenes (carbon nano-onions) using diazonium compounds and "click" chemistry.

    PubMed

    Flavin, Kevin; Chaur, Manuel N; Echegoyen, Luis; Giordani, Silvia

    2010-02-19

    A novel versatile approach for the functionalization of multilayer fullerenes (carbon nano-onions) has been developed, which involves the facile introduction of a variety of simple functionalities onto their surface by treatment with in situ generated diazonium compounds. This approach is complemented by use of "click" chemistry which was used for the covalent introduction of more complex porphyrin molecules.

  13. Reductive electrografting of benzene (p-bisdiazonium hexafluorophosphate): a simple and effective protocol for creating diazonium-functionalized thin films.

    PubMed

    Marshall, Nicholas; Locklin, Jason

    2011-11-01

    In this Article, we describe a protocol for surface functionalization of benzenediazonium hexafluorophosphate monolayers by in situ electrochemical reduction of bis(benzenediazonium) hexafluorophosphate. Due to the considerable difference in potential between the first and second reduction of this species, it is possible to form a high density of surface-bound diazonium groups by use of a mild potential which selectively reduces only one diazonium group per ring. The resulting diazonium-containing monolayer reacts readily with solutions of electron-rich aromatic compounds. The reaction with ferrocene produces a dense (2.7 × 10(-10) mol/cm(2)) ferrocene-containing monolayer through a Gomberg-Bachmann type arylation. The resulting ferrocene group exhibits relatively rapid electron transfer to the electrode due to the conjugated linker layer as measured by alternating current voltammetry (ACV) and cyclic voltammetry. Aromatic systems with π-donor substitutents (N,N-dimethylaniline, N,N,N',N'-tetramethyldiaminobenzophenone, and hydroquinone) react through an azo-coupling to form monolayers linked to the surface through an azobenzene moiety. The redox properties of these electron-rich species tethered to the surface were observed and quantified using cyclic voltammetry. This simple and versatile functionalization procedure has a wide variety of potential applications in surface science and materials research.

  14. Covalent functionalization of reduced graphene oxide with porphyrin by means of diazonium chemistry for nonlinear optical performance

    NASA Astrophysics Data System (ADS)

    Wang, Aijian; Yu, Wang; Huang, Zhipeng; Zhou, Feng; Song, Jingbao; Song, Yinglin; Long, Lingliang; Cifuentes, Marie P.; Humphrey, Mark G.; Zhang, Long; Shao, Jianda; Zhang, Chi

    2016-03-01

    Reduced graphene oxide (RGO)-porphyrin (TPP) nanohybrids (RGO-TPP 1 and RGO-TPP 2) were prepared by two synthetic routes that involve functionalization of the RGO using diazonium salts. The microscopic structures, morphology, photophysical properties and nonlinear optical performance of the resultant RGO-TPP nanohybrids were investigated. The covalent bonding of the porphyrin-functionalized-RGO nanohybrid materials was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin units to the surface of the RGO by diazotization significantly improves the solubility and ease of processing of these RGO-based nanohybrid materials. Ultraviolet/visible absorption and steady-state fluorescence studies indicate considerable π-π interactions and effective photo-induced electron and/or energy transfer between the porphyrin moieties and the extended π-system of RGO. The nonlinear optical properties of RGO-TPP 1 and RGO-TPP 2 were investigated by open-aperture Z-scan measurements at 532 nm with both 4 ns and 21 ps laser pulses, the results showing that the chemical nanohybrids exhibit improved nonlinear optical properties compared to those of the benchmark material C60, and the constituent RGO or porphyrins.

  15. A facile route to steady redox-modulated nitroxide spin-labeled surfaces based on diazonium chemistry.

    PubMed

    Cougnon, Charles; Boisard, Séverine; Cador, Olivier; Dias, Marylène; Levillain, Eric; Breton, Tony

    2013-05-18

    A TEMPO derivative was covalently grafted onto carbon and gold surfaces via the diazonium chemistry. The acid-dependent redox properties of the nitroxyl group were exploited to elaborate electro-switchable magnetic surfaces. ESR characterization demonstrated the reversible and permanent magnetic character of the material.

  16. Polyimide amic acid salts and polyimide membranes formed therefrom

    DOEpatents

    Ding, Yong; Bikson, Benjamin; Nelson, Joyce Katz; Macheras, James Timothy

    2004-04-06

    The invention relates to preparation and uses of novel polymeric materials, polyimide amic acid salts (PIAAS). The use of these materials for the fabrication of fluid separation membranes is further disclosed.

  17. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength

    NASA Astrophysics Data System (ADS)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Wu, Guangshun; Ma, Lichun; Zhao, Min; Huang, Yudong

    2016-01-01

    Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17-10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  18. Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

    NASA Technical Reports Server (NTRS)

    Kolb, V.; Orgel, L. E.; Miller, S. L. (Principal Investigator)

    1994-01-01

    We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

  19. Covalent functionalization of reduced graphene oxide with porphyrin by means of diazonium chemistry for nonlinear optical performance

    PubMed Central

    Wang, Aijian; Yu, Wang; Huang, Zhipeng; Zhou, Feng; Song, Jingbao; Song, Yinglin; Long, Lingliang; Cifuentes, Marie P.; Humphrey, Mark G.; Zhang, Long; Shao, Jianda; Zhang, Chi

    2016-01-01

    Reduced graphene oxide (RGO)-porphyrin (TPP) nanohybrids (RGO-TPP 1 and RGO-TPP 2) were prepared by two synthetic routes that involve functionalization of the RGO using diazonium salts. The microscopic structures, morphology, photophysical properties and nonlinear optical performance of the resultant RGO-TPP nanohybrids were investigated. The covalent bonding of the porphyrin-functionalized-RGO nanohybrid materials was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimetric analysis. Attachment of the porphyrin units to the surface of the RGO by diazotization significantly improves the solubility and ease of processing of these RGO-based nanohybrid materials. Ultraviolet/visible absorption and steady-state fluorescence studies indicate considerable π-π interactions and effective photo-induced electron and/or energy transfer between the porphyrin moieties and the extended π-system of RGO. The nonlinear optical properties of RGO-TPP 1 and RGO-TPP 2 were investigated by open-aperture Z-scan measurements at 532 nm with both 4 ns and 21 ps laser pulses, the results showing that the chemical nanohybrids exhibit improved nonlinear optical properties compared to those of the benchmark material C60, and the constituent RGO or porphyrins. PMID:27011265

  20. Photoinitiated polymerization of PEG-diacrylate with lithium phenyl-2,4,6-trimethylbenzoylphosphinate: polymerization rate and cytocompatibility

    PubMed Central

    Fairbanks, Benjamin D.; Schwartz, Michael P.; Bowman, Christopher N.; Anseth, Kristi S.

    2009-01-01

    Due to mild reaction conditions and temporal and spatial control over material formation, photopolymerization has become a valuable technique for the encapsulation of living cells in three dimensional, hydrated, biomimetic materials. For such applications,2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (I2959) is the most commonly used photoinitiator (by virtue of its moderate water solubility), yet this initiator has an absorption spectrum that is poorly matched with wavelengths of light generally regarded as benign to living cells, limiting the rate at which it may initiate polymerization in their presence. In contrast, acylphosphine oxide photoinitiators, generally exhibit absorption spectra at wavelengths suitable for cell encapsulation, yet commercially available initiators of this class have low water solubility. Here, a water soluble lithium acylphosphinate salt is evaluated for its ability to polymerize diacrylated poly(ethylene glycol) (PEGDA) monomers rapidly into hydrogels, while maintaining high viability during direct encapsulation of cells. Through rheometric measurements, the time to reach gelation of a PEGDA solution with the phosphinate initiator is one tenth the time for that using I2959 at similar concentrations, when exposed to 365 nm light. Further, polymerization with the phosphinate initiator at 405 nm visible light exposure is achieved with low initiator concentrations and light intensities, precluded in polymerizations initiated with I2959 by its absorbance profile. When examined 24 hours after encapsulation, survival rates of human neonatal fibroblasts encapsulated in hydrogels polymerized with the phosphinate initiator exceed 95%, demonstrating the cytocompatibility of this initiating system. PMID:19783300

  1. Design and testing of tubular polymeric capsules for self-healing of concrete

    NASA Astrophysics Data System (ADS)

    Araújo, M.; Van Tittelboom, K.; Feiteira, J.; Gruyaert, E.; Chatrabhuti, S.; Raquez, J.-M.; Šavija, B.; Alderete, N.; Schlangen, E.; De Belie, N.

    2017-10-01

    Polymeric healing agents have proven their efficiency to heal cracks in concrete in an autonomous way. However, the bottleneck for valorisation of self-healing concrete with polymeric healing agents is their encapsulation. In the present work, the suitability of polymeric materials such as poly(methyl methacrylate) (PMMA), polystyrene (PS) and poly(lactic acid) (PLA) as carriers for healing agents in self-healing concrete has been evaluated. The durability of the polymeric capsules in different environments (demineralized water, salt water and simulated concrete pore solution) and their compatibility with various healing agents have been assessed. Next, a numerical model was used to simulate capsule rupture when intersected by a crack in concrete and validated experimentally. Finally, two real-scale self-healing concrete beams were made, containing the selected polymeric capsules (with the best properties regarding resistance to concrete mixing and breakage upon crack formation) or glass capsules and a reference beam without capsules. The self-healing efficiency was determined after crack creation by 3-point-bending tests.

  2. Enhanced Electro-Static Modulation of Ionic Diffusion through Carbon Nanotube Membranes by Diazonium Grafting Chemistry

    PubMed Central

    Majumder, Mainak; Keis, Karin; Zhan, Xin; Meadows, Corey; Cole, Jeggan

    2013-01-01

    A membrane structure consisting of an aligned array of open ended carbon nanotubes (~ 7 nm i.d.) spanning across an inert polymer matrix allows the diffusive transport of aqueous ionic species through CNT cores. The plasma oxidation process that opens CNTs tips inherently introduces carboxylic acid groups at the CNT tips, which allows for a limited amount of chemical functional at the CNT pore entrance. However for numerous applications, it is important to increase the density of carboxylic acid groups at the pore entrance for effective separation processes. Aqueous diazonium based electro-chemistry significantly increases the functional density of carboxylic acid groups. pH dependent dye adsorption-desorption and interfacial capacitance measurements indicate ~ 5–6 times increase in functional density. To further control the spatial location of the functional chemistry, a fast flowing inert liquid column inside the CNT core is found to restrict the diazonium grafting to the CNT tips only. This is confirmed by the increased flux of positively charged Ru(bi-py)3+2 with anionic functionality. The electrostatic enhancement of ion diffusion is readily screened in 0.1(M) electrolyte solution consistent with the membrane pore geometry and increased functional density. PMID:25132719

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

    NASA Astrophysics Data System (ADS)

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

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

  4. Early nucleation events in the polymerization of actin, probed by time-resolved small-angle x-ray scattering

    PubMed Central

    Oda, Toshiro; Aihara, Tomoki; Wakabayashi, Katsuzo

    2016-01-01

    Nucleators generating new F-actin filaments play important roles in cell activities. Detailed information concerning the events involved in nucleation of actin alone in vitro is fundamental to understanding these processes, but such information has been hard to come by. We addressed the early process of salt-induced polymerization of actin using the time-resolved synchrotron small-angle X-ray scattering (SAXS). Actin molecules in low salt solution maintain a monomeric state by an electrostatic repulsive force between molecules. On mixing with salts, the repulsive force was rapidly screened, causing an immediate formation of many of non-polymerizable dimers. SAXS kinetic analysis revealed that tetramerization gives the highest energetic barrier to further polymerization, and the major nucleation is the formation of helical tetramers. Filaments start to grow rapidly with the formation of pentamers. These findings suggest an acceleration mechanism of actin assembly by a variety of nucleators in cells. PMID:27775032

  5. The Onium Compounds

    NASA Astrophysics Data System (ADS)

    Tsarevsky, Nicolay V.; Slaveykova, Vera; Manev, Stefan; Lazarov, Dobri

    1997-06-01

    The onium salts are of a big interest for theoretical and structural chemistry, and for organic synthesis. Some representatives of the group (e.g. ammonium salts) were known from the oldest times. Many onium salts are met the nature: ammonium salts (either as inorganic salts, and organic derivatives, e.g. aminoacids, salts of biogenic amines and alkaloids, etc.); oxonium salts (plant pigments as anthocyans are organic oxonium compounds), etc. In 1894 C. Hartmann and V. Meyer prepared the first iodonium salts - 4-iododiphenyliodonium hydrogensulfate and diphenyliodonium salts, and suggested the ending -onium for all compounds with properties similar to those of ammonium salts. Nowadays onium compounds of almost all nonmetals are synthesised and studied. A great variety of physical methods: diffraction (e.g. XRD) and spectral methods (IR-, NMR-, and UV-spectra), as well as the chemical properties and methods of preparation of onium salts have been used in determination of the structure of these compounds. The application of different onium salts is immense. Ammonium, phosphonium and sulfonium salts are used as phase-transfer catalysts; diazonium salts - for the preparation of dyes, metalochromic and pH-indicators. All the onium salts and especially diazonium and iodonium salts are very useful reagents in organic synthesis.

  6. Grafting of diazonium salts on oxides surface: formation of aryl-O bonds on iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Brymora, Katarzyna; Fouineau, Jonathan; Eddarir, Asma; Chau, François; Yaacoub, Nader; Grenèche, Jean-Marc; Pinson, Jean; Ammar, Souad; Calvayrac, Florent

    2015-11-01

    Combining ab initio modeling and 57Fe Mössbauer spectrometry, we characterized the nature of the chemical linkage of aminoalkyl arenediazonium salt on the surface of iron oxide nanoparticles. We established that it is built through a metal-oxygen-carbon bonding and not a metal-carbon one, as usually suggested and commonly observed in previously studied metal- or carbon-based surfaces.

  7. Amine Enrichment of Thin-Film Composite Membranes via Low Pressure Plasma Polymerization for Antimicrobial Adhesion.

    PubMed

    Reis, Rackel; Dumée, Ludovic F; He, Li; She, Fenghua; Orbell, John D; Winther-Jensen, Bjorn; Duke, Mikel C

    2015-07-15

    Thin-film composite membranes, primarily based on poly(amide) (PA) semipermeable materials, are nowadays the dominant technology used in pressure driven water desalination systems. Despite offering superior water permeation and salt selectivity, their surface properties, such as their charge and roughness, cannot be extensively tuned due to the intrinsic fabrication process of the membranes by interfacial polymerization. The alteration of these properties would lead to a better control of the materials surface zeta potential, which is critical to finely tune selectivity and enhance the membrane materials stability when exposed to complex industrial waste streams. Low pressure plasma was employed to introduce amine functionalities onto the PA surface of commercially available thin-film composite (TFC) membranes. Morphological changes after plasma polymerization were analyzed by SEM and AFM, and average surface roughness decreased by 29%. Amine enrichment provided isoelectric point changes from pH 3.7 to 5.2 for 5 to 15 min of plasma polymerization time. Synchrotron FTIR mappings of the amine-modified surface indicated the addition of a discrete 60 nm film to the PA layer. Furthermore, metal affinity was confirmed by the enhanced binding of silver to the modified surface, supported by an increased antimicrobial functionality with demonstrable elimination of E. coli growth. Essential salt rejection was shown minimally compromised for faster polymerization processes. Plasma polymerization is therefore a viable route to producing functional amine enriched thin-film composite PA membrane surfaces.

  8. Atom-scale covalent electrochemical modification of single-layer graphene on SiC substrates by diaryliodonium salts

    DOE PAGES

    Gearba, Raluca I.; Mueller, Kory M.; Veneman, Peter A.; ...

    2015-05-09

    Owing to its high conductivity, graphene holds promise as an electrode for energy devices such as batteries and photovoltaics. However, to this end, the work function and doping levels in graphene need to be precisely tuned. One promising route for modifying graphene’s electronic properties is via controlled covalent electrochemical grafting of molecules. We show that by employing diaryliodonium salts instead of the commonly used diazonium salts, spontaneous functionalization is avoided. This then allows for precise tuning of the grafting density. Moreover, by employing bis(4-nitrophenyl)iodonium(III) tetrafluoroborate (DNP) salt calibration curves, the surface functionalization density (coverage) of glassy carbon was controlled usingmore » cyclic voltammetry in varying salt concentrations. These electro-grafting conditions and calibration curves translated directly over to modifying single layer epitaxial graphene substrates (grown on insulating 6H-SiC (0 0 0 1)). In addition to quantifying the functionalization densities using electrochemical methods, samples with low grafting densities were characterized by low-temperature scanning tunneling microscopy (LT-STM). We show that the use of buffer-layer free graphene substrates is required for clear observation of the nitrophenyl modifications. Furthermore, atomically-resolved STM images of single site modifications were obtained, showing no preferential grafting at defect sites or SiC step edges as supposed previously in the literature. Most of the grafts exhibit threefold symmetry, but occasional extended modifications (larger than 4 nm) were observed as well.« less

  9. Simultaneous Polymerization and Polypeptide Particle Production via Reactive Spray-Drying.

    PubMed

    Glavas, Lidija; Odelius, Karin; Albertsson, Ann-Christine

    2016-09-12

    A method for producing polypeptide particles via in situ polymerization of N-carboxyanhydrides during spray-drying has been developed. This method was enabled by the development of a fast and robust synthetic pathway to polypeptides using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an initiator for the ring-opening polymerization of N-carboxyanhydrides. The polymerizations finished within 5 s and proved to be very tolerant toward impurities such as amino acid salts and water. The formed particles were prepared by mixing the monomer, N-carboxyanhydride of l-glutamic acid benzyl ester (NCAGlu) and the initiator (DBU) during the atomization process in the spray-dryer and were spherical with a size of ∼1 μm. This method combines two steps; making it a straightforward process that facilitates the production of polypeptide particles. Hence, it furthers the use of spray-drying and polypeptide particles in the pharmaceutical industry.

  10. Mapping nanometric electronic property changes induced by an aryl diazonium sub-monolayer on HOPG.

    PubMed

    González, M C R; Carro, P; Vázquez, L; Creus, A H

    2016-10-26

    The morphology as well as the electric and electronic properties of aryl diazonium, in particular 4-nitrobenzene-diazonium (NBD), films on HOPG surfaces have been studied at the nanoscale level. By controlling the 2,2-diphenyl-1-picrylhydrazyl concentration during the NBD film growth, we have been able to control the thickness of the layer. The implications of NBD submonolayer adsorption on the electrical properties of this system have been analysed through Density Functional Theory (DFT) calculations, Atomic Force (AFM), Electric Force (EFM) and Kelvin Probe Force (KPFM) microscopies. DFT simulations showed that the NBD molecule adsorbs almost perpendicularly to the HOPG surface, which was confirmed experimentally through AFM imaging in the dynamic mode. In addition, DFT calculations showed that the adsorbed NBD has an appreciable dipole moment directed towards the HOPG surface and along the vertical direction of the HOPG surface. The existence of this dipole is the origin of the EFM contrast observed between the NBD-free and NBD-covered regions when a bias of -2 V was applied to the tip. Besides, the KPFM measurements show that the NBD adsorption leads to higher work function values, which is in agreement with the DFT calculations. Noticeably, our studies show that the KPFM signal is sensitive to the partial NBD coverage of the HOPG surface below the monolayer level.

  11. Thiolated graphene - a new platform for anchoring CdSe quantum dots for hybrid heterostructures

    NASA Astrophysics Data System (ADS)

    Debgupta, Joyashish; Pillai, Vijayamohanan K.

    2013-04-01

    Effective organization of small CdSe quantum dots on graphene sheets has been achieved by a simple solution exchange with thiol terminated graphene prepared by diazonium salt chemistry. This generic methodology of CdSe QD attachment to any graphene surface has remarkable implications in designing hybrid heterostructures.Effective organization of small CdSe quantum dots on graphene sheets has been achieved by a simple solution exchange with thiol terminated graphene prepared by diazonium salt chemistry. This generic methodology of CdSe QD attachment to any graphene surface has remarkable implications in designing hybrid heterostructures. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00363a

  12. Polymeric bionanocomposite cast thin films with in situ laccase-catalyzed polymerization of dopamine for biosensing and biofuel cell applications.

    PubMed

    Tan, Yueming; Deng, Wenfang; Li, Yunyong; Huang, Zhao; Meng, Yue; Xie, Qingji; Ma, Ming; Yao, Shouzhuo

    2010-04-22

    We report here on the facile preparation of polymer-enzyme-multiwalled carbon nanotubes (MWCNTs) cast films accompanying in situ laccase (Lac)-catalyzed polymerization for electrochemical biosensing and biofuel cell applications. Lac-catalyzed polymerization of dopamine (DA) as a new substrate was examined in detail by UV-vis spectroscopy, cyclic voltammetry, quartz crystal microbalance, and scanning electron microscopy. Casting the aqueous mixture of DA, Lac and MWCNTs on a glassy carbon electrode (GCE) yielded a robust polydopamine (PDA)-Lac-MWCNTs/GCE that can sense hydroquinone with 643 microA mM(-1) cm(-2) sensitivity and 20-nM detection limit (S/N = 3). The DA substrate yielded the best biosensing performance, as compared with aniline, o-phenylenediamine, or o-aminophenol as the substrate for similar Lac-catalyzed polymerization. Casting the aqueous mixture of DA, glucose oxidase (GOx), Lac, and MWCNTs on a Pt electrode yielded a robust PDA-GOx-Lac-MWCNTs/Pt electrode that exhibits glucose-detection sensitivity of 68.6 microA mM(-1) cm(-2). In addition, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) was also coimmobilized to yield a PDA-Lac-MWCNTs-ABTS/GCE that can effectively catalyze the reduction of O(2), and it was successfully used as the biocathode of a membraneless glucose/O(2) biofuel cell (BFC) in pH 5.0 Britton-Robinson buffer. The proposed biomacromolecule-immobilization platform based on enzyme-catalyzed polymerization may be useful for preparing many other multifunctional polymeric bionanocomposites for wide applications.

  13. Simultaneous Polymerization and Polypeptide Particle Production via Reactive Spray-Drying

    PubMed Central

    2016-01-01

    A method for producing polypeptide particles via in situ polymerization of N-carboxyanhydrides during spray-drying has been developed. This method was enabled by the development of a fast and robust synthetic pathway to polypeptides using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an initiator for the ring-opening polymerization of N-carboxyanhydrides. The polymerizations finished within 5 s and proved to be very tolerant toward impurities such as amino acid salts and water. The formed particles were prepared by mixing the monomer, N-carboxyanhydride of l-glutamic acid benzyl ester (NCAGlu) and the initiator (DBU) during the atomization process in the spray-dryer and were spherical with a size of ∼1 μm. This method combines two steps; making it a straightforward process that facilitates the production of polypeptide particles. Hence, it furthers the use of spray-drying and polypeptide particles in the pharmaceutical industry. PMID:27445061

  14. Electrically controlled polymeric gel actuators

    DOEpatents

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

    1993-01-01

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

  15. Electrically controlled polymeric gel actuators

    DOEpatents

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

    1993-10-05

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

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

    PubMed

    Li, Bin; Yu, Bo; Zhou, Feng

    2013-02-12

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

  17. Precision synthesis of functional materials via RAFT polymerization and click-type chemical reactions

    NASA Astrophysics Data System (ADS)

    Flores, Joel Diez

    2011-12-01

    achieved via reaction with model amine, thiol and alcohol compounds yielding urea, thiourethane and urethane derivatives, respectively. Reactions with amines and thiols (in the presence of base) were rapid, quantitative and efficient. However, the reaction with alcohols catalyzed by dibutyltin dilaurate (DBTDL) was relatively slow but proceeded to completion. Selective reaction pathways for the addition of difunctional ethanolamine and mercaptoethanol were also investigated. A related strategy is described in Section II wherein a hydroxyl-containing diblock copolymer precursor was transformed into a library of functional copolymers via two sequential post-polymerization modification reactions. A diblock copolymer scaffold, poly[(N,N-dimethylacrylamide)-b-( N-(2-hydroxyethyl)acrylamide] (PDMA-b-PHEA) was first prepared. The hydroxyl groups of the HEA block were then reacted with 2-(acryloyloxy)ethylisocyanate (AOI) and allylisocyanate (AI) resulting in acrylate- and allyl-functionalized copolymer precursors, respectively. The efficiencies of Michael-type and free radical thiol addition reactions were investigated using selected thiols having alkyl, aryl, hydroxyl, carboxylic acid, amine and amino acid functionalities. The steps of RAFT polymerization, isocyanate-hydroxyl coupling and thiol-ene addition are accomplished under mild conditions, thus offering facile and modular routes to synthesize functional copolymers. The synthesis and solution studies of pH- and salt-responsive triblock copolymer are described in Section III. This system is capable of forming self-locked micellar structures which may be controlled by changing solution pH as well as ionic strength. A triblock copolymer containing a permanently hydrophilic poly(N,N-dimethylacrylamide) (PDMA) outer block, a salt-sensitive zwitterionic poly(3[2-(N-methylacrylamido)ethyl dimethylammonio]propanesulfonate) (PMAEDAPS) middle block and a pH-responsive 3-acrylamido-3-methylbutanoic acid (PAMBA) core block was

  18. Polymerization and photochromism of ammonium molybdate in porous glass

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  19. Biocompatible Polymeric Nanoparticles as Promising Candidates for Drug Delivery.

    PubMed

    Łukasiewicz, Sylwia; Szczepanowicz, Krzysztof; Błasiak, Ewa; Dziedzicka-Wasylewska, Marta

    2015-06-16

    The use of polymeric nanoparticles (NPs) in pharmacology provides many benefits because this approach can increase the efficacy and selectivity of active compounds. However, development of new nanocarriers requires better understanding of the interactions between NPs and the immune system, allowing for the optimization of NP properties for effective drug delivery. Therefore, in the present study, we focused on the investigation of the interactions between biocompatible polymeric NPs and a murine macrophage cell line (RAW 264.7) and a human monocytic leukemia cell line (THP-1). NPs based on a liquid core with polyelectrolyte shells were prepared by sequential adsorption of polyelectrolytes (LbL) using AOT (docusate sodium salt) as the emulsifier and the biocompatible polyelectrolytes polyanion PGA (poly-l-glutamic acid sodium salt) and polycation PLL (poly l-lysine). The average size of the obtained NPs was 80 nm. Pegylated external layers were prepared using PGA-g-PEG (PGA grafted by PEG poly(ethylene glycol)). The influence of the physicochemical properties of the NPs (charge, size, surface modification) on viability, phagocytosis potential, and endocytosis was studied. Internalization of NPs was determined by flow cytometry and confocal microscopy. Moreover, we evaluated whether addition of PEG chains downregulates particle uptake by phagocytic cells. The presented results confirm that the obtained PEG-grafted NPs are promising candidates for drug delivery.

  20. Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes

    NASA Technical Reports Server (NTRS)

    Narayan, Sri R.; Yen, Shiao-Ping S.; Reddy, Prakash V.; Nair, Nanditha

    2012-01-01

    Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.

  1. Development of polymeric palladium-nanoparticle membrane-installed microflow devices and their application in hydrodehalogenation.

    PubMed

    Yamada, Yoichi M A; Watanabe, Toshihiro; Ohno, Aya; Uozumi, Yasuhiro

    2012-02-13

    We have developed a variety of polymeric palladium-nanoparticle membrane-installed microflow devices. Three types of polymers were convoluted with palladium salts under laminar flow conditions in a microflow reactor to form polymeric palladium membranes at the laminar flow interface. These membranes were reduced with aqueous sodium formate or heat to create microflow devices that contain polymeric palladium-nanoparticle membranes. These microflow devices achieved instantaneous hydrodehalogenation of aryl chlorides, bromides, iodides, and triflates by 10-1000 ppm within a residence time of 2-8 s at 50-90 °C by using safe, nonexplosive, aqueous sodium formate to quantitatively afford the corresponding hydrodehalogenated products. Polychlorinated biphenyl (10-1000 ppm) and polybrominated biphenyl (1000 ppm) were completely decomposed under similar conditions, yielding biphenyl as a fungicidal compound. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Spontaneous grafting: a novel approach to graft diazonium cations on gold nanoparticles in aqueous medium and their self-assembly on electrodes.

    PubMed

    Kesavan, Srinivasan; John, S Abraham

    2014-08-15

    The spontaneous grafting of aminophenyl groups on gold nanoparticles (AuNPs) by reaction with in situ generated 4-aminophenyl diazonium cations (APD) in an aqueous medium was described. The spontaneous grafting was likely to proceed by transfer of electrons from AuNPs to the APD cations to form an aminophenyl radical and subsequent attachment with AuNPs. The aminophenyl (AP) functionalized gold nanoparticles (AP-AuNPs) were characterized by UV-visible spectroscopy, high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction, FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) and surface-enhanced Raman spectroscopy (SERS). The absence of characteristic vibrational bands corresponding to diazonium group in the FT-IR spectrum confirmed the reduction of the aminophenyl diazonium cations at the surface of AuNPs. The spontaneous attachment of AP on AuNPs was confirmed by XPS from the observed binding energy values for -NH2 at 399.4 eV and -N=N- at 400.2 eV. The SERS spectrum reveals the presence Au-C (437 cm(-1)) bond on AP-AuNPs. Further, the AP-AuNPs were self-assembled on GC/ITO electrode (AP-AuNPs modified electrode) with the aid of free amine groups present on the surface of AP-AuNPs via Michael's nucleophilic addition reaction. The AP-AuNPs modified electrode was characterized by cyclic voltammetry, impedance spectroscopy, UV-visible spectroscopy and scanning electron microscopy. Impedance studies show that the electron transfer reaction of [Fe(CN)6](3-/4-) was higher at the AP-AuNPs modified electrode (1.81×10(-4) cm s(-1)) than at bare (3.77×10(-5) cm s(-1)) GC electrode. Finally, the electrocatalytic activity of the AP-AuNPs modified electrode was demonstrated by studying the oxidation of dopamine (DA). Copyright © 2014 Elsevier Inc. All rights reserved.

  3. Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion.

    PubMed

    Bangle, Rachel; Sampaio, Renato N; Troian-Gautier, Ludovic; Meyer, Gerald J

    2018-01-24

    The electrografting of [Ru(ttt)(tpy-C 6 H 4 -N 2 + )] 3+ , where "ttt" is 4,4',4″-tri-tert-butyl-2,2':6',2″-terpyridine, was investigated on several wide band gap metal oxide surfaces (TiO 2 , SnO 2 , ZrO 2 , ZnO, In 2 O 3 :Sn) and compared to structurally analogous sensitizers that differed only by the anchoring group, i.e., -PO 3 H 2 and -COOH. An optimized procedure for diazonium electrografting to semiconductor metal oxides is presented that allowed surface coverages that ranged between 4.7 × 10 -8 and 10.6 × 10 -8 mol cm -2 depending on the nature of the metal oxide. FTIR analysis showed the disappearance of the diazonium stretch at 2266 cm -1 after electrografting. XPS analysis revealed a characteristic peak of Ru 3d at 285 eV as well as a peak at 531.6 eV that was attributed to O 1s in Ti-O-C bonds. Photocurrents were measured to assess electron injection efficiency of these modified surfaces. The electrografted sensitizers exhibited excellent stability across a range of pHs spanning from 1 to 14, where classical binding groups such as carboxylic and phosphonic derivatives were hydrolyzed.

  4. Controlling formation of single-molecule junctions by electrochemical reduction of diazonium terminal groups.

    PubMed

    Hines, Thomas; Díez-Pérez, Ismael; Nakamura, Hisao; Shimazaki, Tomomi; Asai, Yoshihiro; Tao, Nongjian

    2013-03-06

    We report controlling the formation of single-molecule junctions by means of electrochemically reducing two axialdiazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in situ between the molecule and gold electrodes. We report a yield enhancement in molecular junction formation as the electrochemical potential of both junction electrodes approach the reduction potential of the diazonium terminal groups. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond.

  5. Click polymerization for the synthesis of reduction-responsive polymeric prodrug

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

    2018-05-01

    Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

  6. Diazonium-based impedimetric aptasensor for the rapid label-free detection of Salmonella typhimurium in food sample.

    PubMed

    Bagheryan, Zahra; Raoof, Jahan-Bakhsh; Golabi, Mohsen; Turner, Anthony P F; Beni, Valerio

    2016-06-15

    Fast and accurate detection of microorganisms is of key importance in clinical analysis and in food and water quality monitoring. Salmonella typhimurium is responsible for about a third of all cases of foodborne diseases and consequently, its fast detection is of great importance for ensuring the safety of foodstuffs. We report the development of a label-free impedimetric aptamer-based biosensor for S. typhimurium detection. The aptamer biosensor was fabricated by grafting a diazonium-supporting layer onto screen-printed carbon electrodes (SPEs), via electrochemical or chemical approaches, followed by chemical immobilisation of aminated-aptamer. FTIR-ATR, contact angle and electrochemical measurements were used to monitor the fabrication process. Results showed that electrochemical immobilisation of the diazonium-grafting layer allowed the formation of a denser aptamer layer, which resulted in higher sensitivity. The developed aptamer-biosensor responded linearly, on a logarithm scale, over the concentration range 1 × 10(1) to 1 × 10(8)CFU mL(-1), with a limit of quantification (LOQ) of 1 × 10(1) CFU mL(-1) and a limit of detection (LOD) of 6 CFU mL(-1). Selectivity studies showed that the aptamer biosensor could discriminate S. typhimurium from 6 other model bacteria strains. Finally, recovery studies demonstrated its suitability for the detection of S. typhimurium in spiked (1 × 10(2), 1 × 10(4) and 1 × 10(6) CFU mL(-1)) apple juice samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Effects of Hofmeister salt series on gluten network formation: Part II. Anion series.

    PubMed

    Tuhumury, H C D; Small, D M; Day, L

    2016-12-01

    Different anion salts from the Hofmeister series were used to investigate their effects on gluten network formation. The effects of these anion salts on the mixing properties of the dough and the rheological and chemical properties of gluten samples extracted from the dough with these respective salts were compared. The aim of this work was to determine how different anion salts influence the formation of the gluten structure during dough mixing. It was found that the Hofmeister anion salts affected the gluten network formation by interacting directly with specific amino acid residues that resulted in changes in gluten protein composition, specifically the percentage of the unextractable polymeric protein fractions (%UPP). These changes consequently led to remarkable differences in the mixing profiles and microstructural features of the dough, small deformation rheological properties of the gluten and a strain hardening behaviour of both dough and gluten samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Soy-based polymeric surfactants prepared in carbon dioxide media and influence of structure on their surface properties

    USDA-ARS?s Scientific Manuscript database

    Soybean oil (SO) and epoxidized soybean oil (ESO) were polymerized in the CO2 media (supercritical and sub-supercritical) by BF3•OEt2 catalyst. The resulting polymers (PSO and PESO) were hydrolyzed into polysoaps (HPSO) and (HPESO) with Na+, K+, or TEA+ (triethanolamine, ammonium salt) counter ions....

  9. Ion beam promoted lithium absorption in glassy polymeric carbon

    NASA Astrophysics Data System (ADS)

    Zimmerman, R. L.; Ila, D.; Jenkins, G. M.; Maleki, H.; Poker, D. B.

    1995-12-01

    Glassy Polymeric Carbon (GPC) samples prepared from a precursor possess accessible pore volume that depends on the heat treatment temperature [G.M. Jenkins and K. Kawamura, Polymeric Carbons - Carbon Fiber, Glass and Char (Cambridge University Press, Cambridge, 1976) p. 140]. We have shown that lithium percolates without diffusion into the accessible pores of GPC samples immersed in a molten lithium salt bath at 700°C [D. Ila, G.M. Jenkins, L.R. Holland, A.L. Evelyn and H. Jena, Vacuum 45 (1994) 451]. Ion bombardment with 10 MeV Au atoms increases the total pore volume available for lithium occupation even for samples normally impermeable to lithium. The lithium concentration depth profile is measured using Li 7(p,2α) nuclear reaction analysis. We will report on lithium percolation into GPC prepared at temperatures between 500°C and 1000°C and activated by a 10 MeV gold ion bombardment.

  10. Chain Reaction Polymerization.

    ERIC Educational Resources Information Center

    McGrath, James E.

    1981-01-01

    The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

  11. Tailoring the Electrochemical Properties of Carbon Nanotube Modified Indium Tin Oxide via in Situ Grafting of Aryl Diazonium.

    PubMed

    Hicks, Jacqueline M; Wong, Zhi Yi; Scurr, David J; Silman, Nigel; Jackson, Simon K; Mendes, Paula M; Aylott, Jonathan W; Rawson, Frankie J

    2017-05-23

    Our ability to tailor the electronic properties of surfaces by nanomodification is paramount for various applications, including development of sensing, fuel cell, and solar technologies. Moreover, in order to improve the rational design of conducting surfaces, an improved understanding of structure/function relationships of nanomodifications and effect they have on the underlying electronic properties is required. Herein, we report on the tuning and optimization of the electrochemical properties of indium tin oxide (ITO) functionalized with single-walled carbon nanotubes (SWCNTs). This was achieved by controlling in situ grafting of aryl amine diazonium films on the nanoscale which were used to covalently tether SWCNTs. The structure/function relationship of these nanomodifications on the electronic properties of ITO was elucidated via time-of-flight secondary ion mass spectrometry and electrochemical and physical characterization techniques which has led to new mechanistic insights into the in situ grafting of diazonium. We discovered that the connecting bond is a nitro group which is covalently linked to a carbon on the aryl amine. The increased understanding of the surface chemistry gained through these studies enabled us to fabricate surfaces with optimized electron transfer kinetics. The knowledge gained from these studies allows for the rational design and tuning of the electronic properties of ITO-based conducting surfaces important for development of various electronic applications.

  12. Waste Isolation Pilot Plant Salt Decontamination Testing

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

    Demmer, Ricky Lynn; Reese, Stephen Joseph

    2015-03-01

    On February 14, 2014, americium and plutonium contamination was released in the Waste Isolation Pilot Plant (WIPP) salt caverns. Several practical, easily deployable methods of decontaminating WIPP salt, using a surrogate contaminant and americium (241Am), were developed and tested. The effectiveness of the methods is evaluated qualitatively, and to the extent practical, quantitatively. Of the methods tested (dry brushing, vacuum cleaning, water washing, mechanical grinding, strippable coatings, and fixative barriers), the most practical seems to be water washing. Effectiveness is very high, and water washing is easy and rapid to deploy. The amount of wastewater produced (~2 L/m2) would bemore » substantial and may not be easy to manage, but the method is the clear winner from a usability perspective. Removable surface contamination levels (smear results) from water washed coupons found no residual removable contamination. Thus, whatever contamination is left is likely adhered to (or trapped within) the salt. The other option that shows promise is the use of a fixative barrier. Bartlett Nuclear, Inc.’s Polymeric Barrier System proved the most durable of the coatings tested. The coatings were not tested for contaminant entrapment, only for coating integrity and durability.« less

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

    NASA Astrophysics Data System (ADS)

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

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

  14. Ionically fixed polymeric nanoparticles as a novel drug carrier.

    PubMed

    Lee, Sa-Won; Chang, Dong-Hoon; Shim, Myung-Seop; Kim, Bong-Oh; Kim, Sun-Ok; Seo, Min-Hyo

    2007-08-01

    In this study, we have prepared a novel polymeric drug delivery system comprised of ionically fixed polymeric nanoparticles (IFPN) and investigated their potential as a drug carrier for the passive targeting of water-insoluble anticancer drugs. For this purpose, the physicochemical characteristics of the IFPN were investigated by comparing them with conventional polymeric micelles. IFPN containing paclitaxel were prepared and evaluated for in vitro stability and in vivo pharmacokinetics. The IFPN were successfully fabricated using a monomethoxypolyethylene glycol-polylactide (mPEG-PLA) diblock copolymer and a sodium salt of D,L-poly(lactic acid) (D,L-PLACOONa) upon the addition of CaCl2. The transmittance of the IFPN solution was much lower than that of a polymeric micelle solution at the same polymer concentration implicating an increase in the number of appreciable particles. The particle size of the IFPN was approximately 20 approximately 30 nm which is in the range of particle sizes that facilitate sterile filtration using a membrane filter. The IFPN also have a regular spherical shape with a narrow size distribution. The zeta potential of the IFPN was almost neutral, similar to that of the polymeric micelles. In contrast, mixed micelles with a combination of mPEG-PLA and D,L-PLACOONa prior to the addition of Ca2+ showed a negative charge (-17 mV), possibly due to the carboxyl anion of polylactic acid exposed on the surface of the micelles. The IFPN formulation was highly kinetically stable in aqueous medium compared to the polymeric micelle formulation. The molecular weight of D,L-PLACOONa in the IFPN and the mPEG-PLA/D,L-PLACOONa molar ratio had a great influence upon the kinetic stability of the IFPN. Pharmacokinetic studies showed that the area under the concentration vs time curve (AUC) of IFPN in blood was statistically higher (about two times) when compared with that of Cremophor EL-based formulation (Taxol equivalent) or polymeric micelle formulation

  15. Well-defined flake-like polypyrrole grafted graphene nanosheets composites as electrode materials for supercapacitors with enhanced cycling stability

    NASA Astrophysics Data System (ADS)

    Wang, Xue; Wang, Tingmei; Yang, Chao; Li, Haidong; Liu, Peng

    2013-12-01

    Well-defined flake-like polypyrrole grafted graphene nanosheets composites (PPy-g-GNS) were fabricated by the in-situ chemical oxidative grafting polymerization of pyrrole in the presence of the 4-aminophenyl modified graphene nanosheets (AP-GNS), which were prepared via the coupling reaction of the graphene nanosheets (GNS) with diazonium salt. The flake-like PPy-g-GNS composite showed the high conductivity at room temperature. A maximum discharge capacitance of 191.2 F/g at the scan rate of 10 mV/s could be achieved in the three-electrode cell electrochemical testing in 1.0 mol/L NaNO3 electrolyte solution. It is higher than those of the AP-GNS, pure PPy, and the GNS/PPy composite prepared with the unmodified graphene nanosheets (GNS). The flake-like PPy-g-GNS composites also exhibited the excellent electrochemical stability even after 1000 cycles. It revealed the synergistic effect between the conducting polymer and the carbon-based support.

  16. Electrodeposition of gold nanoparticles on aryl diazonium monolayer functionalized HOPG surfaces.

    PubMed

    González, M C R; Orive, A G; Salvarezza, R C; Creus, A H

    2016-01-21

    Gold nanoparticle electrodeposition on a modified HOPG surface with a monolayer organic film based on aryl diazonium chemistry has been studied. This organic monolayer is electrochemically grown with the use of 2,2-diphenyl-1-picrylhydrazyl (DPPH), a radical scavenger. The electrodeposition of gold on this modified surface is highly favored resulting in an AuNP surface density comparable to that found on glassy carbon. AuNPs grow only in the areas covered by the organic monolayer leaving free clean HOPG zones. A progressive mechanism for the nucleation and growth is followed giving hemispherical AuNPs, homogeneously distributed on the surface and their sizes can be well controlled by the applied electrodeposition potential. By using AFM, C-AFM and electrochemical measurements with the aid of two redox probes, namely Fe(CN)6(4-)/Fe(CN)6(3-) and dopamine, relevant results about the electrochemical modified surface as well as the gold nanoparticles electrodeposited on them are obtained.

  17. Chemically grafted carbon-coated LiFePO4 using diazonium chemistry

    NASA Astrophysics Data System (ADS)

    Delaporte, Nicolas; Perea, Alexis; Amin, Ruhul; Zaghib, Karim; Bélanger, Daniel

    2015-04-01

    The effect of surface functionalization of aminophenyl and bromophenyl groups on carbon-coated LiFePO4 and the electrochemical properties of composite electrode containing these materials are reported. The functionalization was performed by spontaneous reduction of the corresponding in situ generated diazonium ions. The resulting chemically grafted LiFePO4/C materials were characterized by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. XRD analyses indicated the cathode material was partially oxidized. Thermogravimetric and elemental analyses revealed the loading of grafted molecules was between 0.2 and 1.1 wt.% depending on the reaction conditions. Interestingly, the electrochemical performances of the modified LiFePO4/C are not adversely affected by the presence of either aminophenyl and bromophenyl groups at the carbon surface, and in fact the grafted LiFePO4/C displayed slightly superior discharge capacity at the highest C rate investigated for a low loading of organic molecules.

  18. Changes in mechanical properties and morphology of elastomer coatings after immersion in salt solutions

    NASA Astrophysics Data System (ADS)

    Terán Arce, Fernando; Avci, Recep; Beech, Iwona; Cooksey, Keith; Wigglesworth-Cooksey, Barbara

    2004-03-01

    RTV11 (^TM GE Silicones) and Intersleek (^TM International Paints) are two elastomers of considerable significance to the navy and maritime industry for their application as fouling release coatings. Both materials are composed of polymeric matrices with embedded filler particles, which provide increased strength and durability to the elastomer. Using Atomic force microscopy (AFM), surface and bulk analysis techniques, we have found surface regions with microelastic properties, which correlate with the locations of filler particles inside the coatings. These particles are able to undergo elastic displacements of hundreds of nm inside the polymeric matrix during compression by the AFM tip. While elastic properties of Intersleek remain largely unchanged after immersion in salt solutions, roughening, embrittlement and stiffening occurs in RTV11 coatings depending on the amount of curing agent and humidity used during preparation and curing, respectively. Interestingly, such transformations are absent after immersion in pure water. In particle free regions, elastic moduli of RTV11 take values of 2 - 3 MPa before immersion in salt solutions. After immersion, those values increase 5 - 10 times.

  19. Identification of cation-binding sites on actin that drive polymerization and modulate bending stiffness

    PubMed Central

    Kang, Hyeran; Bradley, Michael J.; McCullough, Brannon R.; Pierre, Anaëlle; Grintsevich, Elena E.; Reisler, Emil; De La Cruz, Enrique M.

    2012-01-01

    The assembly of actin monomers into filaments and networks plays vital roles throughout eukaryotic biology, including intracellular transport, cell motility, cell division, determining cellular shape, and providing cells with mechanical strength. The regulation of actin assembly and modulation of filament mechanical properties are critical for proper actin function. It is well established that physiological salt concentrations promote actin assembly and alter the overall bending mechanics of assembled filaments and networks. However, the molecular origins of these salt-dependent effects, particularly if they involve nonspecific ionic strength effects or specific ion-binding interactions, are unknown. Here, we demonstrate that specific cation binding at two discrete sites situated between adjacent subunits along the long-pitch helix drive actin polymerization and determine the filament bending rigidity. We classify the two sites as “polymerization” and “stiffness” sites based on the effects that mutations at the sites have on salt-dependent filament assembly and bending mechanics, respectively. These results establish the existence and location of the cation-binding sites that confer salt dependence to the assembly and mechanics of actin filaments. PMID:23027950

  20. 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.

  1. Vehicle effects in ophthalmic bioavailability: an evaluation of polymeric inserts containing pilocarpine.

    PubMed

    Saettone, M F; Giannaccini, B; Chetoni, P; Galli, G; Chiellini, E

    1984-04-01

    A series of polymeric ophthalmic inserts containing pilocarpine were formulated with four different types of polyvinyl alcohol, PVA, and two types of hydroxypropylcellulose. Pilocarpine was present as the nitrate, or as the salt with polyacrylic acid, PAA. In-vivo miosis vs time experiments on albino rabbits, showed that all inserts increased significantly the bioavailability of pilocarpine, with respect to a standard solution of pilocarpine nitrate. Two PVA inserts, containing the PAA-salt of pilocarpine, were particularly effective. The preparations were also submitted to in-vitro release tests and to differential scanning calorimetry, to ascertain the release mechanism, and to verify, via the thermal behaviour, possible interactions between drug and polymers. The chemical and physiochemical factors, most likely to influence the ophthalmic bioavailability of pilocarpine from the present preparations, are briefly reviewed.

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

    NASA Astrophysics Data System (ADS)

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

    2018-02-01

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

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

    PubMed

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

    2018-02-15

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

  4. A facile molten-salt route to graphene synthesis.

    PubMed

    Liu, Xiaofeng; Giordano, Cristina; Antonietti, Markus

    2014-01-15

    Efficient synthetic routes are continuously pursued for graphene in order to implement its applications in different areas. However, direct conversion of simple monomers to graphene through polymerization in a scalable manner remains a major challenge for chemists. Herein, a molten-salt (MS) route for the synthesis of carbon nanostructures and graphene by controlled carbonization of glucose in molten metal chloride is reported. In this process, carbohydrate undergoes polymerization in the presence of strongly interacting ionic species, which leads to nanoporous carbon with amorphous nature and adjustable pore size. At a low precursor concentration, the process converts the sugar molecules (glucose) to rather pure few-layer graphenes. The MS-derived graphenes are strongly hydrophobic and exhibit remarkable selectivity and capacity for absorption of organics. The methodology described may open up a new avenue towards the synthesis and manipulation of carbon materials in liquid media. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Radical-Mediated Enzymatic Polymerizations

    PubMed Central

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

    2016-01-01

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

  6. Role of salt concentration in blend polymer for energy storage conversion devices

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

    Arya, Anil; Sharma, A. L., E-mail: alsharmaiitkgp@gmail.com; Sadiq, M.

    2016-05-06

    Solid Polymer Electrolytes (SPE) are materials of considerable interest worldwide, which serves dual purpose of electrolyte and separator between electrode compartments in renewable energy conversion/storage devices such as; high energy density batteries, electrochromic display devices, and supercapacitors. Polymer blend electrolytes are prepared for various concentration of salt (Ö/Li) with the constant ratio (0.5 gm) of each PEO and PAN polymers (blend polymer) using solution casting technique. Solid polymeric ionic conductor as a separator is the ultimate substitute to eliminate the drawback related to liquid and gel polymer ionic conductors. In the present work, solid polymer electrolyte film consisting of PEO,more » PAN and LiPF{sub 6} are examined for various concentration of lithium salt by keeping PEO/PAN blend ratio as a constant with a view to optimize the dominant salt concentration which could give the maximum conductivity at ambient temperature.« less

  7. Photo-responsive polymeric micelles.

    PubMed

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

    2014-09-07

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

  8. Photoluminescent silicon nanocrystals with chlorosilane surfaces - synthesis and reactivity

    NASA Astrophysics Data System (ADS)

    Höhlein, Ignaz M. D.; Kehrle, Julian; Purkait, Tapas K.; Veinot, Jonathan G. C.; Rieger, Bernhard

    2014-12-01

    We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place.We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place. Electronic supplementary information (ESI) available: Detailed experimental procedures and additional NMR, PL, EDX, DLS and TEM data. See DOI: 10.1039/C4NR05888G

  9. Self-Assembled Polystyrene Beads for Templated Covalent Functionalization of Graphitic Substrates Using Diazonium Chemistry.

    PubMed

    Van Gorp, Hans; Walke, Peter; Bragança, Ana M; Greenwood, John; Ivasenko, Oleksandr; Hirsch, Brandon E; De Feyter, Steven

    2018-04-11

    A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials.

  10. Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

    NASA Astrophysics Data System (ADS)

    Cui, Xin; Qi, Cong; Li, Liang; Li, Yimin; Li, Song

    2017-08-01

    In order to facilitate efficient and clean utilization of coal, a series of Ni-Co ternary molten salt crystals are explored and the catalytic pyrolysis mechanism of Datong coal is investigated. The reaction mechanisms of coal are achieved by thermal gravimetric analyzer (TGA), and a reactive kinetic model is constructed. The microcosmic structure and macerals are observed by scanning electron microscope (SEM). The catalytic effects of ternary molten salt crystals at different stages of pyrolysis are analyzed. The experimental results show that Ni-Co ternary molten salt catalysts have the capability to bring down activation energy required by pyrolytic reactions at its initial phase. Also, the catalysts exert a preferable catalytic action on macromolecular structure decomposition and free radical polycondensation reactions. Furthermore, the high-temperature condensation polymerization is driven to decompose further with a faster reaction rate by the additions of Ni-Co ternary molten salt crystal catalysts. According to pyrolysis kinetic research, the addition of catalysts can effectively decrease the activation energy needed in each phase of pyrolysis reaction.

  11. On the applicability of a hybrid bioreactor operated with polymeric tubing for the biological treatment of saline wastewater.

    PubMed

    Tomei, M Concetta; Mosca Angelucci, Domenica; Stazi, Valentina; Daugulis, Andrew J

    2017-12-01

    Effective biological treatment of high salt content wastewater requires consideration of both salt and organic toxicity. This study treated a synthetic saline wastewater containing NaCl (100gL -1 ) and 2,4-dimethylphenol (1.2gL -1 ) with a hybrid system consisting of a biological reactor containing spiral-coiled polymeric tubing through which the mixed feed was pumped. The tubing wall was permeable to the organic contaminant, but not to the salt, which allowed transfer of the organic into the cell-containing bioreactor contents for degradation, while not exposing the cells to high salt concentrations. Different grades of DuPont Hytrel polymer were examined on the basis of organic affinity predictions and experimental partition and mass transfer tests. Hytrel G3548 tubing showed the highest permeability for 2,4-dimethylphenol while exerting an effective salt barrier, and was used to verify the feasibility of the proposed system. Very high organic removal (99% after just 5h of treatment) and effective biodegradation of the organic fraction of the wastewater (>90% at the end of the test) were observed. Complete salt separation from the microbial culture was also achieved. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Bile salt incorporated polypyrrole thin film for ethanol sensing.

    PubMed

    Sharma, Partha P D; Sarkar, D

    2015-04-01

    Polypyrrole (PPy)-bile salt composite was used for sensing ethanol vapor. PPy was synthesized by interface polymerization for subsequent fabrication of thin film of its composite with bile salt, by in-situ co-dispersion method and then exposed to ethanol vapour. Sensing was visualized through changes in morphological, structural and optical characterizations. The ethanol exposed film showed larger agglomeration as revealed in its surface morphology on scanning electron microscope (SEM) and greater crystallinity as seen through X-Ray diffraction (XRD). Fourier transform infra red (FTIR) and nuclear magnetic resonance spectroscopy (NMR) of the ethanol incorporated film also gave signature of the presence of bile salt and alcohol. Alcohol incorporation pattern resulted in increase in electrical conductance from 7.08539 x 10(-5) mA/V to 8.0356 x 10(-5) mA/V, as determined from current voltage characterizations. Average molecular weight (M(n)) obtained from gel permeation chromatography changed from 6160 to 10300 on ethanol intake. Photoluminescence (PL) intensity was quenched and the PL peak shifted from 430 to 409 on ethanol exposure. Changes in morphological, structural, optical and electrical properties of the composite on ethanol exposure showed its prospective application for sensing ethanol.

  13. Cell membrane-inspired polymeric micelles as carriers for drug delivery.

    PubMed

    Liu, Gongyan; Luo, Quanqing; Gao, Haiqi; Chen, Yuan; Wei, Xing; Dai, Hong; Zhang, Zongcai; Ji, Jian

    2015-03-01

    In cancer therapy, surface engineering of drug delivery systems plays an essential role in their colloidal stability, biocompatibility and prolonged blood circulation. Inspired by the cell membrane consisting of phospholipids and glycolipids, a zwitterionic phosphorylcholine functionalized chitosan oligosaccharide (PC-CSO) was first synthesized to mimic the hydrophilic head groups of those amphipathic lipids. Then hydrophobic stearic acid (SA) similar to lipid fatty acids was grafted onto PC-CSO to form amphiphilic PC-CSO-SA copolymers. Cell membrane-mimetic micelles with a zwitterionic surface and a hydrophobic SA core were prepared by the self-assembly of PC-CSO-SA copolymers, showing excellent stability under extreme conditions including protein containing media, high salt content or a wide pH range. Doxorubicin (DOX) was successfully entrapped into polymeric micelles through the hydrophobic interaction between DOX and SA segments. After fast internalization by cancer cells, sustained drug release from micelles to the cytoplasm and nucleus was achieved. This result suggests that these biomimetic polymeric micelles may be promising drug delivery systems in cancer therapy.

  14. Polymeric microspheres

    DOEpatents

    Walt, David R.; Mandal, Tarun K.; Fleming, Michael S.

    2004-04-13

    The invention features core-shell microsphere compositions, hollow polymeric microspheres, and methods for making the microspheres. The microspheres are characterized as having a polymeric shell with consistent shell thickness.

  15. Cellobiose Dehydrogenase Aryl Diazonium Modified Single Walled Carbon Nanotubes: Enhanced Direct Electron Transfer through a Positively Charged Surface

    PubMed Central

    2011-01-01

    One of the challenges in the field of biosensors and biofuel cells is to establish a highly efficient electron transfer rate between the active site of redox enzymes and electrodes to fully access the catalytic potential of the biocatalyst and achieve high current densities. We report on very efficient direct electron transfer (DET) between cellobiose dehydrogenase (CDH) from Phanerochaete sordida (PsCDH) and surface modified single walled carbon nanotubes (SWCNT). Sonicated SWCNTs were adsorbed on the top of glassy carbon electrodes and modified with aryl diazonium salts generated in situ from p-aminobenzoic acid and p-phenylenediamine, thus featuring at acidic pH (3.5 and 4.5) negative or positive surface charges. After adsorption of PsCDH, both electrode types showed excellent long-term stability and very efficient DET. The modified electrode presenting p-aminophenyl groups produced a DET current density of 500 μA cm−2 at 200 mV vs normal hydrogen reference electrode (NHE) in a 5 mM lactose solution buffered at pH 3.5. This is the highest reported DET value so far using a CDH modified electrode and comes close to electrodes using mediated electron transfer. Moreover, the onset of the electrocatalytic current for lactose oxidation started at 70 mV vs NHE, a potential which is 50 mV lower compared to when unmodified SWCNTs were used. This effect potentially reduces the interference by oxidizable matrix components in biosensors and increases the open circuit potential in biofuel cells. The stability of the electrode was greatly increased compared with unmodified but cross-linked SWCNTs electrodes and lost only 15% of the initial current after 50 h of constant potential scanning. PMID:21417322

  16. Cellobiose dehydrogenase aryl diazonium modified single walled carbon nanotubes: enhanced direct electron transfer through a positively charged surface.

    PubMed

    Tasca, Federico; Harreither, Wolfgang; Ludwig, Roland; Gooding, John Justin; Gorton, Lo

    2011-04-15

    One of the challenges in the field of biosensors and biofuel cells is to establish a highly efficient electron transfer rate between the active site of redox enzymes and electrodes to fully access the catalytic potential of the biocatalyst and achieve high current densities. We report on very efficient direct electron transfer (DET) between cellobiose dehydrogenase (CDH) from Phanerochaete sordida (PsCDH) and surface modified single walled carbon nanotubes (SWCNT). Sonicated SWCNTs were adsorbed on the top of glassy carbon electrodes and modified with aryl diazonium salts generated in situ from p-aminobenzoic acid and p-phenylenediamine, thus featuring at acidic pH (3.5 and 4.5) negative or positive surface charges. After adsorption of PsCDH, both electrode types showed excellent long-term stability and very efficient DET. The modified electrode presenting p-aminophenyl groups produced a DET current density of 500 μA cm(-2) at 200 mV vs normal hydrogen reference electrode (NHE) in a 5 mM lactose solution buffered at pH 3.5. This is the highest reported DET value so far using a CDH modified electrode and comes close to electrodes using mediated electron transfer. Moreover, the onset of the electrocatalytic current for lactose oxidation started at 70 mV vs NHE, a potential which is 50 mV lower compared to when unmodified SWCNTs were used. This effect potentially reduces the interference by oxidizable matrix components in biosensors and increases the open circuit potential in biofuel cells. The stability of the electrode was greatly increased compared with unmodified but cross-linked SWCNTs electrodes and lost only 15% of the initial current after 50 h of constant potential scanning. © 2011 American Chemical Society

  17. Covalent modification of reduced graphene oxide by means of diazonium chemistry and use as a drug-delivery system.

    PubMed

    Wei, Guangcheng; Yan, Miaomiao; Dong, Renhao; Wang, Dong; Zhou, Xiangzhu; Chen, Jingfei; Hao, Jingcheng

    2012-11-12

    Under acidic conditions, reduced graphene oxide (rGO) was functionalized with p-aminobenzoic acid, which formed the diazonium ions through the diazotization with a wet-chemical method. Surfactants or stabilizers were not applied during the diazotization. After the functionalized rGO was treated through mild sonication in aqueous solution, these functionalized rGO sheets were less than two layers, which was determined by atomic force microscopy (AFM) imaging. The water solubility of functionalized rGO after the introduction of polyethyleneimine (PEI) was improved significantly; it was followed by covalent binding of folic acid (FA) molecules to the functionalized rGO to allow us to specifically target CBRH7919 cancer cells by using FA as a receptor. The loading and release behaviors of elsinochrome A (EA) and doxorubicin (DOX) on the functionalized rGO sheets were investigated. The EA loading ratio onto rGO-C(6)H(4)-CO-NH-PEI-NH-CO-FA (abbreviated rGO-PEI-FA, the weight ratio of drug loaded onto rGO-PEI-FA) was approximately 45.56 %, and that of DOX was approximately 28.62 %. It was interesting that the drug release from rGO-PEI-FA was pH- and salt-dependent. The results of cytotoxicity (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and flow cytometry (FCM) assays, as well as cell morphology observations) clearly showed that the concentration of rGO-PEI-FA as the drug-delivery composite should be less than 12.5 mg L(-1). The conjugation of DOX and rGO-PEI-FA can enhance the cancer-cell apoptosis effectively and can also push the cancer cells to the vulnerable G2 phase of the cell cycle, which is most sensitive and susceptible to damage by drugs or radiation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. The Synthesis of Methyl Salicylate: Amine Diazotization.

    ERIC Educational Resources Information Center

    Zanger, Murray; McKee, James R.

    1988-01-01

    Notes that this experiment takes safety and noncarcinogenic reactants into account. Demonstrates the use of diazonium salts for the replacement of an aromatic amine group by a phenolic hydroxyl. Involves two pleasant-smelling organic compounds, methyl anthranilate (grape) and methyl salicylate (oil of wintergreen). (MVL)

  19. Integration of CuAAC Polymerization and Controlled Radical Polymerization into Electron Transfer Mediated "Click-Radical" Concurrent Polymerization.

    PubMed

    Xue, Wentao; Wang, Jie; Wen, Ming; Chen, Gaojian; Zhang, Weidong

    2017-03-01

    The successful chain-growth copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization employing Cu(0)/pentamethyldiethylenetriamine (PMDETA) and alkyl halide as catalyst is first investigated by a combination of nuclear magnetic resonance, gel-permeation chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In addition, the electron transfer mediated "click-radical" concurrent polymerization utilizing Cu(0)/PMDETA as catalyst is successfully employed to generate well-defined copolymers, where controlled CuAAC polymerization of clickable ester monomer is progressed in the main chain acting as the polymer backbone, the controlled radical polymerization (CRP) of acrylic monomer is carried out in the side chain. Furthermore, it is found that there is strong collaborative effect and compatibility between CRP and CuAAC polymerization to improve the controllability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Polymerization Reactor Engineering.

    ERIC Educational Resources Information Center

    Skaates, J. Michael

    1987-01-01

    Describes a polymerization reactor engineering course offered at Michigan Technological University which focuses on the design and operation of industrial polymerization reactors to achieve a desired degree of polymerization and molecular weight distribution. Provides a list of the course topics and assigned readings. (TW)

  1. Covalent modification of graphene and graphite using diazonium chemistry: tunable grafting and nanomanipulation.

    PubMed

    Greenwood, John; Phan, Thanh Hai; Fujita, Yasuhiko; Li, Zhi; Ivasenko, Oleksandr; Vanderlinden, Willem; Van Gorp, Hans; Frederickx, Wout; Lu, Gang; Tahara, Kazukuni; Tobe, Yoshito; Uji-I, Hiroshi; Mertens, Stijn F L; De Feyter, Steven

    2015-05-26

    We shine light on the covalent modification of graphite and graphene substrates using diazonium chemistry under ambient conditions. We report on the nature of the chemical modification of these graphitic substrates, the relation between molecular structure and film morphology, and the impact of the covalent modification on the properties of the substrates, as revealed by local microscopy and spectroscopy techniques and electrochemistry. By careful selection of the reagents and optimizing reaction conditions, a high density of covalently grafted molecules is obtained, a result that is demonstrated in an unprecedented way by scanning tunneling microscopy (STM) under ambient conditions. With nanomanipulation, i.e., nanoshaving using STM, surface structuring and functionalization at the nanoscale is achieved. This manipulation leads to the removal of the covalently anchored molecules, regenerating pristine sp(2) hybridized graphene or graphite patches, as proven by space-resolved Raman microscopy and molecular self-assembly studies.

  2. Molten salt-supported polycondensation of optically active diacid monomers with an aromatic thiazole-bearing diamine using microwave irradiation.

    PubMed

    Mallakpour, Shadpour; Zadehnazari, Amin

    2014-05-01

    Microwave heating was used to prepare optically active thiazole-bearing poly(amide-imide)s. Polymerization reactions were carried out in the molten tetrabutylammonium bromide as a green molten salt medium and triphenyl phosphite as the homogenizer. Structural elucidation of the compounds was performed by Fourier transform infrared and NMR spectroscopic data and elemental analysis results. The polymeric samples were readily soluble in various organic solvents, forming low-colored and flexible thin films via solution casting. They showed high thermal stability with decomposition temperature being above 360 °C. They were assembled randomly in a nanoscale size.

  3. Molten salt-supported polycondensation of optically active diacid monomers with an aromatic thiazole-bearing diamine using microwave irradiation

    PubMed Central

    Mallakpour, Shadpour; Zadehnazari, Amin

    2013-01-01

    Microwave heating was used to prepare optically active thiazole-bearing poly(amide-imide)s. Polymerization reactions were carried out in the molten tetrabutylammonium bromide as a green molten salt medium and triphenyl phosphite as the homogenizer. Structural elucidation of the compounds was performed by Fourier transform infrared and NMR spectroscopic data and elemental analysis results. The polymeric samples were readily soluble in various organic solvents, forming low-colored and flexible thin films via solution casting. They showed high thermal stability with decomposition temperature being above 360 °C. They were assembled randomly in a nanoscale size. PMID:25685498

  4. Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography

    NASA Astrophysics Data System (ADS)

    Wang, Qing Hua; Jin, Zhong; Kim, Ki Kang; Hilmer, Andrew J.; Paulus, Geraldine L. C.; Shih, Chih-Jen; Ham, Moon-Ho; Sanchez-Yamagishi, Javier D.; Watanabe, Kenji; Taniguchi, Takashi; Kong, Jing; Jarillo-Herrero, Pablo; Strano, Michael S.

    2012-09-01

    Graphene has exceptional electronic, optical, mechanical and thermal properties, which provide it with great potential for use in electronic, optoelectronic and sensing applications. The chemical functionalization of graphene has been investigated with a view to controlling its electronic properties and interactions with other materials. Covalent modification of graphene by organic diazonium salts has been used to achieve these goals, but because graphene comprises only a single atomic layer, it is strongly influenced by the underlying substrate. Here, we show a stark difference in the rate of electron-transfer reactions with organic diazonium salts for monolayer graphene supported on a variety of substrates. Reactions proceed rapidly for graphene supported on SiO2 and Al2O3 (sapphire), but negligibly on alkyl-terminated and hexagonal boron nitride (hBN) surfaces, as shown by Raman spectroscopy. We also develop a model of reactivity based on substrate-induced electron-hole puddles in graphene, and achieve spatial patterning of chemical reactions in graphene by patterning the substrate.

  5. Chlorhexidine salt-loaded polyurethane orthodontic chains: in vitro release and antibacterial activity studies.

    PubMed

    Padois, Karine; Bertholle, Valérie; Pirot, Fabrice; Hyunh, Truc Thanh Ngoc; Rossi, Alessandra; Colombo, Paolo; Falson, Françoise; Sonvico, Fabio

    2012-12-01

    The widespread use of indwelling medical devices has enormously increased the interest in materials incorporating antibiotics and antimicrobial agents as a means to prevent dangerous device-related infections. Recently, chlorhexidine-loaded polyurethane has been proposed as a material suitable for the production of devices which are able to resist microbial contamination. The aim of the present study was to characterize the in vitro release of chlorhexidine from new polymeric orthodontic chains realized with polyurethane loaded with two different chlorhexidine salts: chlorhexidine diacetate or chlorhexidine digluconate. The orthodontic chains constituted of three layers: a middle polyurethane layer loaded with chlorhexidine salt inserted between two layers of unloaded polymer. In vitro release of chlorhexidine diacetate and digluconate from orthodontic chains loaded with 10% or 20% (w/w) chlorhexidine salt was sustained for 42 days and followed Fickian diffusion. The drug diffusion through the polyurethane was found to be dependent not only on chlorhexidine loading, but also on the type of chlorhexidine salt. The antibacterial activity of 0.2% (w/w) chlorhexidine diacetate-loaded orthodontic chain was successfully tested towards clinically isolated biofilm forming ica-positive Staphylococcus epidermidis via agar diffusion test. In conclusion, the chlorhexidine salt-loaded chains could provide an innovative approach in the prevention of oral infections related to the use of orthodontic devices.

  6. Ion beam promoted lithium absorption in glassy polymeric carbon

    NASA Astrophysics Data System (ADS)

    Ila, D.; Zimmerman, R. L.; Jenkins, G. M.; Maleki, H.; Poker, D. B.

    1995-12-01

    Glassy Polymeric Carbon (GPC) samples prepared from a precursor possess accessible pore volume that depends on the heat treatment temperature. We have shown that lithium percolates without diffusion into the accessible pores of GPC samples immersed in a molten lithium salt bath at 700°C. Ion bombardment with 10 MeV Au atoms increases the total pore volume available for lithium occupation even for samples normally impermeable to lithium. The lithium concentration depth profile is measured using Li7(p,2α) nuclear reaction analysis. We will report on lithium percolation into GPC prepared at temperatures between 500°C and 1000°C and activated by a 10 MeV gold ion bombardment.

  7. Polymeric micellar pH-sensitive drug delivery system for doxorubicin.

    PubMed

    Hrubý, Martin; Konák, Cestmír; Ulbrich, Karel

    2005-03-02

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

  8. Effect of leaching residual methyl methacrylate concentrations on in vitro cytotoxicity of heat polymerized denture base acrylic resin processed with different polymerization cycles

    PubMed Central

    BURAL, Canan; AKTAŞ, Esin; DENIZ, Günnur; ÜNLÜÇERÇI, Yeşim; BAYRAKTAR, Gülsen

    2011-01-01

    Objectives Residual methyl methacrylate (MMA) may leach from the acrylic resin denture bases and have adverse effects on the oral mucosa. This in vitro study evaluated and correlated the effect of the leaching residual MMA concentrations ([MMA]r) on in vitro cytotoxicity of L-929 fibroblasts. Material and Methods A total of 144 heat-polymerized acrylic resin specimens were fabricated using 4 different polymerization cycles: (1) at 74ºC for 9 h, (2) at 74ºC for 9 h and terminal boiling (at 100ºC) for 30 min, (3) at 74ºC for 9 h and terminal boiling for 3 h, (4) at 74ºC for 30 min and terminal boiling for 30 min. Specimens were eluted in a complete cell culture medium at 37ºC for 1, 2, 5 and 7 days. [MMA]r in eluates was measured using high-performance liquid chromatography. In vitro cytotoxicity of eluates on L-929 fibroblasts was evaluated by means of cell proliferation using a tetrazolium salt XTT (sodium 3´-[1-phenyl-aminocarbonyl)-3,4-tetrazolium]bis(4-methoxy-6-nitro)benzenesulphonic acid) assay. Differences in [MMA]r of eluates and cell proliferation values between polymerization cycles were statistically analyzed by Kruskal-Wallis, Friedman and Dunn's multiple comparison tests. The correlation between [MMA]r of eluates and cell proliferation was analyzed by Pearson's correlation test (p<0.05). Results [MMA]r was significantly (p≤0.001) higher in eluates of specimens polymerized with cycle without terminal boiling after elution of 1 and 2 days. Cell proliferation values for all cycles were significantly (p<0.01) lower in eluates of 1 day than those of 2 days. The correlation between [MMA]r and cell proliferation values was negative after all elution periods, showing significance (p<0.05) for elution of 1 and 2 days. MMA continued to leach from acrylic resin throughout 7 days and leaching concentrations markedly reduced after elution of 1 and 2 days. Conclusion Due to reduction of leaching residual MMA concentrations, use of terminal boiling in the

  9. Lignin nanoparticle synthesis

    DOEpatents

    Dirk, Shawn M.; Cicotte, Kirsten Nicole; Wheeler, David R.; Benko, David A.

    2015-08-11

    A method including reducing a particle size of lignin particles to an average particle size less than 40 nanometers; after reducing the particle size, combining the lignin particles with a polymeric material; and forming a structure of the combination. A method including exposing lignin to a diazonium precursor including a functional group; modifying the lignin by introducing the functional group to the lignin; and combining the modified lignin with a polymeric material to form a composite. An apparatus including a composite of a polymer and lignin wherein the lignin has an average particle size less than 100 micrometers.

  10. Waste Isolation Pilot Plant Salt Decontamination Testing

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

    Rick Demmer; Stephen Reese

    2014-09-01

    On February 14, 2014, americium and plutonium contamination was released in the Waste Isolation Pilot Plant (WIPP) salt caverns. At the request of WIPP’s operations contractor, Idaho National Laboratory (INL) personnel developed several methods of decontaminating WIPP salt, using surrogate contaminants and also americium (241Am). The effectiveness of the methods is evaluated qualitatively, and to the extent possible, quantitatively. One of the requirements of this effort was delivering initial results and recommendations within a few weeks. That requirement, in combination with the limited scope of the project, made in-depth analysis impractical in some instances. Of the methods tested (dry brushing,more » vacuum cleaning, water washing, strippable coatings, and mechanical grinding), the most practical seems to be water washing. Effectiveness is very high, and it is very easy and rapid to deploy. The amount of wastewater produced (2 L/m2) would be substantial and may not be easy to manage, but the method is the clear winner from a usability perspective. Removable surface contamination levels (smear results) from the strippable coating and water washing coupons found no residual removable contamination. Thus, whatever is left is likely adhered to (or trapped within) the salt. The other option that shows promise is the use of a fixative barrier. Bartlett Nuclear, Inc.’s Polymeric Barrier System (PBS) proved the most durable of the coatings tested. The coatings were not tested for contaminant entrapment, only for coating integrity and durability.« less

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

    PubMed

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

    2016-01-21

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

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

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

    Kaetsu, I.; Ito, A.; Hayashi, K.

    1973-06-01

    The effect of homogeneity of polymerization phase and monomer concentration on the temperature dependence of initial polymerization rate was studied in the radiation-induced radical polymerization of binary systems consisting of glass-forming monomer and solvent. In the polymerization of a completely homogeneous system such as HEMA-propylene glycol, a maximum and a minimum in polymerization rates as a function of temperature, characteristic of the polymerization in glass-forming systems, were observed for all monomer concentrations. However, in the heterogeneous polymerization systems such as HEMA-triacetin and HEMAisoamyl acetate, maximum and minimum rates were observed in monomer-rich compositions but not at low monomer concentrations. Furthermore,more » in the HEMA-dioctyl phthalate polymerization system, which is extremely heterogeneous, no maximum and minimum rates were observed at any monomer concentration. The effect of conversion on the temperature dependence of polymerization rate in homogeneous bulk polymerization of HEMA and GMA was investigated. Maximum and minimum rates were observed clearly in conversions less than 10% in the case of HEMA and less than 50% in the case of GMA, but the maximum and minimum changed to a mere inflection in the curve at higher conversions. A similar effect of polymer concentration on the temperature dependence of polymerization rate in the GMA-poly(methyl methacrylate) system was also observed. It is deduced that the change in temperature dependence of polymerization rate is attributed to the decrease in contribution of mutual termination reaction of growing chain radicals to the polymerization rate. (auth)« less

  13. Dynamics and Regulation of RecA Polymerization and De-Polymerization on Double-Stranded DNA

    PubMed Central

    Muniyappa, Kalappa; Yan, Jie

    2013-01-01

    The RecA filament formed on double-stranded (ds) DNA is proposed to be a functional state analogous to that generated during the process of DNA strand exchange. RecA polymerization and de-polymerization on dsDNA is governed by multiple physiological factors. However, a comprehensive understanding of how these factors regulate the processes of polymerization and de-polymerization of RecA filament on dsDNA is still evolving. Here, we investigate the effects of temperature, pH, tensile force, and DNA ends (in particular ssDNA overhang) on the polymerization and de-polymerization dynamics of the E. coli RecA filament at a single-molecule level. Our results identified the optimal conditions that permitted spontaneous RecA nucleation and polymerization, as well as conditions that could maintain the stability of a preformed RecA filament. Further examination at a nano-meter spatial resolution, by stretching short DNA constructs, revealed a striking dynamic RecA polymerization and de-polymerization induced saw-tooth pattern in DNA extension fluctuation. In addition, we show that RecA does not polymerize on S-DNA, a recently identified novel base-paired elongated DNA structure that was previously proposed to be a possible binding substrate for RecA. Overall, our studies have helped to resolve several previous single-molecule studies that reported contradictory and inconsistent results on RecA nucleation, polymerization and stability. Furthermore, our findings also provide insights into the regulatory mechanisms of RecA filament formation and stability in vivo. PMID:23825559

  14. Salt

    USGS Publications Warehouse

    Franson, J.C.; Friend, M.

    1999-01-01

    Animals become victims of salt poisoning or toxicosis when toxic levels of sodium and chloride accumulate in the blood after they ingest large amounts of salt or, in some species, are deprived of water. For birds, salt sources may include saline water and road salt.Normally, the salt glands of birds (Fig. 47.1) excrete sodium and chloride to maintain the proper physiologic chemical balance. However, when there has been insufficient time for acclimation of the salt gland to the saline environment, or when salt gland function is compromised by exposure to certain pesticides or oil, the electrolyte balance of the blood may be upset by the excess sodium and chloride, resulting in toxicosis. Salt accumulation on the outside of the body, or salt encrustation, is a greater problem for waterbirds that use very saline waters than is salt toxicosis. Salt encrustation can lead to exertion, acute muscle degeneration, and eventual drowning during the struggle to escape entrapment.

  15. Polymerization of perfluorobutadiene

    NASA Technical Reports Server (NTRS)

    Newman, J.; Toy, M. S.

    1970-01-01

    Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield.

  16. 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.

  17. Synthesis and application of a triazene-ferrocene modifier for immobilization and characterization of oligonucleotides at electrodes.

    PubMed

    Hansen, Majken N; Farjami, Elaheh; Kristiansen, Martin; Clima, Lilia; Pedersen, Steen Uttrup; Daasbjerg, Kim; Ferapontova, Elena E; Gothelf, Kurt V

    2010-04-16

    A new DNA modifier containing triazene, ferrocene, and activated ester functionalities was synthesized and applied for electrochemical grafting and characterization of DNA at glassy carbon (GC) and gold electrodes. The modifier was synthesized from ferrocenecarboxylic acid by attaching a phenyltriazene derivative to one of the ferrocene Cp rings, while the other Cp ring containing the carboxylic acid was converted to an activated ester. The modifier was conjugated to an amine-modified DNA sequence. For immobilization of the conjugate at Au or GC electrodes, the triazene was activated by dimethyl sulfate for release of the diazonium salt. The salt was reductively converted to the aryl radical which was readily immobilized at the surface. DNA grafted onto electrodes exhibited remarkable hybridization properties, as detected through a reversible shift in the redox potential of the Fc redox label upon repeated hybridization/denaturation procedures with a complementary target DNA sequence. By using a methylene blue (MB) labeled target DNA sequence the hybridization could also be followed through the MB redox potential. Electrochemical studies demonstrated that grafting through the triazene modifier can successfully compete with existing protocols for DNA immobilization through the commonly used alkanethiol linkers and diazonium salts. Furthermore, the triazene modifier provides a practical one-step immobilization procedure.

  18. Photoinitiated polymerization of 1-vinylimidazole

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

    Joshi, M.G.; Rodriguez, F.

    1984-04-01

    The photoinitiated polymerization of 1-vinylimidazole (VI) does not follow the classical kinetic scheme for free radical polymerization. Kinetic results for VI suggest a degradative addition reaction between the macroradical and the monomer to produce a relatively stable, unreactive radical, which does not reinitiate polymerization, is low, 1.5 kcal/mol. Among the 3 photoinitiators used, the highest quantum efficiency was demonstrated by 2,2'-diethoxyacetophenone followed by bezoin methyl ether and benzoin isopropyl ether. Under the experimental conditions used, the polymerization of VI does not proceed to complete conversion, and the phenomenon of dead-end polymerization is observed.

  19. Tris(trimethylsilyl)silane as a co-initiator for dental adhesive: Photo-polymerization kinetics and dynamic mechanical property

    PubMed Central

    Song, Linyong; Ye, Qiang; Ge, Xueping; Misra, Anil; Spencer, Paulette

    2017-01-01

    Objectives The purpose of this study was to evaluate the polymerization behavior of a model dentin adhesive with tris(trimethylsilyl)silane (TTMSS) as a co-initiator, and to investigate the polymerization kinetics and mechanical properties of copolymers in dry and wet conditions. Methods A co-monomer mixture based on HEMA/BisGMA (45/55, w/w) was used as a model dentin adhesive. The photoinitiator system included camphorquinone (CQ) as the photosensitizer and the co-initiator was ethyl-4-(dimethylamino) benzoate (EDMAB) or TTMSS. Iodonium salt, diphenyliodonium hexafluorophosphate (DPIHP) serving as a catalyst, was selectively added into the adhesive formulations. The control and the experimental formulations were characterized with regard to the degree of conversion (DC) and dynamic mechanical properties under dry and wet conditions. Results In two-component photoinitiator system (CQ/TTMSS), with an increase of TTMSS concentration, the polymerization rate and DC of C═C double bond increased, and showed a dependence on the irradiation time and curing light intensity. The copolymers that contained the three-component photoinitiator system (CQ/TTMSS/DPIHP) showed similar dynamic mechanical properties, under both dry and wet conditions, to the EDMAB-containing system. Significance The DC of formulations using TTMSS as co-initiator showed a strong dependence on irradiation time. With the addition of TTMSS, the maximum polymerization rate can be adjusted and the network structure became more homogenous. The results indicated that the TTMSS could be used as a substitute for amine-type co-initiator in visible-light induced free radical polymerization of methacrylate-based dentin adhesives. PMID:26616688

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

    PubMed

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

    2014-10-01

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

  1. Effect of soil salinity on fructan content and polymerization degree in the sprouting tubers of Jerusalem artichoke (Helianthus tuberosus L.).

    PubMed

    Luo, Rui; Song, Xiaoyang; Li, Ziwei; Zhang, Aiqin; Yan, Xiufeng; Pang, Qiuying

    2018-04-01

    In addition to their role as reserve carbohydrates, fructans have been recognized as compounds that are protective against adverse environments. The aim of this study was to identify changes in the content and the degree of polymerization (DP) of fructan in sprouting tubers of Jerusalem artichoke under salt stress. Fructan was extracted from tubers at 1, 3, 5, and 7 days after planting in sandy loam soil irrigated with NaCl solution. Fructan accumulation and polymerization and the expression of genes encoding enzymes for fructan synthesis and degradation were evaluated. No significant differences between the control and treatment groups were observed until 5 days after sowing. The highest level of salinity (250 mM) not only inhibited sprouting and root growth but also decreased the level of fructan in the tubers. The proportion of fructan at DP 2-5 rapidly increased one day after sowing and then decreased over time. Under various NaCl treatments, at 7 days after sowing, all fructans except fructan at DP 6-10 were present in proportions less than or equal to the control. The variation in the DP of fructan was related to the transcription level of fructan metabolism genes. Fructan may support sprouting or resistance to salt stress by changing the DP of fructan molecules through hydrolysis without changing the total amount of fructan. The low-molecular-weight oligosaccharides (DP < 5) may be the major carbohydrates that support tuber sprouting or that are involved in protection from salt stress. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  2. Hydrophobicity and leakage current statistics of polymeric insulators long-term exposed to coastal contamination

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

    Soerqvist, T.; Vlastos, A.E.

    1996-12-31

    The hydrophobicity of polymeric insulators is crucial for their performance. This paper reports the hydrophobicity and the peak leakage current statistics of one porcelain, two ethylene-propylene-diene monomer (EPDM) and four silicone rubber (SIR) commercially available insulators. The insulators have been energized with 130 kV rms phase-to-ground AC voltage under identical outdoor conditions for more than seven years. The results presented show that under wet and polluted conditions the hydrophilic EPDM rubber insulators develop high leakage currents and substantial arcing. During a typical salt-storm the arcing amplitude of the EPDM rubber insulators is at least twice as high as that ofmore » the porcelain insulator. The SIR insulators, on the other hand, preserve a high degree of hydrophobicity after more than seven years in service and maintain very low leakage currents. However, the results show that during heavy salt contaminated conditions a highly stressed SIR insulator can temporarily lose its hydrophobicity and thereby develop considerable surface arcing.« less

  3. Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry.

    PubMed

    Seber, Gonca; Rudnev, Alexander V; Droghetti, Andrea; Rungger, Ivan; Veciana, Jaume; Mas-Torrent, Marta; Rovira, Concepció; Crivillers, Núria

    2017-01-26

    A novel, persistent, electrochemically active perchlorinated triphenylmethyl (PTM) radical with a diazonium functionality has been covalently attached to highly ordered pyrolytic graphite (HOPG) by electrografting in a single-step process. Electrochemical scanning tunneling microscopy (EC-STM) and Raman spectroscopy measurements revealed that PTM molecules had a higher tendency to covalently react at the HOPG step edges. The cross-section profiles from EC-STM images showed that there was current enhancement at the functionalized areas, which could be explained by redox-mediated electron tunneling through surface-confined redox-active molecules. Cyclic voltammetry clearly demonstrated that the intrinsic properties of the organic radical were preserved upon grafting and DFT calculations also revealed that the magnetic character of the PTM radical was preserved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Modification of Silk Fibroin Using Diazonium Coupling Chemistry and the Effects on hMSC Proliferation and Differentiation

    PubMed Central

    Murphy, Amanda R.; John, Peter St.; Kaplan, David L.

    2009-01-01

    A simple chemical modification method using diazonium coupling chemistry was developed to tailor the structure and hydrophilicity of silk fibroin protein. The extent of modification using several aniline derivatives was characterized using UV/vis and 1H NMR spectroscopy, and the resulting protein structure was analyzed with ATR-FTIR spectroscopy. Introduction of hydrophobic functional groups facilitated rapid conversion of the protein from a random coil to a β-sheet structure, while addition of hydrophilic groups inhibited this process. hMSCs were grown on these modified silks to assess the biocompatibility of these materials. The hydrophilicity of the silk derivatives was found to affect the growth rate and morphology, but hMSCs were able to attach, proliferate and differentiate into an osteogenic lineage on all of the silk derivatives. PMID:18417206

  5. Step-Growth Polymerization.

    ERIC Educational Resources Information Center

    Stille, J. K.

    1981-01-01

    Following a comparison of chain-growth and step-growth polymerization, focuses on the latter process by describing requirements for high molecular weight, step-growth polymerization kinetics, synthesis and molecular weight distribution of some linear step-growth polymers, and three-dimensional network step-growth polymers. (JN)

  6. Changes in chroma of two indirect composite materials polymerized with different polymerization systems.

    PubMed

    Ayano, Michiya

    2012-01-01

    This study evaluated chroma change in two composite materials (Sinfony and Pearleste) polymerized with two different systems. Disk specimens were prepared using a metal halide unit (Hyper LII) and an exposure time of 60 to 180 s. The proprietary polymerization systems (Visio and Pearlcure systems) were used as the reference polymerization modes. After storage at 37°C for 24 h, CIE 1976 L*a*b* values were measured by using a dental chroma meter (ShadeEye NCC) with a gray background. The specimens were then immersed in water or tea. Color change from baseline to 4 weeks was evaluated by measuring ΔL*, Δa*, and Δb*, after which ΔE*(ab) values were calculated. The brightness of Sinfony specimens was reduced by tea immersion. The color of both materials shifted to yellow after tea immersion, although color change in Sinfony specimens was greater than that in Pearleste specimens. For both materials, color change was less after polymerization with the metal halide unit. In conclusion, Sinfony polymerized with the Hyper LII unit, and Pearleste polymerized with either system, were stable against discoloration due to tea immersion.

  7. Making Polymeric Microspheres

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

    Combination of advanced techniques yields uniform particles for biomedical applications. Process combines ink-jet and irradiation/freeze-polymerization techniques to make polymeric microspheres of uniform size in diameters from 100 to 400 micrometer. Microspheres used in chromatography, cell sorting, cell labeling, and manufacture of pharmaceutical materials.

  8. The Comparative Nucleophilicity of Naphthoxide Derivatives in Reactions with a Fast-Red TR Dye: A Discovery-Oriented Capstone Project for the Second-Year Organic Laboratory

    ERIC Educational Resources Information Center

    Mascarenhas, Cheryl M.

    2008-01-01

    In this experiment, organic chemistry students perform reactions between three naphthyl acetate derivatives and the diazonium salt Fast-Red TR, under basic conditions. The three naphthyl acetate derivatives used in this study are 2-naphthyl acetate (1a), 6-bromo-2-naphthyl acetate (1b) and 1,6-dibromo-2-naphthyl acetate (1c). The two-step, one-pot…

  9. A new concept in polymeric thin-film composite nanofiltration membranes with antibacterial properties.

    PubMed

    Mollahosseini, Arash; Rahimpour, Ahmad

    2013-01-01

    A new, thin film, biofouling resistant, nanofiltration (NF) membrane was fabricated with two key characteristics, viz. a low rate of silver (Ag) release and long-lasting antibacterial properties. In the new approach, nanoparticles were embedded completely in a polymeric thin-film layer. A comparison was made between the new thin-film composite (TFC), NF membrane and thin-film nanocomposite (TFN), and antibacterial NF membranes. Both types of NF membrane were fabricated by interfacial polymerization on a polysulphone sublayer using m-phenylenediamine and trimesoyl chloride as an amine monomer and an acid chloride monomer, respectively. Energy dispersive X-ray (EDX) microanalysis demonstrated the presence of Ag nanoparticles. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to study the cross-sectional and surface morphological properties of the NF membranes. Permeability and salt rejection were tested using a dead-end filtration cell. Ag leaching from the membranes was measured using inductively coupled mass spectrometry (ICP-MS). Morphological studies showed that the TFC NF membranes had better thin-film formation (a more compact structure and a smoother surface) than TFN NF membranes. Performance experiments on TFC NF membranes revealed that permeability was good, without sacrificing salt rejection. The antibacterial properties of the fabricated membranes were tested using the disk diffusion method and viable plate counts. The antibiofouling properties of the membranes were examined by measuring the quantity of bacterial cells released from the biofilm formed (as a function of the amount of biofilm present). A more sensitive surface was observed compared to that of a typical antibacterial NF membrane. The Ag leaching rates were low, which will likely result in long-lasting antibacterial and biofouling resistant properties.

  10. 21 CFR 177.2250 - Filters, microporous polymeric.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Filters, microporous polymeric. 177.2250 Section... Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in... liquid food. (a) Microporous polymeric filters consist of a suitably permeable, continuous, polymeric...

  11. A Nanophase-Separated, Quasi-Solid-State Polymeric Single-Ion Conductor: Polysulfide Exclusion for Lithium–Sulfur Batteries

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

    Lee, Jinhong; Song, Jongchan; Lee, Hongkyung

    Formation of soluble polysulfide (PS), which is a key feature of lithium sulfur (Li–S) batteries, provides a fast redox kinetic based on a liquid–solid mechanism; however, it imposes the critical problem of PS shuttle. Here, we address the dilemma by exploiting a solvent-swollen polymeric single-ion conductor (SPSIC) as the electrolyte medium of the Li–S battery. The SPSIC consisting of a polymeric single-ion conductor and lithium salt-free organic solvents provides Li ion hopping by forming a nanoscale conducting channel and suppresses PS shuttle according to the Donnan exclusion principle when being employed for Li–S batteries. The organic solvents at the interfacemore » of the sulfur/carbon composite and SPSIC eliminate the poor interfacial contact and function as a soluble PS reservoir for maintaining the liquid–solid mechanism. Furthermore, the quasi-solid-state SPSIC allows the fabrication of a bipolar-type stack, which promises the realization of a high-voltage and energy-dense Li–S battery.« less

  12. Liking, salt taste perception and use of table salt when consuming reduced-salt chicken stews in light of South Africa's new salt regulations.

    PubMed

    De Kock, H L; Zandstra, E H; Sayed, N; Wentzel-Viljoen, E

    2016-01-01

    This study investigated the impact of salt reduction on liking, salt taste perception, and use of table salt when consuming chicken stew in light of South Africa's new salt recommendations. In total, 432 South-African consumers (aged 35.2 ± 12.3 years) consumed a full portion of a chicken stew meal once at a central location. Four stock cube powders varying in salt content were used to prepare chicken stews: 1) no reduction - 2013 Na level; regular salt level as currently available on the South African market (24473 mg Na/100 g), 2) salt reduction smaller than 2016 level, i.e. 10%-reduced (22025 mg Na/100 g), 3) 2016 salt level, as per regulatory prescriptions (18000 mg Na/100 g), 4) 2019 salt level, as per regulatory prescriptions (13000 mg Na/100 g). Consumers were randomly allocated to consume one of the four meals. Liking, salt taste perception, and use of table salt and pepper were measured. Chicken stews prepared with reduced-salt stock powders were equally well-liked as chicken stews with the current salt level. Moreover, a gradual reduction of the salt in the chicken stews resulted in a reduced salt intake, up to an average of 19% for the total group compared to the benchmark 2013 Na level stew. However, 19% of consumers compensated by adding salt back to full compensation in some cases. More salt was added with increased reductions of salt in the meals, even to the point of full compensation. Further investigation into the impacts of nutrition communication and education about salt reduction on salt taste perception and use is needed. This research provides new consumer insights on salt use and emphasises the need for consumer-focused behaviour change approaches, in addition to reformulation of products. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Sea Salt vs. Table Salt: What's the Difference?

    MedlinePlus

    ... Nutrition and healthy eating What's the difference between sea salt and table salt? Answers from Katherine Zeratsky, R.D., L.D. The main differences between sea salt and table salt are in their taste, ...

  14. A biomolecule friendly photolithographic process for fabrication of protein microarrays on polymeric films coated on silicon chips.

    PubMed

    Petrou, Panagiota S; Chatzichristidi, Margarita; Douvas, Antonios M; Argitis, Panagiotis; Misiakos, Konstantinos; Kakabakos, Sotirios E

    2007-04-15

    The last years, there is a steadily growing demand for methods and materials appropriate to create patterns of biomolecules for bioanalytical applications. Here, a photolithographic method for patterning biomolecules onto a silicon surface coated with a polymeric layer of high protein binding capacity is presented. The patterning process does not affect the polymeric film and the activity of the immobilized onto the surface biomolecules. Therefore, it permits sequential immobilization of different biomolecules on spatially distinct areas on the same solid support. The polymeric layer is based on a commercially available photoresist (AZ5214) that is cured at high temperature in order to provide a stable substrate for creation of protein microarrays by the developed photolithographic process. The photolithographic material consists of a (meth)acrylate copolymer and a sulfonium salt as a photoacid generator, and it is lithographically processed by thermal treatment at temperatures polymeric layer coated silicon surface, protein spots with diameters ranging from 2 to 50 microm were created. The proposed methodology provided good intra-spot homogeneity (CV polymeric film selected for immobilization of biomolecules presented high protein binding capacity, which was at least three folds higher than that obtained using aminosilanized surfaces. The proposed methodology is expected to facilitate considerably the fabrication of dense protein microarrays for bioanalytical applications.

  15. Radiation-induced polymerization of glass-forming systems. V. Initial polymerization rate in binary glass-forming systems

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

    Kaetsu, Isao; Okubo, Hiroshi; Ito, Akihiko

    1973-06-01

    The radiation-induced polymerization of binary systems consisting of glass-forming monomer and glass-forming solvent in supercooled phase was studied. The initial polymerization rates were markedly affected by T/sub g/ (glass transition temperature) and T/sub v/ of the system (30-50 deg C higher than T/sub g/), which are functions of the composition. The composition and temperature dependence of initial polymerization rate in binary glass-forming systems were much affected by homogeneity of the polymerization system and the T of the glass- forming solvent. The composition and temperature dependences in the glycidyl methacrylate --triacetin system as a typical homogeneous polymerization system were studied inmore » detail, and the polymerizations of hydroxyethyl methacrylate triacetln and hydroxyethyl methacrylate --isoamyl acetate systems were studied for the heterogeneous polymerization systems; the former illustrates the combination of lower T/sub g/ monomer and higher T/sub g/ solvent and the latter typifies a system consisting of higher T/sub g/ monomer and lower T/sub g/ solvent. All experimental results for the composition and temperature dependence of initial polymerization rate in binary glass-forming systems could be explained by considering the product of the effect of the physical effect relating to T/sub v/ and T/sub g/ of the system and the effect of composition in normal solution polymerization at higher temperature, which was also the product of a dilution effect and a chemical or physical acceleration effect. (auth)« less

  16. Polymeric nanoparticles

    PubMed Central

    Bolhassani, Azam; Javanzad, Shabnam; Saleh, Tayebeh; Hashemi, Mehrdad; Aghasadeghi, Mohammad Reza; Sadat, Seyed Mehdi

    2014-01-01

    Nanocarriers with various compositions and biological properties have been extensively applied for in vitro/in vivo drug and gene delivery. The family of nanocarriers includes polymeric nanoparticles, lipid-based carriers (liposomes/micelles), dendrimers, carbon nanotubes, and gold nanoparticles (nanoshells/nanocages). Among different delivery systems, polymeric carriers have several properties such as: easy to synthesize, inexpensive, biocompatible, biodegradable, non-immunogenic, non-toxic, and water soluble. In addition, cationic polymers seem to produce more stable complexes led to a more protection during cellular trafficking than cationic lipids. Nanoparticles often show significant adjuvant effects in vaccine delivery since they may be easily taken up by antigen presenting cells (APCs). Natural polymers such as polysaccharides and synthetic polymers have demonstrated great potential to form vaccine nanoparticles. The development of new adjuvants or delivery systems for DNA and protein immunization is an expanding research field. This review describes polymeric carriers especially PLGA, chitosan, and PEI as vaccine delivery systems. PMID:24128651

  17. Supramolecular "Step Polymerization" of Preassembled Micelles: A Study of "Polymerization" Kinetics.

    PubMed

    Yang, Chaoying; Ma, Xiaodong; Lin, Jiaping; Wang, Liquan; Lu, Yingqing; Zhang, Liangshun; Cai, Chunhua; Gao, Liang

    2018-03-01

    In nature, sophisticated functional materials are created through hierarchical self-assembly of nanoscale motifs, which has inspired the fabrication of man-made materials with complex architectures for a variety of applications. Herein, a kinetic study on the self-assembly of spindle-like micelles preassembled from polypeptide graft copolymers is reported. The addition of dimethylformamide and, subsequently, a selective solvent (water) can generate a "reactive point" at both ends of the spindles as a result of the existence of structural defects, which induces the "polymerization" of the spindles into nanowires. Experimental results combined with dissipative particle dynamics simulations show that the polymerization of the micellar subunits follows a step-growth polymerization mechanism with a second-order reaction characteristic. The assembly rate of the micelles is dependent on the subunit concentration and on the activity of the reactive points. The present work reveals a law governing the self-assembly kinetics of micelles with structural defects and opens the door for the construction of hierarchical structures with a controllable size through supramolecular step polymerization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. 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.

  19. Nonlinear optical and conductive polymeric material

    DOEpatents

    Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

    1992-05-19

    A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl.sub.5 or W(CO).sub.6 /hv.

  20. Nonlinear optical and conductive polymeric material

    DOEpatents

    Barton, T.J.; Ijadi-Maghsooodi, S; Yi Pang.

    1993-10-19

    A polymeric material is described which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl[sub 5] or W(CO)[sub 6].

  1. Nonlinear optical and conductive polymeric material

    DOEpatents

    Barton, T.J.; Ijadi-Maghsoodi, S.; Pang, Y.

    1992-05-19

    A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl[sub 5] or W(CO)[sub 6]/hv.

  2. Nonlinear optical and conductive polymeric material

    DOEpatents

    Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

    1993-10-19

    A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl.sub.5 or W(CO).sub.6 /hv.

  3. Polyion selective polymeric membrane-based pulstrode as a detector in flow-injection analysis.

    PubMed

    Bell-Vlasov, Andrea K; Zajda, Joanna; Eldourghamy, Ayman; Malinowska, Elzbieta; Meyerhoff, Mark E

    2014-04-15

    A method for the detection of polyions using fully reversible polyion selective polymeric membrane type pulstrodes as detectors in a flow-injection analysis (FIA) system is examined. The detection electrode consists of a plasticized polymeric membrane doped with 10 wt % of tridodecylmethylammonium-dinonylnaphthalene sulfonate (TDMA/DNNS) ion-exchanger salt. The pulse sequence used involves a short (1 s) galvanostatic pulse, an open-circuit pulse (0.5 s) during which the EMF of the cell is measured, and a longer (15 s) potentiostatic pulse to return the membrane to its original chemical composition. It is shown that total pulse sequence times can be optimized to yield reproducible real-time detection of injected samples of protamine and heparin at up to 20 samples/h. Further, it is shown that the same membrane detector can be employed for FIA detection of both polycations at levels ≥10 μg/mL and polyanions at levels of ≥40 μg/mL by changing the direction of the galvanostatic pulse. The methodology described may also be applicable in the detection of polyionic species at low levels in other flowing configurations, such as in liquid chromatography and capillary electrophoresis.

  4. Temperature dependent electrical properties of polyaniline film grown on paper through aniline vapor polymerization

    NASA Astrophysics Data System (ADS)

    Deb, K.; Bhowmik, K. L.; Bera, A.; Chattopadhyay, K. K.; Saha, B.

    2016-05-01

    Polyaniline thin film has been prepared on paper by aniline vapor deposition technique. Ferric chloride has been used as polymerizing agent in this approach. The prepared films were studied through electrical resistivity and optical properties measurements. The electrical resistivity of the polyaniline film shows significant temperature dependence. The resistance sharply falls with the increase in temperature. The optical absorbance measurements shows characteristics absorbance peak indicating the formation of conducting emeraldine salt form of polyaniline. The optical energy band gap of the film was calculated from the transmittance spectra. The optical energy band gap and electrical conductivity of the polyaniline film is well suited for their applications in electronic devices.

  5. Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates

    NASA Technical Reports Server (NTRS)

    Simpson, Joycely O. (Inventor); St.Clair, Terry L. (Inventor)

    1999-01-01

    A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers. acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors, in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors. weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 1000 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

  6. In vivo toxic and lethal cardiovascular effects of a synthetic polymeric 1,3-dodecylpyridinium salt in rodents

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

    Grandic, Marjana; Sepcic, Kristina; Turk, Tom

    2011-08-15

    APS12-2 is one in a series of synthetic analogs of the polymeric alkylpyridinium salts isolated from the marine sponge Reniera sarai. As it is a potential candidate for treating non small cell lung cancer (NSCLC), we have studied its possible toxic and lethal effects in vivo. The median lethal dose (LD{sub 50}) of APS12-2 in mice was determined to be 11.5 mg/kg. Electrocardiograms, arterial blood pressure and respiratory activity were recorded under general anesthesia in untreated, pharmacologically vagotomized and artificially ventilated rats injected with APS12-2. In one group, the in vivo effects of APS12-2 were studied on nerve-evoked muscle contraction.more » Administration of APS12-2 at a dose of 8 mg/kg caused a progressive reduction of arterial blood pressure to a mid-circulatory value, accompanied by bradycardia, myocardial ischemia, ventricular extrasystoles, and second degree atrio-ventricular block. Similar electrocardiogram and arterial blood pressure changes caused by APS12-2 (8 mg/kg) were observed in animals pretreated with atropine and in artificially ventilated animals, indicating that hypoxia and cholinergic effects do not play a crucial role in the toxicity of APS12-2. Application of APS12-2 at sublethal doses (4 and 5.5 mg/kg) caused a decrease of arterial blood pressure, followed by an increase slightly above control values. We found that APS12-2 causes lysis of rat erythrocytes in vitro, therefore it is reasonable to expect the same effect in vivo. Indeed, hyperkalemia was observed in the blood of experimental animals. Hyperkalemia probably plays an important role in APS12-2 cardiotoxicity since no evident changes in histopathology of the heart were found. However, acute lesions were observed in the pulmonary vessels of rats after application of 8 mg/kg APS12-2. Predominant effects were dilation of interalveolar blood vessels and lysis of aggregated erythrocytes within their lumina. - Highlights: > LD{sub 50} estimated in mice (11.5 mg

  7. Mutation of the Salt Bridge-forming Residues in the ETV6-SAM Domain Interface Blocks ETV6-NTRK3-induced Cellular Transformation*

    PubMed Central

    Cetinbas, Naniye; Huang-Hobbs, Helen; Tognon, Cristina; Leprivier, Gabriel; An, Jianghong; McKinney, Steven; Bowden, Mary; Chow, Connie; Gleave, Martin; McIntosh, Lawrence P.; Sorensen, Poul H.

    2013-01-01

    The ETV6-NTRK3 (EN) chimeric oncogene is expressed in diverse tumor types. EN is generated by a t(12;15) translocation, which fuses the N-terminal SAM (sterile α-motif) domain of the ETV6 (or TEL) transcription factor to the C-terminal PTK (protein-tyrosine kinase) domain of the neurotrophin-3 receptor NTRK3. SAM domain-mediated polymerization of EN leads to constitutive activation of the PTK domain and constitutive signaling of the Ras-MAPK and PI3K-Akt pathways, which are essential for EN oncogenesis. Here we show through complementary biophysical and cellular biological techniques that mutation of Lys-99, which participates in a salt bridge at the SAM polymer interface, reduces self-association of the isolated SAM domain as well as high molecular mass complex formation of EN and abrogates the transformation activity of EN. We also show that mutation of Asp-101, the intermolecular salt bridge partner of Lys-99, similarly blocks transformation of NIH3T3 cells by EN, reduces EN tyrosine phosphorylation, inhibits Akt and Mek1/2 signaling downstream of EN, and abolishes tumor formation in nude mice. In contrast, mutations of Glu-100 and Arg-103, residues in the vicinity of the interdomain Lys-99–Asp-101 salt bridge, have little or no effect on these oncogenic characteristics of EN. Our results underscore the importance of specific electrostatic interactions for SAM polymerization and EN transformation. PMID:23798677

  8. Mutation of the salt bridge-forming residues in the ETV6-SAM domain interface blocks ETV6-NTRK3-induced cellular transformation.

    PubMed

    Cetinbas, Naniye; Huang-Hobbs, Helen; Tognon, Cristina; Leprivier, Gabriel; An, Jianghong; McKinney, Steven; Bowden, Mary; Chow, Connie; Gleave, Martin; McIntosh, Lawrence P; Sorensen, Poul H

    2013-09-27

    The ETV6-NTRK3 (EN) chimeric oncogene is expressed in diverse tumor types. EN is generated by a t(12;15) translocation, which fuses the N-terminal SAM (sterile α-motif) domain of the ETV6 (or TEL) transcription factor to the C-terminal PTK (protein-tyrosine kinase) domain of the neurotrophin-3 receptor NTRK3. SAM domain-mediated polymerization of EN leads to constitutive activation of the PTK domain and constitutive signaling of the Ras-MAPK and PI3K-Akt pathways, which are essential for EN oncogenesis. Here we show through complementary biophysical and cellular biological techniques that mutation of Lys-99, which participates in a salt bridge at the SAM polymer interface, reduces self-association of the isolated SAM domain as well as high molecular mass complex formation of EN and abrogates the transformation activity of EN. We also show that mutation of Asp-101, the intermolecular salt bridge partner of Lys-99, similarly blocks transformation of NIH3T3 cells by EN, reduces EN tyrosine phosphorylation, inhibits Akt and Mek1/2 signaling downstream of EN, and abolishes tumor formation in nude mice. In contrast, mutations of Glu-100 and Arg-103, residues in the vicinity of the interdomain Lys-99-Asp-101 salt bridge, have little or no effect on these oncogenic characteristics of EN. Our results underscore the importance of specific electrostatic interactions for SAM polymerization and EN transformation.

  9. Acrylic esters in radiation polymerization

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

    Fomina, N.V.; Khoromskaya, V.A.; Shiryaeva, G.V.

    1988-03-01

    The radiation behavior of (meth)acrylic esters of varying structure was studied. It was shown that in radiation polymerization, in contrast to thermal polymerization, the structure of the ester part can significantly affect the reaction rate and capacity for polymerization in the presence of oxygen. The experimental data are explained from the point of view of consideration of nonvalence effects of the substitutent on the reactivity of the double bond.

  10. Equilibrium polymerization on the equivalent-neighbor lattice

    NASA Technical Reports Server (NTRS)

    Kaufman, Miron

    1989-01-01

    The equilibrium polymerization problem is solved exactly on the equivalent-neighbor lattice. The Flory-Huggins (Flory, 1986) entropy of mixing is exact for this lattice. The discrete version of the n-vector model is verified when n approaches 0 is equivalent to the equal reactivity polymerization process in the whole parameter space, including the polymerized phase. The polymerization processes for polymers satisfying the Schulz (1939) distribution exhibit nonuniversal critical behavior. A close analogy is found between the polymerization problem of index the Schulz r and the Bose-Einstein ideal gas in d = -2r dimensions, with the critical polymerization corresponding to the Bose-Einstein condensation.

  11. Modification of thin-film polyamide membrane with multi-walled carbon nanotubes by interfacial polymerization

    NASA Astrophysics Data System (ADS)

    Al-Hobaib, Abdullah S.; Al-Sheetan, Kh. M.; Shaik, Mohammed Rafi; Al-Suhybani, M. S.

    2017-12-01

    Polyamide thin-film composite (TFC) was fabricated on polysulfone (PS-20) base by interfacial polymerization of aqueous m-phenylenediamine (MPD) solution and 1,3,5-benzenetricarbonyl trichloride (TMC) in hexane organic solution. Multi-wall carbon nanotubes (MWCNT) were carboxylated by heating MWCNT powder in a mixture of HNO3 and H2SO4 (1:3 v/v) at 70 °C under constant sonication for different periods. Polyamide nanocomposites were prepared by incorporating MWCNT and the carboxylated MWCNT (MWCNT-COOH) at different concentrations (0.001-0.009 wt%). The developed composites were analyzed by Fourier transform infrared spectroscopy-attenuated total reflection, scanning electron microscopy, transmission electron microscopy, contact angle measurement, determination of salt rejection and water permeate flux capabilities. The surface morphological studies displayed that the amalgamation of MWCNT considerably changed the surface properties of modified membranes. The surface hydrophilicity was increased as observed in the enhancement in water flux and pure water permeance, due to the presence of hydrophilic nanotubes. Salt rejection was obtained between 94 and 99% and varied water flux values for TFC-reference membrane, pristine-MWCNT in MPD, pristine-MWCNT in TMC and MWCNT-COOH in MPD were 20.5, 38, 40 and 43 L/m2h. The water flux and salt rejection performances revealed that the MWCNT-COOH membrane was superior membrane as compared to the other prepared membranes.

  12. 21 CFR 100.155 - Salt and iodized salt.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 2 2010-04-01 2010-04-01 false Salt and iodized salt. 100.155 Section 100.155 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION GENERAL Specific Administrative Rulings and Decisions § 100.155 Salt and iodized salt. (a) For the purposes of this section, the...

  13. Tracking metal ions with polypyrrole thin films adhesively bonded to diazonium-modified flexible ITO electrodes.

    PubMed

    Lo, Momath; Diaw, Abdou K D; Gningue-Sall, Diariatou; Aaron, Jean-Jacques; Oturan, Mehmet A; Chehimi, Mohamed M

    2018-05-09

    Adhesively bonded polypyrrole thin films doped with benzene sulfonic acid (BSA) were electrodeposited on aminobenzenediazonium-modified flexible ITO electrodes and further employed for the detection of Pb 2+ , Cu 2+ , and Cd 2+ metal ions in aqueous medium. The aminophenyl (AP) adhesive layer was grafted to ITO by electroreduction of the in situ generated parent diazonium compound. Polypyrrole (PPy) thin films exhibited remarkable adhesion to aminophenyl (ITO-AP). The strongly adherent polypyrrole films exhibited excellent electroactivity in the doped state with BSA which itself served to chelate the metal ions in aqueous medium. The surface of the resulting, modified flexible electrode was characterized by XPS, SEM, and electrochemical methods. The ITO-AP-PPy electrodes were then used for the simultaneous detection of Cu 2+ , Cd 2+ , and Pb 2+ by differential pulse voltammetry (DPV). The detection limits were 11.1, 8.95, and 0.99 nM for Cu 2+ , Cd 2+ , and Pb 2+ , respectively. In addition, the modified electrodes displayed a good reproducibility, making them suitable for the determination of heavy metals in real wastewater samples.

  14. The micro-element dynamic in hortic antrosoils conditioned with polymeric materials

    NASA Astrophysics Data System (ADS)

    Filipov, F.; Bulgariu, D.; Jitareanu, G.; Bulgariu, L.

    2009-04-01

    The studies regarding the dynamic of microelements in hortic anthrosols (soils from glasshouses and solariums) are important both from scientific point of view and in special, for the implementation of durable ecological technologies of amelioration, conservation and superior capitalization of soil resources from protected areas (glasshouses and solariums). In case of hortic anthrosols, the application of intensive technologies for plants cultivation determined brusque and intense perturbations of equilibriums between microelements and mineral and organic components of anthrosols, which is reflected by a fast degradation of morphological and physic-chemical properties. But, in case of hortic anthrosols, the exploitation conditions determined a particular evolution of microelements, and of distributions and interactions way with soil components, respectively. The conditioning and the amelioration of hortic antrosols with ecologic polymeric materials is one of the method approved in this moment and according with the opinion of most of specialists, represent one of method with large applications in modern agriculture. The utilization of polymeric materials to the conditioning of soils have been studied over 50 years, their effects on morphological, physical and chemical properties of soils being know, in special for agricultural and polluted soils. Ours studied have been performed using soil profiles drawing from Copou-glass house, Iasi (Romania). Has been followed the modification of distribution for speciation forms of some micro-elements (Zn, Cu, Ni, Mn, Cr, P), between hortic antrosol horizons, and between chemical-mineralogical components of this, with the progressive salinization of superior horizons, in 2007-2008 period. For the experimental study have been used three types of water-soluble polymers, with different hydrophobicities: polyethylene glycol (molecular mass 2000, 4000 and 8000), vinyl acetate - ammonia maleate salt copolymer (AM-VA) and

  15. Diclofenac salts. III. Alkaline and earth alkaline salts.

    PubMed

    Fini, Adamo; Fazio, Giuseppe; Rosetti, Francesca; Angeles Holgado, M; Iruín, Ana; Alvarez-Fuentes, Josefa

    2005-11-01

    Diclofenac salts containing the alkaline and two earth alkaline cations have been prepared and characterized by scanning electron microscopy (SEM) and EDAX spectroscopy; and by thermal and thermogravimetric analysis (TGA): all of them crystallize as hydrate when precipitated from water. The salts dehydrate at room temperature and more easily on heating, but recovery the hydration, when placed in a humid environment. X-ray diffraction spectra suggest that on dehydration new peaks appear on diffractograms and the lattice of the salts partially looses crystallinity. This phenomenon is readily visible in the case of the calcium and magnesium salts, whose thermograms display a crystallization exotherm, before melting or decomposing at temperatures near or above 200 degrees C; these last salts appear to form solvates, when prepared from methanol. The thermogram of each salt shows a complex endotherm of dehydration about 100 degrees C; the calcium salt displays two endotherms, well separated at about 120 and 160 degrees C, which disappear after prolonged heating. Decomposition exotherms, before or soon after the melting, appear below 300 degrees C. The ammonium salt is thermally unstable and, when heated to start dehydration, dissociates and leaves acidic diclofenac.

  16. Exceptionally high lactide polymerization activity of zirconium complexes with bridged diketiminate ligands.

    PubMed

    El-Zoghbi, Ibrahim; Whitehorne, Todd J J; Schaper, Frank

    2013-07-07

    A cyclohexanediyl-bridged, bis(N-xylyl) diketiminate ligand, (±)-C6H10(nacnac(Xyl)H)2, LH2 (Xyl = 2,6-dimethylphenyl), was obtained from the reaction of [(2,6-dimethylphenyl)amino]-pent-3-en-2-one first with Meerwein's salt, then with (±)-cyclohexanediamine. The reaction of the ligand with Zr(NMe2)4 yielded LZr(NMe2)2. Protonation of the remaining diamide ligands with EtOH or [H2NMe2]Cl yielded LZr(OEt)2 and LZrCl2, respectively. The latter complex was also obtained by the reaction of LH2 first with nBuLi and then with ZrCl4(THF)2. The dichloride complex yielded LZr(OEt)2 and LZrMe2 upon reaction with NaOEt or MeLi/AlMe3, respectively. X-ray diffraction studies showed a trans-configuration of the ancillary ligands in LZrCl2 and LZrMe2, and a cis-configuration in LZr(NMe2)2 and LZr(OEt)2. LZr(OEt)2 was tested as a catalyst for the polymerization of rac-lactide. Kinetic investigations yielded a rate law first order in catalyst and monomer and a rate constant k = 14(1) L mol(-1) s(-1), the latter being orders of magnitude higher than typical activities for group 4 complexes in lactide polymerization. Analyses of the obtained polymer revealed an atactic polymer and broad polymer molecular weight distributions with sizeable fractions of cyclic oligomers. The influence of contaminants on the polymerization activity was examined: while lactic acid deactivates the catalyst, addition of up to 1 equiv. of water or para-toluenesulfonic acid revitalized catalysts not showing maximum activity.

  17. Versatile Tandem Ring-Opening/Ring-Closing Metathesis Polymerization: Strategies for Successful Polymerization of Challenging Monomers and Their Mechanistic Studies.

    PubMed

    Park, Hyeon; Kang, Eun-Hye; Müller, Laura; Choi, Tae-Lim

    2016-02-24

    Tandem ring-opening/ring-closing metathesis (RO/RCM) results in extremely fast living polymerization; however, according to previous reports, only monomers containing certain combinations of cycloalkenes, terminal alkynes, and nitrogen linkers successfully underwent tandem polymerization. After examining the polymerization pathways, we proposed that the relatively slow intramolecular cyclization might lead to competing side reactions such as intermolecular cross metathesis reactions to form inactive propagating species. Thus, we developed two strategies to enhance tandem polymerization efficiency. First, we modified monomer structures to accelerate tandem RO/RCM cyclization by enhancing the Thorpe-Ingold effect. This strategy increased the polymerization rate and suppressed the chain transfer reaction to achieve controlled polymerization, even for challenging syntheses of dendronized polymers. Alternatively, reducing the reaction concentration facilitated tandem polymerization, suggesting that the slow tandem RO/RCM cyclization step was the main reason for the previous failure. To broaden the monomer scope, we used monomers containing internal alkynes and observed that two different polymer units with different ring sizes were produced as a result of nonselective α-addition and β-addition on the internal alkynes. Thorough experiments with various monomers with internal alkynes suggested that steric and electronic effects of the alkyne substituents influenced alkyne addition selectivity and the polymerization reactivity. Further polymerization kinetics studies revealed that the rate-determining step of monomers containing certain internal alkynes was the six-membered cyclization step via β-addition, whereas that for other monomers was the conventional intermolecular propagation step, as observed in other chain-growth polymerizations. This conclusion agrees well with all those polymerization results and thus validates our strategies.

  18. Antimicrobial Peptide Mimicking Primary Amine and Guanidine Containing Methacrylamide Copolymers Prepared by Raft Polymerization

    PubMed Central

    Exley, Sarah E.; Paslay, Lea C.; Sahukhal, Gyan S.; Abel, Brooks A.; Brown, Tyler D.; McCormick, Charles L.; Heinhorst, Sabine; Koul, Veena; Choudhary, Veena; Elasri, Mohamed O.; Morgan, Sarah E.

    2016-01-01

    Naturally occurring antimicrobial peptides (AMPs) display the ability to eliminate a wide variety of bacteria, without toxicity to the host eukaryotic cells. Synthetic polymers containing moieties mimicking lysine and arginine components found in AMPs have been reported to show effectiveness against specific bacteria, with the mechanism of activity purported to depend on the nature of the amino acid mimic. In an attempt to incorporate the antimicrobial activity of both amino acids into a single water-soluble copolymer, a series of copolymers containing lysine mimicking aminopropyl methacrylamide (APMA) and arginine mimicking guanadinopropyl methacrylamide (GPMA) were prepared via aqueous RAFT polymerization. Copolymers were prepared with varying ratios of the comonomers, with degree of polymerization of 35–40 and narrow molecular weight distribution to simulate naturally occurring AMPs. Antimicrobial activity was determined against Gram-negative and Gram-positive bacteria under conditions with varying salt concentration. Toxicity to mammalian cells was assessed by hemolysis of red blood cells and MTT assays of MCF-7 cells. Antimicrobial activity was observed for APMA homopolymer and copolymers with low concentrations of GPMA against all bacteria tested, with low toxicity toward mammalian cells. PMID:26558609

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

    PubMed

    Yu, W H; Kang, E T; Neoh, K G

    2005-01-04

    Surface modification of poly(tetrafluoroethylene) (PTFE) films by well-defined comb copolymer brushes was carried out. Peroxide initiators were generated directly on the PTFE film surface via radio frequency Ar plasma pretreatment, followed by air exposure. Poly(glycidyl methacrylate) (PGMA) brushes were first prepared by surface-initiated reversible addition-fragmentation chain transfer polymerization from the peroxide initiators on the PTFE surface in the presence of a chain transfer agent. Kinetics study revealed a linear increase in the graft concentration of PGMA with the reaction time, indicating that the chain growth from the surface was consistent with a "controlled" or "living" process. alpha-Bromoester moieties were attached to the grafted PGMA by reaction of the epoxide groups with 2-bromo-2-methylpropionic acid. The comb copolymer brushes were subsequently prepared via surface-initiated atom transfer radical polymerization of two hydrophilic vinyl monomers, including poly(ethylene glycol) methyl ether methacrylate and sodium salt of 4-styrenesulfonic acid. The chemical composition of the modified PTFE surfaces was characterized by X-ray photoelectron spectroscopy.

  20. Determination of bilirubin glucuronide and assay of glucuronyltransferase with bilirubin as acceptor

    PubMed Central

    Van Roy, F. P.; Heirwegh, K. P. M.

    1968-01-01

    1. Conjugated bilirubin is conveniently determined by coupling with the diazonium salt of ethyl anthranilate. 2. This method has been used in the development of assays for UDP-glucuronyltransferase (EC 2.4.1.17), with bilirubin as substrate, in rat liver homogenates, microsomal preparations and partly purified fractions. 3. Chromatographic analysis suggests that bilirubin monoglucuronide is the product of the enzyme systems studied. PMID:5660631

  1. Absorption of polycyclic aromatic hydrocarbons by a highly absorptive polymeric medium.

    PubMed

    Francisco, Olga; Idowu, Ifeoluwa; Friesen, Kelsey L; McDougall, Matthew; Choi, Sara Seoin; Bolluch, Patrique; Daramola, Oluwadamilola; Johnson, Wesley; Palace, Vince; Stetefeld, Jörg; Tomy, Gregg T

    2018-06-01

    The efficacy of a lightly cross-linked polymeric bead to absorb polycyclic aromatic hydrocarbons (PAHs) from the surface of fresh- and salt-water in a simulated oil-spill scenario was assessed in this study. A layer of PAHs at the water surface was created by first preparing the PAHs in hexane and then carefully spiking this mixture onto the surface of water. Beads were then applied to the surface of the organic phase and the amount of hydrocarbons absorbed by the beads was examined at prescribed time intervals and at different temperatures. Absorption of PAHs into the beads was exhaustive with ∼86 ± 4% being selectively removed from the organic phase by 120 s. First order reaction rates best described the uptake kinetics and absorption rates ranged from 0.0085 (naphthalene) to 0.0325 s- 1 (dibenzo[a,h]anthracene). Absorption of PAHs into the beads was driven by molecular volume (A 3 ). Uptake rates increased markedly for PAHs with molecular volumes between 130 A 3 and 190 A 3 . Beyond this molecular volume there was no apparent change in the rate of uptake. This study shows that these polymeric beads have a high affinity for PAHs and can be used under various environmental conditions with negligible difference in absorptive efficacy. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. Signal amplification strategies for DNA and protein detection based on polymeric nanocomposites and polymerization: A review.

    PubMed

    Zhou, Shaohong; Yuan, Liang; Hua, Xin; Xu, Lingling; Liu, Songqin

    2015-06-02

    Demand is increasing for ultrasensitive bioassays for disease diagnosis, environmental monitoring and other research areas. This requires novel signal amplification strategies to maximize the signal output. In this review, we focus on a series of significant signal amplification strategies based on polymeric nanocomposites and polymerization. Some common polymers are used as carriers to increase the local concentration of signal probes and/or biomolecules on their surfaces or in their interiors. Some polymers with special fluorescence and optical properties can efficiently transfer the excitation energy from a single site to the whole polymer backbone. This results in superior fluorescence signal amplification due to the resulting collective effort (integration of signal). Recent polymerization-based signal amplification strategies that employ atom transfer radical polymerization (ATRP) and photo-initiated polymerization are also summarized. Several distinctive applications of polymers in ultrasensitive bioanalysis are highlighted. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Consumer knowledge and attitudes to salt intake and labelled salt information.

    PubMed

    Grimes, Carley A; Riddell, Lynn J; Nowson, Caryl A

    2009-10-01

    The objective of this study was to investigate consumers' knowledge of health risks of high salt intake and frequency of use and understanding of labelled salt information. We conducted a cross-sectional survey in shopping centres within Metropolitan Melbourne. A sample of 493 subjects was recruited. The questionnaire assessed salt related shopping behaviours, attitudes to salt intake and health and their ability to interpret labelled sodium information. Four hundred and seventy four valid surveys were collected (65% female, 64% being the main shopper). Most participants knew of the relationship between salt intake and high blood pressure (88%). Sixty five percent of participants were unable to correctly identify the relationship between salt and sodium. Sixty nine percent reported reading the salt content of food products when shopping. Salt label usage was significantly related to shoppers concern about the amount of salt in their diet and the belief that their health could improve by lowering salt intake. Approximately half of the sample was unable to accurately use labelled sodium information to pick low salt options. Raising consumer awareness of the health risks associated with high salt consumption may increase salt label usage and purchases of low salt foods. However, for food labels to be effective in helping consumers select low salt foods a more 'user friendly' labelling format is needed.

  4. Effect of the Polymeric Stabilizer in the Aqueous Phase Fischer-Tropsch Synthesis Catalyzed by Colloidal Cobalt Nanocatalysts

    PubMed Central

    Delgado, Jorge A.; Claver, Carmen; Castillón, Sergio; Curulla-Ferré, Daniel; Godard, Cyril

    2017-01-01

    A series of small and well defined cobalt nanoparticles were synthesized by the chemical reduction of cobalt salts in water using NaBH4 as a reducing agent and using various polymeric stabilizers. The obtained nanocatalysts of similar mean diameters (ca. 2.6 nm) were fully characterized and tested in the aqueous phase Fischer-Tropsch Synthesis (AFTS). Interestingly, the nature and structure of the stabilizers used during the synthesis of the CoNPs affected the reduction degree of cobalt and the B-doping of these NPs and consequently, influenced the performance of these nanocatalysts in AFTS. PMID:28336892

  5. Temperature dependent electrical properties of polyaniline film grown on paper through aniline vapor polymerization

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

    Deb, K.; Bera, A.; Saha, B., E-mail: biswajit.physics@gmail.com

    2016-05-23

    Polyaniline thin film has been prepared on paper by aniline vapor deposition technique. Ferric chloride has been used as polymerizing agent in this approach. The prepared films were studied through electrical resistivity and optical properties measurements. The electrical resistivity of the polyaniline film shows significant temperature dependence. The resistance sharply falls with the increase in temperature. The optical absorbance measurements shows characteristics absorbance peak indicating the formation of conducting emeraldine salt form of polyaniline. The optical energy band gap of the film was calculated from the transmittance spectra. The optical energy band gap and electrical conductivity of the polyaniline filmmore » is well suited for their applications in electronic devices.« less

  6. Developing a polymeric sensor to monitor intracellular conditions

    NASA Astrophysics Data System (ADS)

    Mudarri, Timothy C.; Leo, Donald J.; Wood, Brett C.; Shires, Peter K.

    2004-07-01

    Ionic electroactive polymers have been developed as mechanical sensors or actuators, taking advantage of the electromechanical coupling of the materials. This research attempts to take advantage of the chemomechanical and chemoelectrical coupling by characterizing the transient response as the polymer undergoes an ion exchange, thus using the polymer for ionic sensing. Nafion is a biocompatible material, and an implantable polymeric ion sensor which has applications in the biomedical field for bone healing research. An ion sensor and a strain gauge could determine the effects of motion allowed at the fracture site, thus improving rehabilitation procedures for bone fractures. The charge sensitivity of the material and the capacitance of the material were analyzed to determine the transient response. Both measures indicate a change when immersed in ionic salt solutions. It is demonstrated that measuring the capacitance is the best indicator of an ion exchange. Relative to a flat response in deionized water (+/-2%), the capacitance of the polymer exhibits an exponential decay of ~25% of its peak when placed in a salt solution. A linear correlation between the time constant of the decay and the ionic size of the exchanging ion was developed that could reasonably predict a diffusing ion. Tests using an energy dispersive spectrometer (EDS) indicate that 90% of the exchange occurs in the first 20 minutes, shown by both capacitance decay and an atomic level scan. The diffusion rate time constant was found to within 0.3% of the capacitance time constant, confirming the ability of capacitance to measure ion exchange.

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

    PubMed

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

    2017-04-10

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

  8. Investigation of salt loss from the Bonneville Salt Flats, northwestern Utah

    USGS Publications Warehouse

    Mason, James L.; Kipp, Kenneth L.

    1997-01-01

    The Bonneville Salt Flats study area is located in the western part of the Great Salt Lake Desert in northwestern Utah, about 110 miles west of Salt Lake City. The salt crust covers about 50 square miles, but the extent varies yearly as a result of salt being dissolved by the formation and movement of surface ponds during the winter and redeposited with the evaporation of these ponds during the summer.A decrease in thickness and extent of the salt crust on the Bonneville Salt Flats has been documented during 1960-88 (S. Brooks, Bureau of Land Management, written commun., 1989). Maximum salt-crust thickness was 7 feet in 1960 and 5.5 feet in 1988. No definitive data are available to identify and quantify the processes that cause salt loss. More than 55 million tons of salt are estimated to have been lost from the salt crust during the 28-year period. The Bureau of Land Management needs to know the causes of salt loss to make appropriate management decisions.

  9. Mucoadhesive ophthalmic vehicles: evaluation of polymeric low-viscosity formulations.

    PubMed

    Saettone, M F; Monti, D; Torracca, M T; Chetoni, P

    1994-01-01

    A series of polyanionic natural or semi-synthetic polymers (polygalacturonic acid, hyaluronic acid, carboxymethylamylose, carboxymethylchitin, chondroitin sulfate, heparan sulfate and mesoglycan) were evaluated as potential mucoadhesive carriers for ophthalmic drugs. Solutions containing cyclopentolate (CY) or pilocarpine (PI) as salts (or polyanionic complexes) with the acidic polymers, all showing a low viscosity, were tested for miotic (resp. mydriatic) activity in albino rabbits. In the case of some polymeric complexes, small but significant increases of the areas under the activity vs. time curves (AUC) over reference cyclopentolate hydrochloride (CYHC1) or pilocarpine nitrate (PINO3) vehicles, and significant AUC decreases after removal of precorneal mucin by treatment with N-acetylcysteine were observed. A correlation was found between these data, considered indicative of the occurrence of a mucoadhesive interaction "in vivo", and "in vitro" viscometric data expressing the polymers-mucin force of interaction. The advantages and limitations of the mucoadhesive non-viscous approach in the formulation of ophthalmic vehicles are presented and discussed.

  10. Polymeric membrane materials for artificial organs.

    PubMed

    Kawakami, Hiroyoshi

    2008-01-01

    Many polymeric materials have already been used in the field of artificial organs. However, the materials used in artificial organs are not necessarily created with the best material selectivity and materials design; therefore, the development of synthesized polymeric membrane materials for artificial organs based on well-defined designs is required. The approaches to the development of biocompatible polymeric materials fall into three categories: (1) control of physicochemical characteristics on material surfaces, (2) modification of material surfaces using biomolecules, and (3) construction of biomimetic membrane surfaces. This review will describe current issues regarding polymeric membrane materials for use in artificial organs.

  11. 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

  12. Effects of organic solvents on drug incorporation into polymeric carriers and morphological analyses of drug-incorporated polymeric micelles.

    PubMed

    Harada, Yoshiko; Yamamoto, Tatsuhiro; Sakai, Masaru; Saiki, Toshiharu; Kawano, Kumi; Maitani, Yoshie; Yokoyama, Masayuki

    2011-02-14

    We incorporated an anticancer agent, camptothecin (CPT), into polymeric micelle carriers by using two different solvents (TFE and chloroform) in the solvent-evaporation drug incorporation process. We observed significant differences in the drug-incorporation behaviors, in the morphologies of the incorporated drug and the polymeric micelles, and in the pharmacokinetic behaviors between the two solvents' cases. In particular, the CPT-incorporated polymeric micelles prepared with TFE as the incorporation solvent exhibited more stable circulation in blood than those prepared with chloroform. This contrast indicates a novel technological perspective regarding the drug incorporation into polymeric micelle carriers. Morphological analyses of the inner core have revealed the presence of the directed alignment of the CPT molecules and CPT crystals in the micelle inner core. This is the first report of the morphologies of the drug incorporated into the polymeric micelle inner cores. We believe these analyses are very important for further pharmaceutical developments of polymeric micelle drug-carrier systems. Copyright © 2010 Elsevier B.V. All rights reserved.

  13. 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.

  14. 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

  15. Where Does Road Salt Go - a Static Salt Model

    NASA Astrophysics Data System (ADS)

    Yu, C. W.; Liu, F.; Moriarty, V. W.

    2017-12-01

    Each winter, more than 15 million tons of road salt is applied in the United States for the de-icing purpose. Considerable amount of chloride in road salt flows into streams/drainage systems with the snow melt runoff and spring storms, and eventually goes into ecologically sensitive low-lying areas in the watershed, such as ponds and lakes. In many watersheds in the northern part of US, the chloride level in the water body has increased significantly in the past decades, and continues an upward trend. The environmental and ecological impact of the elevated chloride level can no longer be ignored. However although there are many studies on the biological impact of elevated chloride levels, there are few investigations on how the spatially distributed road salt application affects various parts of the watershed. In this presentation, we propose a static road salt model as a first-order metric to address spacial distribution of salt loading. Derived from the Topological Wetness Index (TWI) in many hydrological models, this static salt model provides a spatial impact as- sessment of road salt applications. To demonstrate the effectiveness of the static model, National Elevation Dataset (NED) of ten-meter resolution of Lake George watershed in New York State is used to generate the TWI, which is used to compute a spatially dis- tributed "salt-loading coefficient" of the whole watershed. Spatially varying salt applica- tion rate is then aggregated, using the salt-loading coefficients as weights, to provide salt loading assessments of streams in the watershed. Time-aggregated data from five CTD (conductivity-temperature-depth) sensors in selected streams are used for calibration. The model outputs and the sensor data demonstrate a strong linear correlation, with the R value of 0.97. The investigation shows that the static modeling approach may provide an effective method for the understanding the input and transport of road salt to within watersheds.

  16. A study of diazonium couplings with aromatic nucleophiles both in solution and on a polymer surface

    NASA Astrophysics Data System (ADS)

    Chng, Shuyun; Parker, Emily M.; Griffiths, Jon-Paul; Moloney, Mark G.; Wu, Linda Y. L.

    2017-04-01

    Diazonium coupling is a technique finding wider application to materials and biological science, for hybridization and linking processes, and for the construction of responsive surface functionality. For this reason, detailed examination of solution and surface processes was warranted, and results of such a study are reported here. The modification of polystyrene surfaces was examined as a model, and the process compared to a solution mimic using N,N-dimethylaniline. It was confirmed that solution and solid surface reactions proceed in a similar manner in terms of the chemical functionality generated, but with lower chemical efficiency and reaction times slower for the latter, in a reaction which was pH dependent. The solution process was shown to give only the trans-azo para- coupled products. Whilst there are clear similarities between the solution and surface chemistry, the efficiency of coupling at a surface is not necessarily replicated in the chemical yield of the mimicking solution processes, but nonetheless provides an alternative to other Click-type surface modifications. It should not be assumed that such couplings occur with quantitative efficiency at the surface.

  17. INNER SALTS

    DTIC Science & Technology

    been characterized include: (1) mesomeric phosphonium salts possessing phototropic properties; (2) pentavalent phosphorus compounds; and (3) a...Products that have been characterized include: (1) mesomeric phosphonium salts possessing phototropic properties; (2) pentavalent phosphorus compounds; and (3) a mesomeric inner salt. (Author)

  18. Hydration effects on the photoionization energy of 2‧-deoxyguanosine 5‧-phosphate and activation barriers for guanine methylation by carcinogenic methane diazonium ions

    NASA Astrophysics Data System (ADS)

    Eichler, Daniel R.; Hamann, Haley A.; Harte, Katherine A.; Papadantonakis, George A.

    2017-07-01

    Results from DFT calculations indicate that states originating from gas-phase ionization of the phosphate and the base are degenerate in syn-5‧-dGMP- and that bulk hydration lowers the base-localized ionization energy by <0.5 eV. Local ionization maps show that micro-hydration leads to the formation of donor and acceptor hydrogen bonds and the ionization energy decreases or increases in each case respectively. The SN2 transition states of the methylation reactions of guanine with methane diazonium ions are lower at the N7 than at the O6 sites and they are influenced by local ionization energy and steric interference.

  19. A novel conversion of C(19)-diterpenoid alkaloids into aconane-type diterpenes with eight-membered ring system via skeletal rearrangement of corresponding diazonium derivatives.

    PubMed

    Ji, Hong; Chen, Qiao-Hong; Wang, Feng-Peng

    2009-03-01

    A new and efficient approach toward the conversion of C(19)-diterpenoid alkaloids into diterpenes with [6+8+5+6] ring system is reported. Treatment of imines 5, 14, and 24 derived from the C(19)-diterpenoid alkaloids with NaNO(2)-NaOAc-HOAc afforded a series of novel rearrangement diterpenes 6-8, 15-19, and 25-27, respectively. The lactone 11 was obtained in 41% yield by treating 5 with NaNO(2)-HBr-Br(2). The formation of diazonium intermediate is postulated, which was subsequently subjected to skeletal rearrangement, leading to the enlargement of B ring. All the new compounds were isolated and fully characterized.

  20. Dual Visible Light Photoredox and Gold-Catalyzed Arylative Ring Expansion

    PubMed Central

    2015-01-01

    A combination of visible light photocatalysis and gold catalysis is applied to a ring expansion–oxidative arylation reaction. The reaction provides an entry into functionalized cyclic ketones from the coupling reaction of alkenyl and allenyl cycloalkanols with aryl diazonium salts. A mechanism involving generation of an electrophilic gold(III)–aryl intermediate is proposed on the basis of mechanistic studies, including time-resolved FT-IR spectroscopy. PMID:24730447

  1. Synthesis and polymerization of vinyl triazolium ionic liquids

    DOEpatents

    Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof; Adzima, Brian

    2018-05-15

    Herein, we describe polymerized ionic liquids, demonstrate the synthesis of polymerized ionic liquids, and demonstrate the polymerization of triazolium monomers. One embodiment shows the polymeriazation of the triazolium monomers with bis(trifluoromethanesulfonyl)imide anions. In another embodiment we show the feasibility of copolymerizing with commodity monomers such as styrene using free radical polymerization techniques.

  2. Molten salt oxidation of organic hazardous waste with high salt content.

    PubMed

    Lin, Chengqian; Chi, Yong; Jin, Yuqi; Jiang, Xuguang; Buekens, Alfons; Zhang, Qi; Chen, Jian

    2018-02-01

    Organic hazardous waste often contains some salt, owing to the widespread use of alkali salts during industrial manufacturing processes. These salts cause complications during the treatment of this type of waste. Molten salt oxidation is a flameless, robust thermal process, with inherent capability of destroying the organic constituents of wastes, while retaining the inorganic ingredients in the molten salt. In the present study, molten salt oxidation is employed for treating a typical organic hazardous waste with a high content of alkali salts. The hazardous waste derives from the production of thiotriazinone. Molten salt oxidation experiments have been conducted using a lab-scale molten salt oxidation reactor, and the emissions of CO, NO, SO 2 , HCl and dioxins are studied. Impacts are investigated from the composition of the molten salts, the types of feeding tube, the temperature of molten carbonates and the air factor. Results show that the waste can be oxidised effectively in a molten salt bath. Temperature of molten carbonates plays the most important role. With the temperature rising from 600 °C to 750 °C, the oxidation efficiency increases from 91.1% to 98.3%. Compared with the temperature, air factor has but a minor effect, as well as the composition of the molten salts and the type of feeding tube. The molten carbonates retain chlorine with an efficiency higher than 99.9% and the emissions of dioxins are below 8 pg TEQ g -1 sample. The present study shows that molten salt oxidation is a promising alternative for the disposal of organic hazardous wastes containing a high salt content.

  3. Production of monodisperse, polymeric microspheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chang, Manchium (Inventor)

    1990-01-01

    Very small, individual polymeric microspheres with very precise size and a wide variation in monomer type and properties are produced by deploying a precisely formed liquid monomer droplet, suitably an acrylic compound such as hydroxyethyl methacrylate into a containerless environment. The droplet which assumes a spheroid shape is subjected to polymerizing radiation such as ultraviolet or gamma radiation as it travels through the environment. Polymeric microspheres having precise diameters varying no more than plus or minus 5 percent from an average size are recovered. Many types of fillers including magnetic fillers may be dispersed in the liquid droplet.

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

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

    Kaetsu, I.; Ito, A.; Hayashi, K.

    1973-08-01

    The effect of temperature and composition on the inflection point in the time-conversion curve and the saturated conversion was investigated in the gamma -radio-induced radical polymerization of binary systems consisting of a glass- forming monomer and a solvent. In the polymerization of completely homogeneous systems such as glycidyl methacrylate (GMA) -triacetin and hydroxyethyl methacrylate (HEMA) --propylene glycol systems, the time-conversion curve has an inflection point at polymerization temperatures between T/sub vm/(T/sub v/ of monomer system) and T/sub vp/ (T/sub v/ of polymer system). Such conversions at the inflection point changed monotonically between 0 and 100% in this temperature range. T/submore » v/ was found to be 30 to 50 deg C higher than T/sub g/ (glass transition temperature) and a monotonic function of composition (monomer -- polymer -- solvent). The acceleration effect continued to 100% conversion above T/sub vp/, and no acceleration effect was observed below T/sub vm/. The saturated conversion in homogeneous systems changed monotonically between 0 and 100% for polymerization temperatures between T/sub gm/ (T/sub g/ of monomer system) and T/sub gp/(T of polymer system). T/sub g/ was also a monotonic function of composition. No saturation in conversion was observed above T/sub gp/ , and no polymerization occurred below T/sub gm/. In the polymerization of completely heterogeneous systems such as HEMA-dioctyl phthalate, no acceleration effect was observed at any temperature and composition. The saturated conversion was 100% sbove T/sub g/ of pure HEMA, and no polymerization occurred below this temperature in this system. (auth)« less

  5. Ionic Hydrogel Based on Chitosan Cross-Linked with 6-Phosphogluconic Trisodium Salt as a Drug Delivery System.

    PubMed

    Martínez-Martínez, Mayte; Rodríguez-Berna, Guillermo; Gonzalez-Alvarez, Isabel; Hernández, Ma Jesús; Corma, Avelino; Bermejo, Marival; Merino, Virginia; Gonzalez-Alvarez, Marta

    2018-04-09

    In this work, 6-phosphogluconic trisodium salt (6-PG - Na + ) is introduced as a new aqueous and nontoxic cross-linking agent to obtain ionic hydrogels. Here, it is shown the formation of hydrogels based on chitosan cross-linked with 6-PG - Na + . This formulation is obtained by ionic interaction of cationic groups of polymer with anionic groups of the cross-linker. These hydrogels are nontoxic, do not cause dermal irritation, are easy to extend, and have an adequate adhesion force to be applied as polymeric film over the skin. This formulation exhibits a first order release kinetic and can be applied as drug vehicle for topical administration or as wound dressing for wound healing. The primary goal of this communication is to report the identification and utility of 6-phosphogluconic trisodium salt (6-PG - Na + ) as a nontoxic cross-linker applicable for cationic polymers.

  6. Highly permeable polymeric membranes based on the incorporation of the functional water channel protein Aquaporin Z

    PubMed Central

    Kumar, Manish; Grzelakowski, Mariusz; Zilles, Julie; Clark, Mark; Meier, Wolfgang

    2007-01-01

    The permeability and solute transport characteristics of amphiphilic triblock-polymer vesicles containing the bacterial water-channel protein Aquaporin Z (AqpZ) were investigated. The vesicles were made of a block copolymer with symmetric poly-(2-methyloxazoline)-poly-(dimethylsiloxane)-poly-(2-methyloxazoline) (PMOXA15-PDMS110-PMOXA15) repeat units. Light-scattering measurements on pure polymer vesicles subject to an outwardly directed salt gradient in a stopped-flow apparatus indicated that the polymer vesicles were highly impermeable. However, a large enhancement in water productivity (permeability per unit driving force) of up to ≈800 times that of pure polymer was observed when AqpZ was incorporated. The activation energy (Ea) of water transport for the protein-polymer vesicles (3.4 kcal/mol) corresponded to that reported for water-channel-mediated water transport in lipid membranes. The solute reflection coefficients of glucose, glycerol, salt, and urea were also calculated, and indicated that these solutes are completely rejected. The productivity of AqpZ-incorporated polymer membranes was at least an order of magnitude larger than values for existing salt-rejecting polymeric membranes. The approach followed here may lead to more productive and sustainable water treatment membranes, whereas the variable levels of permeability obtained with different concentrations of AqpZ may provide a key property for drug delivery applications. PMID:18077364

  7. 21 CFR 177.2250 - Filters, microporous polymeric.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Filters, microporous polymeric. 177.2250 Section... as Components of Articles Intended for Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in paragraph (a) of this section may be safely used, subject to the...

  8. 21 CFR 177.2250 - Filters, microporous polymeric.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Filters, microporous polymeric. 177.2250 Section... as Components of Articles Intended for Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in paragraph (a) of this section may be safely used, subject to the...

  9. 21 CFR 177.2250 - Filters, microporous polymeric.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Filters, microporous polymeric. 177.2250 Section... as Components of Articles Intended for Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in paragraph (a) of this section may be safely used, subject to the...

  10. 21 CFR 177.2250 - Filters, microporous polymeric.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Filters, microporous polymeric. 177.2250 Section... as Components of Articles Intended for Repeated Use § 177.2250 Filters, microporous polymeric. Microporous polymeric filters identified in paragraph (a) of this section may be safely used, subject to the...

  11. [Salt and cancer].

    PubMed

    Strnad, Marija

    2010-05-01

    Besides cardiovascular disease, a high salt intake causes other adverse health effects, i.e., gastric and some other cancers, obesity (risk factor for many cancer sites), Meniere's disease, worsening of renal disease, triggering an asthma attack, osteoporosis, exacerbation of fluid retention, renal calculi, etc. Diets containing high amounts of food preserved by salting and pickling are associated with an increased risk of cancers of the stomach, nose and throat. Because gastric cancer is still the most common cancer in some countries (especially in Japan), its prevention is one of the most important aspects of cancer control strategy. Observations among Japanese immigrants in the U.S.A. and Brazil based on the geographic differences, the trend in cancer incidence with time, and change in the incidence patterns indicate that gastric cancer is closely associated with dietary factors such as the intake of salt and salted food. The findings of many epidemiological studies suggest that high dietary salt intake is a significant risk factor for gastric cancer and this association was found to be strong in the presence of Helicobacter (H.) pylori infection with atrophic gastritis. A high-salt intake strips the lining of the stomach and may make infection with H. pylori more likely or may exacerbate the infection. Salting, pickling and smoking are traditionally popular ways of preparing food in Japan and some parts of Asia. In addition to salt intake, cigarette smoking and low consumption of fruit and vegetables increase the risk of stomach cancer. However, it is not known whether it is specifically the salt in these foods or a combination of salt and other chemicals that can cause cancer. One study identified a mutagen in nitrite-treated Japanese salted fish, and chemical structure of this mutagen suggests that it is derived from methionine and that salt and nitrite are precursors for its formation. Working under conditions of heat stress greatly increased the workers

  12. Fabrication of hydrophobic fluorinated silica-polyamide thin film nanocomposite reverse osmosis membranes with dramatically improved salt rejection.

    PubMed

    Pang, Ruizhi; Zhang, Kaisong

    2018-01-15

    Thin film nanocomposite reverse osmosis (TFN RO) membranes incorporated with hydrophilic nanoparticles show a potential problem that the salt rejection can not be improved significantly. In this study, novel TFN RO membranes incorporated with hydrophobic fluorinated silica nanoparticles were fabricated to improve the salt rejection. Fluorinated silica nanoparticles were well dispersed in organic phase during the interfacial polymerization (IP) process. The TFN RO membranes were characterized with attenuated total reflectance infra-red, field emission scanning electron microscopy, atomic force microscopy and water contact angle measurements. The preparation conditions of TFN RO membranes, including IP reaction time, organic solvent removal time, and fluorinated silica loading, were optimized by characterizing desalination performance using 2000ppm NaCl aqueous solution at 1.55MPa and 25°C. The salt rejection increased significantly from 96.0% without fluorinated silica nanoparticles to 98.6% with the optimal 0.12% (w/v) fluorinated silica nanoparticles, while the water flux decreased slightly from 0.99m 3 /m 2 /day to 0.93m 3 /m 2 /day. This study demonstrated the potential use of hydrophobic nanoparticles in high-performance TFN RO membranes. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. 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.

  14. Design of a bioresorbable polymeric scaffold for osteoblast culture

    NASA Astrophysics Data System (ADS)

    Ditaranto, Vincent M., Jr.

    Bioresorbable polymeric scaffolds were designed for the purpose of growing rat osteosarcoma cells (ROS 17/2.8) using the compression molding method. The material used in the construction of the scaffolds was a mixture of polycaprolactone (PCL), Hydroxyapatite (HA), Glycerin (GL) and salt (NaCl) for porosity. The concentration of the several materials utilized, was determined by volume. Past research at the University of Massachusetts Lowell (UML) has successfully utilized the compression molding method for the construction of scaffolds, but was unable to accomplish the goal of long term cell survival and complete cellular proliferation throughout a three dimensional scaffold. This research investigated various concentrations of the materials and molding temperatures used for the manufacture of scaffolds in order to improve the scaffold design and address those issues. The design of the scaffold using the compression molding process is detailed in the Method and Materials section of this thesis. The porogen (salt) used for porosity was suspected as a possible source of contamination causing cell apoptosis in past studies. This research addressed the issues for cell survival and proliferation throughout a three dimensional scaffold. The leaching of the salt was one major design modification. This research successfully used ultrasonic leaching in addition to the passive method. Prior to cell culture, the scaffolds were irradiated to 2.75 Mrad, with cobalt-60 gamma radionuclide. The tissue culture consisted of two trials: (1) cell culture in scaffolds cleaned with passive leaching; (2) cell culture with scaffolds cleaned with ultrasonic leaching. Cell survival and proliferation was accomplished only with the addition of ultrasonic leaching of the scaffolds. Analysis of the scaffolds included Scanning Electron Microscopy (SEM), Nikon light microscopy and x-ray mapping of the calcium, sodium and chloride ion distribution. The cells were analyzed by Environmental Scanning

  15. Profiling Groundwater Salt Concentrations in Mangrove Swamps and Tropical Salt Flats

    NASA Astrophysics Data System (ADS)

    Ridd, Peter V.; Sam, Renagi

    1996-11-01

    The salt concentration of groundwater in mangrove swamps is an important parameter controlling the growth of mangrove species. Extremely high salt concentrations of groundwater in tropical salt flats are responsible for the complete absence of macrophytes. Determining groundwater salt concentrations can be a very time-consuming and laborious process if conventional techniques are used. Typically, groundwater samples must be extracted for later laboratory analysis. In this work, a simple conductivity probe has been developed which may be inserted easily to a depth of 2 m into the sediment. The changes in conductivity of the sediment is due primarily to porewater salt concentration, and thus ground conductivity is useful in determining changes in groundwater salt concentrations. Using the conductivity probe, transects of sediment conductivity can be undertaken quickly. As an example of a possible application of the probe, transects of ground conductivity were taken on a mangrove swamp/saltflat system. The transects show clearly the sharp delineation in conductivity between the salt flat and mangrove swamp due to a change in groundwater salt concentrations. Horizontal and vertical salt concentration gradients of up to 50 g l -1 m -1and 150 g l -1 m -1, respectively, were found. Very sharp changes in groundwater salt concentrations at the interface between salt flats and mangroves indicate that the mangroves may be modifying the salinity of the groundwater actively.

  16. Protic Salt Polymer Membranes: High-Temperature Water-Free Proton-Conducting Membranes

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

    Gervasio, Dominic Francis

    2010-09-30

    at ambient pressures. Synthesis and processing of these protic salts into proton-conducting membrane is far from optimized. This protic salt approach has great promise for more improvements in proton conducting membranes for making practical compact, lightweight and inexpensive fuel cells with uses ranging from small electronics (Power = 1 to 100 Watts) to transportation (kiloWatts) to stationary applications (>100 kiloWatts). This work clearly showed that proton can be conducted without water using protoic ionic liquids which are Bronsted salts which contain a proton and whose acid and base moieties have pK separated by more than 4 units and less than 14. A key finding is that the base used should be significantly different than the basicity of water or else water displaces the base and an ordinary acid membrane is left behind. This is the case where the acid moiety is sulfonic acid found on perfluorinated polymeric membranes. This PI suggests that a fruitful route for attaining highly proton-conductive stable protic salt membranes is to use the STABLE poly-phosphazene (-P=N-) polymer backbone with electrochemically STABLE pendant acid or base units on the phosphorous of poly-phosphazene and with suitable pK so the base is NOT the same pK as water. From this work this should give stable water-free proton conductors which should allow for stable fuel cells with Pt catalysts and possible with non-platinum catalyst for the hydrogen anode and oxygen cathode.« less

  17. On the hydrophilicity of polyzwitterion poly (N,N-dimethyl-N-(3-(methacrylamido)propyl)ammoniopropane sulfonate) in water, deuterated water, and aqueous salt solutions.

    PubMed

    Hildebrand, Viet; Laschewsky, André; Zehm, Daniel

    2014-01-01

    A series of zwitterionic model polymers with defined molar masses up to 150,000 Da and defined end groups are prepared from sulfobetaine monomer N,N-dimethyl-N-(3-(methacrylamido)propyl)ammoniopropanesulfonate (SPP). Polymers are synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT) using a functional chain transfer agent labeled with a fluorescent probe. Their upper critical solution temperature-type coil-to-globule phase transition in water, deuterated water, and various salt solutions is studied by turbidimetry. Cloud points increase with polyzwitterion concentration and molar mass, being considerably higher in D2O than in H2O. Moreover, cloud points are strongly affected by the amount and nature of added salts. Typically, they increase with increasing salt concentration up to a maximum value, whereas further addition of salt lowers the cloud points again, mostly down to below freezing point. The different salting-in and salting-out effects of the studied anions can be correlated with the Hofmeister series. In physiological sodium chloride solution and in phosphate buffered saline (PBS), the cloud point is suppressed even for high molar mass samples. Accordingly, SPP-polymers behave strongly hydrophilic under most conditions encountered in biomedical applications. However, the direct transfer of results from model studies in D2O, using, e.g. (1)H NMR or neutron scattering techniques, to 'normal' systems in H2O is not obvious.

  18. Structural basis of reverse nucleotide polymerization

    PubMed Central

    Nakamura, Akiyoshi; Nemoto, Taiki; Heinemann, Ilka U.; Yamashita, Keitaro; Sonoda, Tomoyo; Komoda, Keisuke; Tanaka, Isao; Söll, Dieter; Yao, Min

    2013-01-01

    Nucleotide polymerization proceeds in the forward (5′-3′) direction. This tenet of the central dogma of molecular biology is found in diverse processes including transcription, reverse transcription, DNA replication, and even in lagging strand synthesis where reverse polymerization (3′-5′) would present a “simpler” solution. Interestingly, reverse (3′-5′) nucleotide addition is catalyzed by the tRNA maturation enzyme tRNAHis guanylyltransferase, a structural homolog of canonical forward polymerases. We present a Candida albicans tRNAHis guanylyltransferase-tRNAHis complex structure that reveals the structural basis of reverse polymerization. The directionality of nucleotide polymerization is determined by the orientation of approach of the nucleotide substrate. The tRNA substrate enters the enzyme’s active site from the opposite direction (180° flip) compared with similar nucleotide substrates of canonical 5′-3′ polymerases, and the finger domains are on opposing sides of the core palm domain. Structural, biochemical, and phylogenetic data indicate that reverse polymerization appeared early in evolution and resembles a mirror image of the forward process. PMID:24324136

  19. Measurement and Analysis of in vitro Actin Polymerization

    PubMed Central

    Doolittle, Lynda K.; Rosen, Michael K.; Padrick, Shae B.

    2014-01-01

    Summary The polymerization of actin underlies force generation in numerous cellular processes. While actin polymerization can occur spontaneously, cells maintain control over this important process by preventing actin filament nucleation and then allowing stimulated polymerization and elongation by several regulated factors. Actin polymerization, regulated nucleation and controlled elongation activities can be reconstituted in vitro, and used to probe the signaling cascades cells use to control when and where actin polymerization occurs. Introducing a pyrene fluorophore allows detection of filament formation by an increase in pyrene fluorescence. This method has been used for many years and continues to be broadly used, owing to its simplicity and flexibility. Here we describe how to perform and analyze these in vitro actin polymerization assays, with an emphasis on extracting useful descriptive parameters from kinetic data. PMID:23868594

  20. Escalation of polymerization in a thermal gradient

    PubMed Central

    Mast, Christof B.; Schink, Severin; Gerland, Ulrich; Braun, Dieter

    2013-01-01

    For the emergence of early life, the formation of biopolymers such as RNA is essential. However, the addition of nucleotide monomers to existing oligonucleotides requires millimolar concentrations. Even in such optimistic settings, no polymerization of RNA longer than about 20 bases could be demonstrated. How then could self-replicating ribozymes appear, for which recent experiments suggest a minimal length of 200 nt? Here, we demonstrate a mechanism to bridge this gap: the escalated polymerization of nucleotides by a spatially confined thermal gradient. The gradient accumulates monomers by thermophoresis and convection while retaining longer polymers exponentially better. Polymerization and accumulation become mutually self-enhancing and result in a hyperexponential escalation of polymer length. We describe this escalation theoretically under the conservative assumption of reversible polymerization. Taking into account the separately measured thermophoretic properties of RNA, we extrapolate the results for primordial RNA polymerization inside a temperature gradient in pores or fissures of rocks. With a dilute, nanomolar concentration of monomers the model predicts that a pore length of 5 cm and a temperature difference of 10 K suffice to polymerize 200-mers of RNA in micromolar concentrations. The probability to generate these long RNAs is raised by a factor of >10600 compared with polymerization in a physical equilibrium. We experimentally validate the theory with the reversible polymerization of DNA blocks in a laser-driven thermal trap. The results confirm that a thermal gradient can significantly enlarge the available sequence space for the emergence of catalytically active polymers. PMID:23630280

  1. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

    PubMed

    Coari, Kristin M; Martin, Rebecca C; Jain, Kopal; McGown, Linda B

    2017-09-01

    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  2. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

    NASA Astrophysics Data System (ADS)

    Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.

    2017-09-01

    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  3. 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.

  4. Spring-loaded polymeric gel actuators

    DOEpatents

    Shahinpoor, Mohsen

    1995-01-01

    Spring-loaded electrically controllable polymeric gel actuators are disclosed. The polymeric gels can be polyvinyl alcohol, polyacrylic acid, or polyacrylamide, and are contained in an electrolytic solvent bath such as water plus acetone. The action of the gel is mechanically biased, allowing the expansive and contractile forces to be optimized for specific applications.

  5. Visible‐Light‐Mediated Selective Arylation of Cysteine in Batch and Flow

    PubMed Central

    Bottecchia, Cecilia; Rubens, Maarten; Gunnoo, Smita B.; Hessel, Volker; Madder, Annemieke

    2017-01-01

    Abstract A mild visible‐light‐mediated strategy for cysteine arylation is presented. The method relies on the use of eosin Y as a metal‐free photocatalyst and aryldiazonium salts as arylating agents. The reaction can be significantly accelerated in a microflow reactor, whilst allowing the in situ formation of the required diazonium salts. The batch and flow protocol described herein can be applied to obtain a broad series of arylated cysteine derivatives and arylated cysteine‐containing dipeptides. Moreover, the method was applied to the chemoselective arylation of a model peptide in biocompatible reaction conditions (room temperature, phosphate‐buffered saline (PBS) buffer) within a short reaction time. PMID:28805276

  6. Investigation of Solution Polymerizations in Microgravity and 1 G

    NASA Technical Reports Server (NTRS)

    Kennedy, Alvin P.

    1998-01-01

    The in-situ dielectric spectra for the solution polymerization of polydiacetylene has been successfully measured. The results show a distinct difference between the response for the bulk solution and surface polymerization. It also shows a low frequency peak in the dissipation factor which is present in both the bulk and surface polymerizations. These features may prove to be significant indicators for important polymerization processes. Future studies will investigate the mechanisms responsible for these dielectric responses. This technique will eventually be used to monitor microgravity polymerizations and provide in-situ data on how microgravity affects solution polymerization.

  7. Microporous carbons derived from melamine and isophthalaldehyde: One-pot condensation and activation in a molten salt medium for efficient gas adsorption.

    PubMed

    Rehman, Adeela; Park, Soo-Jin

    2018-04-17

    In the present work, mixture of melamine and isophthalaldehyde undergo simultaneous polymerization, carbonization, and in situ activation in the presence of molten salt media through a single all-in-one route to design microporous carbons with high specific surface areas (~3000 m 2 /g). The effect of the activation temperature and molten salts on the polymerization process and final texture of the carbon was explored. Carbon materials prepared at 700 °C, in the presence of KOH (referred as MIK-700), exhibited a narrower pore-size distribution ~1.05 nm than those prepared in the presence of the eutectic KOH-NaOH mixture (MIKN). Additionally, MIK-700 possesses an optimum micropore volume (1.33 cm 3 /g) along with a high nitrogen content (2.66 wt%), resulting in the excellent CO 2 adsorption capacity of 9.7 mmol/g at 273 K and 1 bar. Similarly, the high specific area and highest total pore volume play an important role in H 2 storage at 77 K, with 4.0 wt% uptake by MIKN-800 (specific surface area and pore volume of 2984 m 2 /g and 1.98 cm 3 /g, respectively.) Thus, the facile one-step solvent-free synthesis and activation strategy is an economically favorable avenue for designing microporous carbons as an efficient gas adsorbents.

  8. Distillation and condensation of LiCl-KCl eutectic salts for a separation of pure salts from salt wastes from an electrorefining process

    NASA Astrophysics Data System (ADS)

    Eun, Hee Chul; Yang, Hee Chul; Lee, Han Soo; Kim, In Tae

    2009-12-01

    Salt separation and recovery from the salt wastes generated from a pyrochemical process is necessary to minimize the high-level waste volumes and to stabilize a final waste form. In this study, the thermal behavior of the LiCl-KCl eutectic salts containing rare earth oxychlorides or oxides was investigated during a vacuum distillation and condensation process. LiCl was more easily vaporized than the other salts (KCl and LiCl-KCl eutectic salt). Vaporization characteristics of LiCl-KCl eutectic salts were similar to that of KCl. The temperature to obtain the vaporization flux (0.1 g min -1 cm -2) was decreased by much as 150 °C by a reduction of the ambient pressure from 5 Torr to 0.5 Torr. Condensation behavior of the salt vapors was different with the ambient pressure. Almost all of the salt vapors were condensed and were formed into salt lumps during a salt distillation at the ambient pressure of 0.5 Torr and they were collected in the condensed salt storage. However, fine salt particles were formed when the salt distillation was performed at 10 Torr and it is difficult for them to be recovered. Therefore, it is thought that a salt vacuum distillation and condensation should be performed to recover almost all of the vaporized salts at a pressure below 0.5 Torr.

  9. Spring-loaded polymeric gel actuators

    DOEpatents

    Shahinpoor, M.

    1995-02-14

    Spring-loaded electrically controllable polymeric gel actuators are disclosed. The polymeric gels can be polyvinyl alcohol, polyacrylic acid, or polyacrylamide, and are contained in an electrolytic solvent bath such as water plus acetone. The action of the gel is mechanically biased, allowing the expansive and contractile forces to be optimized for specific applications. 5 figs.

  10. Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing

    DOEpatents

    Anderson, Brian L.

    2017-01-24

    A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.

  11. Micro-fluidic partitioning between polymeric sheets for chemical amplification and processing

    DOEpatents

    Anderson, Brian L.

    2015-05-26

    A system for fluid partitioning for chemical amplification or other chemical processing or separations of a sample, comprising a first dispenser of a first polymeric sheet, wherein the first polymeric sheet contains chambers; a second dispenser of a second polymeric sheet wherein the first dispenser and the second dispenser are positioned so that the first polymeric sheet and the second polymeric sheet become parallel; a dispenser of the fluid positioned to dispense the fluid between the first polymeric sheet and the second polymeric sheet; and a seal unit that seals the first polymeric sheet and the second polymeric sheet together thereby sealing the sample between the first polymeric sheet and the second polymeric sheet and partitioning the fluid for chemical amplification or other chemical processing or separations.

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

    NASA Astrophysics Data System (ADS)

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

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

  13. Effect of sodium chloride and sodium bicarbonate on the physicochemical properties of soft wheat flour doughs and gluten polymerization.

    PubMed

    Chen, Gengjun; Ehmke, Laura; Miller, Rebecca; Faa, Pierre; Smith, Gordon; Li, Yonghui

    2018-06-07

    Soft wheat flour doughs were prepared with different levels of salt (NaCl) and/or baking soda (NaHCO3). Oscillation rheology, elongational viscosity, and extensibility of doughs were tested to evaluate the effect of salt and/or baking soda on the physical properties of doughs. Furthermore, a series of physical-biochemical analytical techniques were used to investigate gluten polymerization in doughs, including Zeta potential analyzer, Fourier transform infrared spectroscopy (FTIR), spectrophotometer, and reversed phase high performance liquid chromatography (RP-HPLC). Addition of high levels of NaHCO3 (1.0 % fwb), either by itself or in combination with NaCl, increased dough strength, elongational viscosity, and viscoelasticity. RP-HPLC results demonstrated macromolecular aggregation of gluten proteins in the presence of NaCl and/or NaHCO3. Addition of NaHCO3 or NaCl also decreased both free sulfhydryl content and random coil structure of gluten isolated from the doughs. Overall, NaCl and/or NaHCO3 induced the changes of molecular conformation of gluten, which impacted the physicochemical qualities of soft wheat flour dough. Our study provides a better understanding of salt and baking soda functionality in the formation of soft flour dough, which will support the searching of feasible sodium reduction strategies in soft flour bakery products.

  14. Nonperturbative Renormalization Group Approach to Polymerized Membranes

    NASA Astrophysics Data System (ADS)

    Essafi, Karim; Kownacki, Jean-Philippe; Mouhanna, Dominique

    2014-03-01

    Membranes or membrane-like materials play an important role in many fields ranging from biology to physics. These systems form a very rich domain in statistical physics. The interplay between geometry and thermal fluctuations lead to exciting phases such flat, tubular and disordered flat phases. Roughly speaking, membranes can be divided into two group: fluid membranes in which the molecules are free to diffuse and thus no shear modulus. On the other hand, in polymerized membranes the connectivity is fixed which leads to elastic forces. This difference between fluid and polymerized membranes leads to a difference in their critical behaviour. For instance, fluid membranes are always crumpled, whereas polymerized membranes exhibit a phase transition between a crumpled phase and a flat phase. In this talk, I will focus only on polymerized phantom, i.e. non-self-avoiding, membranes. The critical behaviour of both isotropic and anisotropic polymerized membranes are studied using a nonperturbative renormalization group approach (NPRG). This allows for the investigation of the phase transitions and the low temperature flat phase in any internal dimension D and embedding d. Interestingly, graphene behaves just as a polymerized membrane in its flat phase.

  15. Targeted polymeric nanoparticles for cancer gene therapy

    PubMed Central

    Kim, Jayoung; Wilson, David R.; Zamboni, Camila G.; Green, Jordan J.

    2015-01-01

    In this article, advances in designing polymeric nanoparticles for targeted cancer gene therapy are reviewed. Characterization and evaluation of biomaterials, targeting ligands, and transcriptional elements are each discussed. Advances in biomaterials have driven improvements to nanoparticle stability and tissue targeting, conjugation of ligands to the surface of polymeric nanoparticles enable binding to specific cancer cells, and the design of transcriptional elements has enabled selective DNA expression specific to the cancer cells. Together, these features have improved the performance of polymeric nanoparticles as targeted non-viral gene delivery vectors to treat cancer. As polymeric nanoparticles can be designed to be biodegradable, non-toxic, and to have reduced immunogenicity and tumorigenicity compared to viral platforms, they have significant potential for clinical use. Results of polymeric gene therapy in clinical trials and future directions for the engineering of nanoparticle systems for targeted cancer gene therapy are also presented. PMID:26061296

  16. Relationship between the adjuvant and cytotoxic effects of the positive charges and polymerization in liposomes.

    PubMed

    Gasparri, Julieta; Speroni, Lucía; Chiaramoni, Nadia Silvia; del Valle Alonso, Silvia

    2011-06-01

    Vaccine development today encounters a main obstacle, which is the need for effective adjuvants suitable for clinical trials. Aluminum salts, discovered 70 years ago and, very recently, MF59, are the only types of adjuvants currently used in vaccines licensed by the U.S. Food and Drug Administration. Liposomes represent an alternative approach to vaccine adjuvants. In this article, we describe the inflammatory response and biological effect of polymerization and the addition of positive charges in liposome formulations. Nonpolymerized cationic (NP(+)) liposomes significantly reduce metabolism in Vero cells after 24 hours. Correspondingly, both NP(+) and polymerized cationic (P(+)) liposomes reduce cell viability following a 48-hour incubation. Similar results were obtained with cells from the peritoneal cavities of mice. Paradoxically, those liposomes that presented clearly cytostatic or cytotoxic effects in vitro stimulated metabolism and had a mitogenic effect in vivo. Finally, the adjuvant effect was tested by immunization in BALB/c mice. The major effect was obtained with NP(+) liposomes. Accordingly, we also demonstrated that NP(+) liposomes injected into the dermis produced an outstanding inflammatory reaction, showing the histopathological characteristics of an inoculation granuloma. Thus, positive charge would play an important role in the immunoadjuvant effect of liposomes by conferring them cytotoxic capacity.

  17. Molten Salt Promoting Effect in Double Salt CO2 Absorbents

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

    Zhang, Keling; Li, Xiaohong S.; Chen, Haobo

    2016-01-01

    The purpose of this paper is to elaborate on the concept of molten salts as catalysts for CO2 absorption by MgO, and extend these observations to the MgO-containing double salt oxides. We will show that the phenomena involved with CO2 absorption by MgO and MgO-based double salts are similar and general, but with some important differences. This paper focuses on the following key concepts: i) identification of conditions that favor or disfavor participation of isolated MgO during double salt absorption, and investigation of methods to increase the absorption capacity of double salt systems by including MgO participation; ii) examination ofmore » the relationship between CO2 uptake and melting point of the promoter salt, leading to the recognition of the role of pre-melting (surface melting) in these systems; and iii) extension of the reaction pathway model developed for the MgO-NaNO3 system to the double salt systems. This information advances our understanding of MgO-based CO2 absorption systems for application with pre-combustion gas streams.« less

  18. Triply responsive films in bioelectrocatalysis with a binary architecture: combined layer-by-layer assembly and hydrogel polymerization.

    PubMed

    Yao, Huiqin; Hu, Naifei

    2011-05-26

    In this work, triply responsive films with a specific binary architecture combining layer-by-layer assembly (LbL) and hydrogel polymerization were successfully prepared. First, concanavalin A (Con A) and dextran (Dex) were assembled into {Con A/Dex}(5) LbL layers on electrode surface by the lectin-sugar biospecific interaction between them. The poly(N,N-diethylacrylamide) (PDEA) hydrogels with entrapped horseradish peroxidase (HRP) were then synthesized by polymerization on the surface of LbL inner layers, forming {Con A/Dex}(5)-(PDEA-HRP) films. The films demonstrated reversible pH-, thermo-, and salt-responsive on-off behavior toward electroactive probe Fe(CN)(6)(3-) in its cyclic voltammetric responses. This multiple stimuli-responsive films could be further used to realize triply switchable electrochemical reduction of H(2)O(2) catalyzed by HRP immobilized in the films and mediated by Fe(CN)(6)(3-) in solution. The responsive mechanism of the films was explored and discussed. The pH-sensitive property of the system was attributed to the electrostatic interaction between the {Con A/Dex}(5) inner layers and the probe at different pH, and the thermo- and salt-responsive behaviors should be ascribed to the structure change of PDEA hydrogels for the PDEA-HRP outermost layers under different conditions. The concept of binary architecture was also used to fabricate {Con A/Dex}(5)-(PDEA-GOD) films on electrodes, where GOD = glucose oxidase, which was applied to realize the triply switchable bioelectrocatalysis of glucose by GOD in the films with ferrocenedicarboxylic acid as the mediator in solution. This film system with the unique binary architecture may establish a foundation for fabricating a novel type of multicontrollable biosensors based on bioelectrocatalysis with immobilized enzymes.

  19. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ultraviolet activator for polymerization. 872.6070 Section 872.6070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... polymerization. (a) Identification. An ultraviolet activator for polymerization is a device that produces...

  20. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet activator for polymerization. 872.6070 Section 872.6070 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... polymerization. (a) Identification. An ultraviolet activator for polymerization is a device that produces...

  1. Tubulin polymerization-stimulating activity of Ganoderma triterpenoids.

    PubMed

    Kohno, Toshitaka; Hai-Bang, Tran; Zhu, Qinchang; Amen, Yhiya; Sakamoto, Seiichi; Tanaka, Hiroyuki; Morimoto, Satoshi; Shimizu, Kuniyoshi

    2017-04-01

    Tubulin polymerization is an important target for anticancer therapies. Even though the potential of Ganoderma triterpenoids against various cancer targets had been well documented, studies on their tubulin polymerization-stimulating activity are scarce. This study was conducted to evaluate the effect of Ganoderma triterpenoids on tubulin polymerization. A total of twenty-four compounds were investigated using an in vitro tubulin polymerization assay. Results showed that most of the studied triterpenoids exhibited microtuble-stabilizing activity to different degrees. Among the investigated compounds, ganoderic acid T-Q, ganoderiol F, ganoderic acid S, ganodermanontriol and ganoderic acid TR were found to have the highest activities. A structure-activity relationship (SAR) analysis was performed. Extensive investigation of the SAR suggests the favorable structural features for the tubulin polymerization-stimulating activity of lanostane triterpenes. These findings would be helpful for further studies on the potential mechanisms of the anticancer activity of Ganoderma triterpenoids and give some indications on the design of tubulin-targeting anticancer agents.

  2. Spatial control of actin polymerization during neutrophil chemotaxis

    PubMed Central

    Weiner, Orion D.; Servant, Guy; Welch, Matthew D.; Mitchison, Timothy J.; Sedat, John W.; Bourne, Henry R.

    2010-01-01

    Neutrophils respond to chemotactic stimuli by increasing the nucleation and polymerization of actin filaments, but the location and regulation of these processes are not well understood. Here, using a permeabilized-cell assay, we show that chemotactic stimuli cause neutrophils to organize many discrete sites of actin polymerization, the distribution of which is biased by external chemotactic gradients. Furthermore, the Arp2/3 complex, which can nucleate actin polymerization, dynamically redistributes to the region of living neutrophils that receives maximal chemotactic stimulation, and the least-extractable pool of the Arp2/3 complex co-localizes with sites of actin polymerization. Our observations indicate that chemoattractant-stimulated neutrophils may establish discrete foci of actin polymerization that are similar to those generated at the posterior surface of the intracellular bacterium Listeria monocytogenes. We propose that asymmetrical establishment and/or maintenance of sites of actin polymerization produces directional migration of neutrophils in response to chemotactic gradients. PMID:10559877

  3. Spatial control of actin polymerization during neutrophil chemotaxis.

    PubMed

    Weiner, O D; Servant, G; Welch, M D; Mitchison, T J; Sedat, J W; Bourne, H R

    1999-06-01

    Neutrophils respond to chemotactic stimuli by increasing the nucleation and polymerization of actin filaments, but the location and regulation of these processes are not well understood. Here, using a permeabilized-cell assay, we show that chemotactic stimuli cause neutrophils to organize many discrete sites of actin polymerization, the distribution of which is biased by external chemotactic gradients. Furthermore, the Arp2/3 complex, which can nucleate actin polymerization, dynamically redistributes to the region of living neutrophils that receives maximal chemotactic stimulation, and the least-extractable pool of the Arp2/3 complex co-localizes with sites of actin polymerization. Our observations indicate that chemoattractant-stimulated neutrophils may establish discrete foci of actin polymerization that are similar to those generated at the posterior surface of the intracellular bacterium Listeria monocytogenes. We propose that asymmetrical establishment and/or maintenance of sites of actin polymerization produces directional migration of neutrophils in response to chemotactic gradients.

  4. Design of smart optical sensor using polyvinyl alcohol/Fluorescein sodium salt: Laser filters and optical limiting effect

    NASA Astrophysics Data System (ADS)

    Yahia, I. S.; Bouzidi, A.; Zahran, H. Y.; Jilani, W.; AlFaify, S.; Algarni, H.; Guermazi, H.

    2018-03-01

    Pure poly (vinyl alcohol) (PVA) and PVA doped Fluorescein-Sodium salt (FSS/PVA composite films) have synthesized on wide scale laser optical filters. The investigated polymeric composite films have been characterized using several methods. The XRD patterns exhibit a decrease of the average crystalline size and an increase of the internal strain, which explained the imperfection and distortion in the prepared films. The optical characterizations showed a decrease in the transmission of the incident light for different samples, which may be explained to the layer formed by intermolecular hydrogen bonding between the PVA matrix and the FSS particles. The FSS/PVA polymeric composite films are being a completely blocking in the UV-Vis light at the range between 190 and 560 nm, agreement with the optical limiting effect, which makes the composite films suitable for CUT-OFF laser filters applications. The decrease in its, directly and indirectly, allowed transition band gaps were controlled by the added FSS dyes molecules. The variation of the exponent frequency (s) of the power law for FSS/PVA polymeric composite films has been characterized to improve the hopping conduction mechanism in the materials. The dielectric permittivity (e‧) and dielectric loss (e'') have been decreased with increasing the applied frequency, and the incorporated FSS molecules due to the DC electric conductivity can cause the decreases of the polarization of the as-prepared films over the studied ranges.

  5. Polymerization properties of the Thermotoga maritima actin MreB: roles of temperature, nucleotides, and ions.

    PubMed

    Bean, Greg J; Amann, Kurt J

    2008-01-15

    MreB is a bacterial orthologue of actin that affects cell shape, polarity, and chromosome segregation. Although a significant body of work has explored its cellular functions, we know very little about the biochemical behavior of MreB. We have cloned, overexpressed in Escherichia coli, and purified untagged MreB1 from Thermotoga maritima. We have characterized the conditions that regulate its monomer-to-polymer assembly reaction, the critical concentrations of that reaction, the manner in which MreB uses nucleotides, its stability, and the structure of the assembled polymer. MreB requires a bound purine nucleotide for polymerization and rapidly hydrolyzes it following assembly. MreB assembly contains two distinct components, one that does not require divalent cations and one that does, which may comprise the nucleation and elongation phases of assembly, respectively. MreB assembly is strongly favored by increasing temperature or protein concentration but inhibited differentially by high concentrations of monovalent salts. The polymerization rate increases and the bulk critical concentration decreases with increasing temperature, but in contrast to previous reports, MreB is capable of polymerizing across a broad range of temperatures. MreB polymers are shorter and stiffer and scatter more light than eukaryotic actin filaments. Due to rapid ATP hydrolysis and phosphate release, we suggest that most assembled MreB in cells is in the ADP-bound state. Because of only moderate differences between the ATP and ADP critical concentrations, treadmilling may occur, but we do not predict dynamic instability in cells. Because of the relatively low cellular concentration of MreB and the observed structural properties of the polymer, a single MreB assembly may exist in cells.

  6. 21 CFR 870.3650 - Pacemaker polymeric mesh bag.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

  7. 21 CFR 870.3650 - Pacemaker polymeric mesh bag.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

  8. 21 CFR 870.3650 - Pacemaker polymeric mesh bag.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

  9. 21 CFR 870.3650 - Pacemaker polymeric mesh bag.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Pacemaker polymeric mesh bag. 870.3650 Section 870...) MEDICAL DEVICES CARDIOVASCULAR DEVICES Cardiovascular Prosthetic Devices § 870.3650 Pacemaker polymeric mesh bag. (a) Identification. A pacemaker polymeric mesh bag is an implanted device used to hold a...

  10. Glycine Polymerization on Oxide Minerals.

    PubMed

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  11. Deformation of allochthonous salt and evolution of related salt-structural systems, eastern Louisiana Gulf Coast

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

    Schuster, D.C.

    1996-12-31

    Salt tectonics in the northern Gulf of Mexico involves both vertical diapirism and lateral silling or flow of salt into wings and tablets (sheets). Combinations of these two modes of salt deformation, concurrent with sediment loading and salt evacuation, have produced complex structures in the coastal and offshore region of southeastern Louisiana, a prolific oil and gas province. Many large growth faults and salt domes in the study area root into intra-Tertiary salt welds that were formerly occupied by allochthonous salt tablets. Two end-member structural systems involving evacuation of former tabular salt are recognized: roho systems and stepped counter-regional systems.more » Both end-member systems share a similar multi-staged evolution, including (1) initial formation of a south-leaning salt dome or wall sourced from the Jurassic salt level; (2) progressive development into a semi-tabular allochthonous salt body; and (3) subsequent loading, evacuation, and displacement of the tabular salt into secondary domes. In both systems, it is not uncommon to find salt displaced as much as 16-24 km south of its autochthonous source, connected by a horizontal salt weld to an updip, deflated counter-regional feeder. Although both end-member structural systems may originate before loading of allochthonous salt having grossly similar geometry, their final structural configurations after loading and salt withdrawal are distinctly different. Roho systems are characterized by large-displacement, listric, south-dipping growth faults that sole into intra-Tertiary salt welds marked by high-amplitude reflections continuous with residual salt masses. Salt from the former salt tablets has been loaded and squeezed laterally and downdip. Stepped counter-regional systems, in contrast, comprise large salt domes and adjacent large-displacement, north-dipping growth faults that sole into intra-Tertiary salt welds before stepping down again farther north.« less

  12. New iodide-based molten salt systems for high temperature molten salt batteries

    NASA Astrophysics Data System (ADS)

    Fujiwara, Syozo; Kato, Fumio; Watanabe, Syouichiro; Inaba, Minoru; Tasaka, Akimasa

    Novel multi-component molten salt systems containing iodides, LiF-LiBr-LiI, LiF-NaBr-LiI, and LiF-LiCl-LiBr-LiI, were investigated for use as electrolytes in high temperature molten salt batteries to improve the discharge rate-capability. The iodide-based molten salts showed higher ionic conductivity (∼3 S cm -1 at 500 °C) than conventional LiCl-KCl, and had low enough melting points (below 400 °C) that can be used in practical high temperature molten salt batteries. The iodide-based salts showed instability at temperatures higher than 280 °C in dried air. The decomposition mechanism of iodide-based molten salts was discussed, and it was found that elimination of oxygen from the environment is effective to stabilize the iodide-based molten salts at high temperatures.

  13. Salt-responsive lytic polysaccharide monooxygenases from the mangrove fungus Pestalotiopsis sp. NCi6.

    PubMed

    Patel, Ilabahen; Kracher, Daniel; Ma, Su; Garajova, Sona; Haon, Mireille; Faulds, Craig B; Berrin, Jean-Guy; Ludwig, Roland; Record, Eric

    2016-01-01

    Lytic polysaccharide monooxygenases (LPMOs) belong to the "auxiliary activities (AA)" enzyme class of the CAZy database. They are known to strongly improve the saccharification process and boost soluble sugar yields from lignocellulosic biomass, which is a key step in the efficient production of sustainable economic biofuels. To date, most LPMOs have been characterized from terrestrial fungi, but novel fungal LPMOs isolated from more extreme environments such as an estuary mangrove ecosystem could offer enzymes with unique properties in terms of salt tolerance and higher stability under harsh condition. Two LPMOs secreted by the mangrove-associated fungus Pestalotiopsis sp. NCi6 (PsLPMOA and PsLPMOB) were expressed in the yeast Pichia pastoris and produced in a bioreactor with >85 mg L(-1) for PsLPMOA and >260 mg L(-1) for PsLPMOB. Structure-guided homology modeling of the PsLPMOs showed a high abundance of negative surface charges, enabling enhanced protein stability and activity in the presence of sea salt. Both PsLPMOs were activated by a cellobiose dehydrogenase (CDH) from Neurospora crassa, with an apparent optimum of interaction at pH 5.5. Investigation into their regioselective mode of action revealed that PsLPMOA released C1- and C4-oxidized cello-oligosaccharide products, while PsLPMOB released only C4-oxidized products. PsLPMOA was found to cleave polymeric cellulose in the presence of up to 6 % sea salt, which emphasizes the use of sea water in the industrial saccharification process with improved ecological footprints. Two new LPMOs from the mangrove fungus Pestalotiopsis sp. NCi6 were found to be fully reactive against cellulose. The combined hydrolytic activities of these salt-responsive LPMOs could therefore facilitate the saccharification process using sea water as a reaction medium for large-scale biorefineries.

  14. Method of Making Thermally Stable, Piezoelectric and Proelectric Polymeric Substrates

    NASA Technical Reports Server (NTRS)

    Simpson, Joycelyn O. (Inventor); St.Clair, Terry L. (Inventor)

    1999-01-01

    A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium: applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

  15. Phosphoniums as catalysts for metal-free polymerization: Synthesis of well-defined poly(propylene oxide)

    NASA Astrophysics Data System (ADS)

    Zhang, Jie; Liu, Quan; Ren, Haojun; Zhang, Nanjie; Li, Pengfei; Yang, Kang

    2017-11-01

    The anionic ring-opening polymerization of propylene oxide (PO) was initiated with glycerol and catalyzed by three new synthetic phosphonium salts, tetrakis (pyrrolidino) phosphonium (Py4P1+), tetrakis (piperidino) phosphonium (Pi4P1+), tetrakis (morpholino) phosphonium (Mo4P1+), and the known tetrakis [cyclohexyl (methyl) amino] phosphonium (Cy4P1+) and tetrakis [tris (dimethylamino) phosphonoamino] phosphazene (P5+). The effects of substituents on the polymerization behavior, especially the molecular weight and its distribution, degree of unsaturation, and the sequential structures of poly (propylene oxide) (PPO) were investigated. The structures of these catalysts and PPOs were characterized by FT-IR, 1H and 13C NMR, and GPC. The results indicate that Cy4P1+, Py4P1+, and Pi4P1+ have lower optimum reaction temperatures at 90, 70, and 70 °C, respectively, and are better than traditional catalysts KOH and double metal cyanide. PPO samples with high molecular weight, narrow polydispersity, and high functionality were accessible when catalyzed with Cy4P1+, Pi4P1+, and P5+ at the optimum temperature. Notably, Pi4P1+ formed unimodal distribution PPO with 9000 g/mol, 2.93 of functionality, and 0.008 mmol/g degree of unsaturation. Majority segments of PPO from five catalysts adopted the stereoregular head-to-tail structure, exhibiting excellent regularity.

  16. Effect of salt intake on beat-to-beat blood pressure nonlinear dynamics and entropy in salt-sensitive versus salt-protected rats.

    PubMed

    Fares, Souha A; Habib, Joseph R; Engoren, Milo C; Badr, Kamal F; Habib, Robert H

    2016-06-01

    Blood pressure exhibits substantial short- and long-term variability (BPV). We assessed the hypothesis that the complexity of beat-to-beat BPV will be differentially altered in salt-sensitive hypertensive Dahl rats (SS) versus rats protected from salt-induced hypertension (SSBN13) maintained on high-salt versus low-salt diet. Beat-to-beat systolic and diastolic BP series from nine SS and six SSBN13 rats (http://www.physionet.org) were analyzed following 9 weeks on low salt and repeated after 2 weeks on high salt. BP complexity was quantified by detrended fluctuation analysis (DFA), short- and long-range scaling exponents (αS and αL), sample entropy (SampEn), and traditional standard deviation (SD) and coefficient of variation (CV(%)). Mean systolic and diastolic BP increased on high-salt diet (P < 0.01) particularly for SS rats. SD and CV(%) were similar across groups irrespective of diet. Salt-sensitive and -protected rats exhibited similar complexity indices on low-salt diet. On high salt, (1) SS rats showed increased scaling exponents or smoother, systolic (P = 0.007 [αL]) and diastolic (P = 0.008 [αL]) BP series; (2) salt-protected rats showed lower SampEn (less complex) systolic and diastolic BP (P = 0.046); and (3) compared to protected SSBN13 rats, SS showed higher αL for systolic (P = 0.01) and diastolic (P = 0.005) BP Hypertensive SS rats are more susceptible to high salt with a greater rise in mean BP and reduced complexity. Comparable mean pressures in sensitive and protective rats when on low-salt diet coupled with similar BPV dynamics suggest a protective role of low-salt intake in hypertensive rats. This effect likely reflects better coupling of biologic oscillators. © 2016 The Authors. Physiological Reports published by Wiley Periodicals, Inc. on behalf of the American Physiological Society and The Physiological Society.

  17. Synthesis and antibacterial properties of water-dispersible silver nanoparticles stabilized by metal-carbon σ-bonds

    NASA Astrophysics Data System (ADS)

    Kawai, Koji; Narushima, Takashi; Kaneko, Kotaro; Kawakami, Hayato; Matsumoto, Miyuki; Hyono, Atsushi; Nishihara, Hiroshi; Yonezawa, Tetsu

    2012-12-01

    The synthesis of 4-diazoniumcarboxylbenzene fluoroborate, a new water-soluble stabilizer for metal nanoparticles (NPs), is described. A stable dispersion of Ag NPs in water was successfully produced by a simultaneous aqueous reduction of this diazonium salt and silver nitrate by NaBH4. UV-vis spectra, TEM images, XRD patterns, and XPS spectra of the obtained Ag NPs revealed that they were stabilized by Ag-C σ-bonds. These NPs showed excellent antimicrobial properties against Staphylococcus aureus.

  18. Frontal Polymerization of Dicyclopentadiene: A Numerical Study.

    PubMed

    Goli, Elyas; Robertson, Ian D; Geubelle, Philippe H; Moore, Jeffrey S

    2018-04-26

    As frontal polymerization is being considered as a faster and more energy efficient manufacturing technique for polymer-matrix fiber-reinforced composites, we perform a finite-element-based numerical study of the initiation and propagation of a polymerization front in dicyclopentadiene (DCPD). The transient thermochemical simulations are complemented by an analytical study of the steady-state propagation of the polymerization front, allowing to draw a direct link between the cure kinetics model and the key characteristics of the front, i.e., front velocity and characteristic length scales. The second part of this study focuses on the prediction of the temperature spike associated with the merger of two polymerization fronts. The thermal peak, which might be detrimental to the properties of the polymerized material, is due to the inability of the heat associated with the highly exothermic reaction to be dissipated when the two fronts merge. The analysis investigates how the amplitude of the thermal spike is affected by the degree of cure at the time of the front merger.

  19. Electrolyte salts for power sources

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

    Doddapaneni, Narayan; Ingersoll, David

    Electrolyte salts for power sources comprising salts of phenyl polysulfonic acids and phenyl polyphosphonic acids. The preferred salts are alkali and alkaline earth metal salts, most preferably lithium salts.

  20. Highly Transparent, Nanofiller-Reinforced Scratch-Resistant Polymeric Composite Films Capable of Healing Scratches.

    PubMed

    Li, Yang; Chen, Shanshan; Li, Xiang; Wu, Mengchun; Sun, Junqi

    2015-10-27

    Integration of healability and mechanical robustness is challenging in the fabrication of highly transparent films for applications as protectors in optical and displaying devices. Here we report the fabrication of healable, highly transparent and scratch-resistant polymeric composite films that can conveniently and repeatedly heal severe damage such as cuts of several tens of micrometers wide and deep. The film fabrication process involves layer-by-layer (LbL) assembly of a poly(acrylic acid) (PAA) blend and branched poly(ethylenimine) (bPEI) blend, where each blend contains the same polyelectrolytes of low and high molecular weights, followed by annealing the resulting PAA/bPEI films with aqueous salt solution and incorporation of CaCO3 nanoparticles as nanofillers. The rearrangement of low-molecular-weight PAA and bPEI under aqueous salt annealing plays a critical role in eliminating film defects to produce optically highly transparent polyelectrolyte films. The in situ formation of tiny and well-dispersed CaCO3 nanoparticles gives the resulting composite films enhanced scratch-resistance and also retains the healing ability of the PAA/bPEI matrix films. The reversibility of noncovalent interactions among the PAA, bPEI, and CaCO3 nanoparticles and the facilitated migration of PAA and bPEI triggered by water enable healing of the structural damage and restoration of optical transparency of the PAA/bPEI films reinforced with CaCO3 nanoparticles.

  1. 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).

  2. Method for forming polymerized microfluidic devices

    DOEpatents

    Sommer, Gregory J [Livermore, CA; Hatch, Anson V [Tracy, CA; Wang, Ying-Chih [Pleasanton, CA; Singh, Anup K [Danville, CA; Renzi, Ronald F [Tracy, CA; Claudnic, Mark R [Livermore, CA

    2011-11-01

    Methods for making a micofluidic device according to embodiments of the present invention include defining a cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

  3. Method for forming polymerized microfluidic devices

    DOEpatents

    Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.

    2013-03-12

    Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

  4. DFT analysis of the structure and IR spectrum of potassium salt of diphenylsulfophthalide - A model compound for polydiphenylenesulfophthalide salts

    NASA Astrophysics Data System (ADS)

    Shishlov, N. M.; Akhmetzyanov, Sh S.; Khursan, S. L.

    2017-02-01

    Experimental IR spectra of crystalline dried and non-dried potassium diphenylsulfophthalide (TAC-K) as a model compound for polymeric salts are presented. DFT analysis (B3LYP/6-311G(d,p)) of the structure and IR spectra of a series of compounds similar in structure to TAC-K as well as their dimers indicates that the sulfonate group environment strongly affects the positions of absorption bands (ABs) of vibrations of Ssbnd O bonds and demonstrates that information on the exact structure of ion clusters is needed for reliable and unambiguous assignment of the ABs in experimental IR spectra of real sulfonate ion containing systems to particular vibrational modes. Various ways of metal ion coordination with sulfonate ion, as well as their reflection in IR spectra of model compounds, are considered and discussed. Using TAC-K as an example, the effect of an intramolecular hydrogen bond on the vibrational modes of sulfonate group and hydroxy group is considered. The effect of ion aggregation on the shape of the IR spectrum of TAC-K is analyzed for an energetically favorable dimer of this salt as an example. Based on a combination of calculated, literature and reference data, a number of ABs in the IR spectra of TAC-K have been tentatively assigned. In particular, the bands in the region of 3230-3180 cm-1 have been assigned to ν(Osbnd H); those at 1240-1160 cm-1, to νas(SO3-); the AB at 1080 cm-1, to νs(SO3-); that at 616 cm-1, to δ(oop)s(SO3-); and that at 570 cm-1, to δ(ip)as(SO3-).

  5. Probing actin polymerization by intermolecular cross-linking.

    PubMed

    Millonig, R; Salvo, H; Aebi, U

    1988-03-01

    We have used N,N'-1,4-phenylenebismaleimide, a bifunctional sulfhydryl cross-linking reagent, to probe the oligomeric state of actin during the early stages of its polymerization into filaments. We document that one of the first steps in the polymerization of globular monomeric actin (G-actin) under a wide variety of ionic conditions is the dimerization of a significant fraction of the G-actin monomer pool. As polymerization proceeds, the yield of this initial dimer ("lower" dimer with an apparent molecular mass of 86 kD by SDS-PAGE [LD]) is attenuated, while an actin filament dimer ("upper" dimer with an apparent molecular mass of 115 kD by SDS-PAGE [UD] as characterized [Elzinga, M., and J. J. Phelan. 1984. Proc. Natl. Acad. Sci. USA. 81:6599-6602]) is formed. This shift from LD to UD occurs concomitant with formation of filaments as assayed by N-(1-pyrenyl)iodoacetamide fluorescence enhancement and electron microscopy. Isolated cross-linked LD does not form filaments, while isolated cross-linked UD will assemble into filaments indistinguishable from those polymerized from unmodified G-actin under typical filament-forming conditions. The presence of cross-linked LD does not effect the kinetics of polymerization of actin monomer, whereas cross-linked UD shortens the "lag phase" of the polymerization reaction in a concentration-dependent fashion. Several converging lines of evidence suggest that, although accounting for a significant oligomeric species formed during early polymerization, the LD is incompatible with the helical symmetry defining the mature actin filament; however, it could represent the interfilament dimer found in paracrystalline arrays or filament bundles. Furthermore, the LD is compatible with the unit cell structure and symmetry common to various types of crystalline actin arrays (Aebi, U., W. E. Fowler, G. Isenberg, T. D. Pollard, and P. R. Smith. 1981. J. Cell Biol. 91:340-351) and might represent the major structural state in which a mutant

  6. Chemical Polymerization and Langmuir-Blodgett Techniques. 2. The Polymerization of Monolayers of 3-Substituted Pyrroles

    DTIC Science & Technology

    1993-09-12

    the liquid -air interface could be monitored by changes in the surface area. Deposition of monolayers by Langmuir - Blodgett technique is possible and...polymerization product from the LB trough in chloroform solution. Figure 10 Langmuir - Blodgett transfer of poly (3-hexadecyl pyrrole) onto hydrophobized glass... Langmuir - Blodgett Techniques, 2: The Polymerization of Monolayers of 3-Substituted Pyrroles by W.M. Sigmund, C. Marestin, S. Keil, H. Zhou and R.S

  7. Balancing sub- and supra-salt strain in salt-influenced rifts: Implications for extension estimates

    NASA Astrophysics Data System (ADS)

    Coleman, Alexander J.; Jackson, Christopher A.-L.; Duffy, Oliver B.

    2017-09-01

    The structural style of salt-influenced rifts may differ from those formed in predominantly brittle crust. Salt can decouple sub- and supra-salt strain, causing sub-salt faults to be geometrically decoupled from, but kinematically coupled to and responsible for, supra-salt forced folding. Salt-influenced rifts thus contain more folds than their brittle counterparts, an observation often ignored in extension estimates. Fundamental to determining whether sub- and supra-salt structures are kinematically coherent, and the relative contributions of thin- (i.e. gravity-driven) and thick-skinned (i.e. whole-plate stretching) deformation to accommodating rift-related strain, is our ability to measure extension at both structural levels. We here use published physical models of salt-influenced extension to show that line-length estimates yield more accurate values of sub- and supra-salt extension compared to fault-heave, before applying these methods to seismic data from the Halten Terrace, offshore Norway. We show that, given the abundance of ductile deformation in salt-influenced rifts, significant amounts of extension may be ignored, leading to the erroneous interpretations of thin-skinned, gravity-gliding. If a system is kinematically coherent, supra-salt structures can help predict the occurrence and kinematics of sub-salt faults that may be poorly imaged and otherwise poorly constrained.

  8. Reducing the Salt Added to Takeaway Food: Within-Subjects Comparison of Salt Delivered by Five and 17 Holed Salt Shakers in Controlled Conditions

    PubMed Central

    Goffe, Louis; Wrieden, Wendy; Penn, Linda; Hillier-Brown, Frances; Lake, Amelia A.; Araujo-Soares, Vera; Summerbell, Carolyn; White, Martin; Adamson, Ashley J.

    2016-01-01

    Objectives To determine if the amount of salt delivered by standard salt shakers commonly used in English independent takeaways varies between those with five and 17 holes; and to determine if any differences are robust to variations in: the amount of salt in the shaker, the length of time spent shaking, and the person serving. Design Four laboratory experiments comparing the amount of salt delivered by shakers. Independent variables considered were: type of shaker used (five or 17 holes), amount of salt in the shaker before shaking commences (shaker full, half full or nearly empty), time spent shaking (3s, 5s or 10s), and individual serving. Setting Controlled, laboratory, conditions. Participants A quota-based convenience sample of 10 participants (five women) aged 18–59 years. Main Outcome Measures Amount of salt delivered by salt shakers. Results Across all trials, the 17 holed shaker delivered a mean (SD) of 7.86g (4.54) per trial, whilst the five holed shaker delivered 2.65g (1.22). The five holed shaker delivered a mean of 33.7% of the salt of the 17 holed shaker. There was a significant difference in salt delivered between the five and 17 holed salt shakers when time spent shaking, amount of salt in the shaker and participant were all kept constant (p<0.001). This difference was robust to variations in the starting weight of shakers, time spent shaking and participant shaking (pssalt shakers have the potential to reduce the salt content of takeaway food, and particularly food from Fish & Chip shops, where these shakers are particularly used. Further research will be required to determine the effects of this intervention on customers’ salt intake with takeaway food and on total dietary salt intake. PMID:27668747

  9. Diazonium modification of porous graphitic carbon with catechol and amide groups for hydrophilic interaction and attenuated reversed phase liquid chromatography.

    PubMed

    Iverson, Chad D; Zhang, Ya; Lucy, Charles A

    2015-11-27

    Porous graphitic carbon (PGC) is an increasingly popular and attractive phase for HPLC on account of its chemical and thermal stability, and its unique separation mechanism. However, native PGC is strongly hydrophobic and in some instances excessively retentive. As part of our effort to build a library of hydrophilic covalently modified PGC phases, we functionalized PGC with catechol and amide groups by means of aryl diazonium chemistry to produce two new phases. Successful grafting was confirmed by X-ray photoelectron spectroscopy (XPS). Under HILIC conditions, the Catechol-PGC showed up to 5-fold increased retention relative to unmodified PGC and selectivity that differed from four other HILIC phases. Under reversed phase conditions, the Amide-PGC reduced the retentivity of PGC by almost 90%. The chromatographic performance of Catechol-PGC and Amide-PGC is demonstrated by separations of nucleobases, nucleosides, phenols, alkaline pharmaceuticals, and performance enhancing stimulants. These compounds had retention factors (k) ranging from 0.5 to 13. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Kunststoffe (Polymere)

    NASA Astrophysics Data System (ADS)

    Weißbach, Wolfgang

    Polymere bestehen aus Riesen- oder Makromolekülen, die durch chemische Reaktionen aus einfachen, niedermolekularen Verbindungen entstehen, den Monomeren. Ausgangsstoffe sind überwiegend Kohlenwasserstoffe (KW), die größte Gruppe der C-Verbindungen. Sie müssen reaktionsfähige Stellen besitzen, das sind OH-Gruppen oder Dopppelbindungen.

  11. One-pot formation of 1,3,4-oxadiazol-2(3H)-ones and dibenzo[c,e]azepines by concomitant cathodic reduction of diazonium salts and phenanthrenequinones.

    PubMed

    Batanero, Belen; Barba, Fructuoso; Martin, Avelino

    2013-09-20

    The one-pot concomitant electrochemical reduction of phenanthrenequinones (1, 2) and arenediazonium salts (3a-f) led to the formation of 1,3,4-oxadiazol-2(3H)-ones (4a-f, 5a) and dibenzo[c,e]azepines (6a-f) when N-methylformamide was used as the solvent. A new pathway, different from those previously described with other aprotic solvents, is proposed. The experimental data support a radical mechanism for the electrochemical process followed by an internal rearrangement to give the products.

  12. Polymerization of Conducting Polymers Confined to Free Surfaces: A comparison of the Langmuir-Blodgett Polymerization of 3-Alkyl Pyrroles and 2- Alkyl Anilines

    DTIC Science & Technology

    1992-05-19

    Confined to Free Surfaces: A Comparison of the Langmuir-Blodgett Polymerization of 3- Alkyl Pyrroles and 2- Alkyl Anilines Submitted for Publication in...Surfaces: A Comparison of the Langmuir Blodgett Polymerizations of 3- alkyl pyrroles and 2- alkyl anilines R. S. Duran and H.C. Zhou Dept. of Chemistry...polymerization reactions in more detail and compare them. To do this, the polymerization reactions were run under two conditions. In the first case

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

    PubMed

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

    2013-09-01

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

  14. On-demand photoinitiated polymerization

    DOEpatents

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2015-01-13

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  15. On-demand photoinitiated polymerization

    DOEpatents

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2013-12-10

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  16. Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

    NASA Astrophysics Data System (ADS)

    Visentin, Adam F.

    Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was

  17. Distribution of Particles, Small Molecules and Polymeric Formulation Excipients in the Suprachoroidal Space after Microneedle Injection

    PubMed Central

    Chiang, Bryce; Venugopal, Nitin; Edelhauser, Henry F.; Prausnitz, Mark R.

    2016-01-01

    The purpose of this work was to determine the effect of injection volume, formulation composition, and time on circumferential spread of particles, small molecules and polymeric formulation excipients in the suprachoroidal space (SCS) after microneedle injection into New Zealand White rabbit eyes ex vivo and in vivo. Microneedle injections of 25–150 μL Hank’s Balanced Salt Solution (HBSS) containing 0.2 μm red-fluorescent particles and a model small molecule (fluorescein) were performed in rabbit eyes ex vivo, and visualized via flat mount. Particles with diameters of 0.02 – 2 μm were co-injected into SCS in vivo with fluorescein or a polymeric formulation excipient: fluorescein isothiocyanate (FITC)-labeled Discovisc or FITC-labeled carboxymethyl cellulose (CMC). Fluorescent fundus images were acquired over time to determine area of particle, fluorescein and polymeric formulation excipient spread, as well as their co-localization. We found that fluorescein covered a significantly larger area than co-injected particles when suspended in HBSS, and that this difference was present from 3 min post-injection onwards. We further showed that there was no difference in initial area covered by FITC-Discovisc and particles; the transport time (i.e., the time until the FITC-Discovisc and particle area began dissociating) was 2 d. There was also no difference in initial area covered by FITC-CMC and particles; the transport time in FITC-CMC was 4 d. We also found that particle size (20 nm – 2 μm) had no effect on spreading area when delivered in HBSS or Discovisc. We conclude that (i) the area of particle spread in SCS during injection generally increased with increasing injection volume, was unaffected by particle size and was significantly less than the area of fluorescein spread, (ii) particles suspended in low-viscosity HBSS formulation were entrapped in the SCS after injection, whereas fluorescein was not and (iii) particles co-injected with viscous polymeric

  18. Distribution of particles, small molecules and polymeric formulation excipients in the suprachoroidal space after microneedle injection.

    PubMed

    Chiang, Bryce; Venugopal, Nitin; Edelhauser, Henry F; Prausnitz, Mark R

    2016-12-01

    The purpose of this work was to determine the effect of injection volume, formulation composition, and time on circumferential spread of particles, small molecules, and polymeric formulation excipients in the suprachoroidal space (SCS) after microneedle injection into New Zealand White rabbit eyes ex vivo and in vivo. Microneedle injections of 25-150 μL Hank's Balanced Salt Solution (HBSS) containing 0.2 μm red-fluorescent particles and a model small molecule (fluorescein) were performed in rabbit eyes ex vivo, and visualized via flat mount. Particles with diameters of 0.02-2 μm were co-injected into SCS in vivo with fluorescein or a polymeric formulation excipient: fluorescein isothiocyanate (FITC)-labeled Discovisc or FITC-labeled carboxymethyl cellulose (CMC). Fluorescent fundus images were acquired over time to determine area of particle, fluorescein, and polymeric formulation excipient spread, as well as their co-localization. We found that fluorescein covered a significantly larger area than co-injected particles when suspended in HBSS, and that this difference was present from 3 min post-injection onwards. We further showed that there was no difference in initial area covered by FITC-Discovisc and particles; the transport time (i.e., the time until the FITC-Discovisc and particle area began dissociating) was 2 d. There was also no difference in initial area covered by FITC-CMC and particles; the transport time in FITC-CMC was 4 d. We also found that particle size (20 nm-2 μm) had no effect on spreading area when delivered in HBSS or Discovisc. We conclude that (i) the area of particle spread in SCS during injection generally increased with increasing injection volume, was unaffected by particle size, and was significantly less than the area of fluorescein spread, (ii) particles suspended in low-viscosity HBSS formulation were entrapped in the SCS after injection, whereas fluorescein was not and (iii) particles co-injected with viscous

  19. Great Salt Lake and Bonneville Salt Flats, UT, USA

    NASA Technical Reports Server (NTRS)

    1992-01-01

    This is a view of the Great Salt Lake and nearby Bonneville Salt Flats, UT, (41.0N, 112.5W). A railroad causeway divides the lake with a stark straight line changing the water level and chemistry of the lake as a result. Fresh water runoff enters from the south adding to the depth and reducing the salinity. The north half receives little frsh water and is more saline and shallow. The Bonnieville Salt Flats is the lakebed of a onetime larger lake.

  20. Great Salt Lake and Bonneville Salt Flats, UT, USA

    NASA Image and Video Library

    1992-04-02

    This is a view of the Great Salt Lake and nearby Bonneville Salt Flats, UT, (41.0N, 112.5W). A railroad causeway divides the lake with a stark straight line changing the water level and chemistry of the lake as a result. Fresh water runoff enters from the south adding to the depth and reducing the salinity. The north half receives little frsh water and is more saline and shallow. The Bonnieville Salt Flats is the lakebed of a onetime larger lake.

  1. Molecular Probe Fluorescence Monitoring of Polymerization

    NASA Technical Reports Server (NTRS)

    Bunton, Patrick

    2002-01-01

    This project investigated the feasibility of using fluorescence spectroscopy to determine viscosity of polymer/monomer in support of Transient Interfacial Phenomena in Miscible Polymer Systems (TIPMPS). This project will attempt to measure gradient induced flow at a miscible interface during and / or after in-flight polymerization of dodecyl acrylate (lauryl acrylate). Concentration and temperature gradients will be intentionally introduced during polymerization and the resultant fluid flow determined by Particle Imaging Velocimetry (PIV). This report describes an investigation of the feasibility of using fluorescence of a probe molecule to monitor viscosity and/or concentration during and after polymerization. The probe used was pyrene which has been shown to be sensitive to its local environment in methyl methacrylate.

  2. Two-Photon Polymerization of Defects in Photonic Crystals

    DTIC Science & Technology

    2006-01-01

    technique employs two-photon polymerization (TPP) (for description, see Section 2.2) to fabricate high-resolution 3D embedded polymer features within... polymer , and therefore does not influence the polymerization . The image contrast is from the different reflectivities of the interfaces in the system due...Spectroscopy also confirmed for the first time the successful polymerization of a uniform, dense polymer feature throughout the thickness of the

  3. [Historical roles of salt].

    PubMed

    Ritz, E; Ritz, C

    2004-12-17

    Recently increasing evidence has been provided pointing to a close relation of salt consumption to hypertension as well as to target organ damage. It is interesting to note that the discussion concerning salt is unusually emotional. This may be explained, at least in part, by the fact that since ancient times salt had deep symbolic significance, as exemplified, mostly subconsciously, by many customs and expressions still in current use. In the past salt was essential to preserve food. The past importance of salt as a commodity can well be compared with that of oil today. These and further historical aspects of the role of salt are briefly dealt with in this article.

  4. Self-Sacrificial Salt Templating: Simple Auxiliary Control over the Nanoporous Structure of Porous Carbon Monoliths Prepared through the Solvothermal Route

    PubMed Central

    Feng, Junzong; Jiang, Yonggang; Liu, Ping; Zhang, Qiuhua; Wei, Ronghui; Chen, Xiang; Feng, Jian

    2018-01-01

    The conventional sol-gel method for preparing porous carbons is tedious and high-cost to prepare porous carbons and the control over the nanoporous architecture by solvents and carbonization is restricted. A simple and novel self-sacrificial salt templating method was first presented to adjust the microporous structure of porous carbon monoliths synthesized via the solvothermal method. Apart from good monolithic appearance, the solvothermal route allowed for ambient drying because it made sure that the polymerization reaction was completed quickly and thoroughly. The intact and crack-free porous carbon monoliths were investigated by scanning electron microscopy (SEM), thermogravimetric differential scanning calorimetry (TG-DSC), Fourier transform infrared (FT-IR), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and nitrogen sorption measurements. It was proven that the self-sacrificial salts NH4SCN had been removed during pyrolyzing and so, porous carbon monoliths could be directly obtained after carbonization without the need of washing removal of salts. Most importantly, the microporous specific surface area of the resultant porous carbon monoliths was dramatically increased up to 770 m2/g and the Brunauer–Emmett–Teller (BET) specific surface area was up to 1131 m2/g. That was because the salts NH4SCN as self-sacrificial templating helped to form more around 0.6 nm, 0.72 nm and 1.1 nm micropores. The self-sacrificial salt templating is also a suitable and feasible method for controlling the nanoporous structure of other porous materials. PMID:29671818

  5. Polymeric Additives For Graphite/Epoxy Composites

    NASA Technical Reports Server (NTRS)

    Kourtides, D. A.; Nir, Z.

    1990-01-01

    Report describes experimental studies of properties of several graphite/epoxy composites containing polymeric additives as flexibilizing or toughening agents. Emphasizes effects of brominated polymeric additives (BPA's) with or without carboxy-terminated butadiene acrylonitrile rubber. Reviews effects of individual and combined additives on fracture toughnesses, environmental stabilities, hot/wet strengths, thermomechanical behaviors, and other mechanical properties of composites.

  6. A diazonium ion cascade from the nitrosation of tolazoline, an imidazoline-containing drug.

    PubMed

    Loeppky, Richard N; Shi, Jianzheng; Barnes, Charles L; Geddam, Sailaja

    2008-02-01

    Tolazoline (1-benzylimidazoline), a representative imidazoline-containing drug, reacts readily with nitrite in acetic acid to produce a complex product mixture. Fourteen compounds have been identified as products of this transformation when an 8-fold excess of HNO2 is used. The products, which include N-nitrosoamides, esters, alcohols, and phenylacetic acid, are rationalized as arising from a cascade of reactive diazonium ions. N-Nitrosotolazoline can be isolated from the nitrosation reaction in good yield when the mixture is extracted with CH2Cl2 as the transformation progresses. It nitrosates much more rapidly (50x) than tolazoline to give, among other products, the oxime [1-( N-nitroso-2-imidazolinyl)benzylidene]hydroxylamine, which can also be produced in good yield from the reaction of tolazoline with isopropyl nitrite. At low substrate and nitrite concentrations, the main reaction products are N-nitrosotolazoline, its decomposition product N-2-hydroxyethylphenylacetamide, the above-mentioned oxime, phenyl acetic acid, and 2-hydroxyethyl phenylacetate. The tolazoline nitrosation rate in three buffer systems has been determined at pH 3.4 and 37 degrees C ( kobs = 6.25 x 10 (-5) s (-1) in 0.5 M acetate buffer with a 10 * [NO2(-)] = 250 mM). Because N-nitrosotolazoline exhibits the chemical properties of a direct-acting mutagen and carcinogen, we have used the rate data to estimate its level of formation at nitrite concentrations <3 mM. Cursory examination of the nitrosation chemistry of oxymetazoline, a related drug, is primarily focused at its electron-rich aromatic ring.

  7. Balance between salt stress and endogenous hormones influence dry matter accumulation in Jerusalem artichoke.

    PubMed

    Shao, Tianyun; Li, Lingling; Wu, Yawen; Chen, Manxia; Long, Xiaohua; Shao, Hongbo; Liu, Zhaopu; Rengel, Zed

    2016-10-15

    Salinity is one of the most serious environmental stresses limiting agricultural production. Production of Jerusalem artichoke on saline land is strategically important for using saline land resources. The interaction between plant hormones and salinity stress in governing Jerusalem artichoke (Helianthus tuberosus) growth is unclear. Jerusalem artichoke (variety Nanyu-1) was grown under variable salinity stress in the field, and a role of endogenous hormones [zeatin (ZT), auxins (IAA), gibberellins (GA3) and abscisic acid (ABA)] in regulating sugar and dry matter accumulation in tubers was characterized. Under mild salt stress (≤2.2gNaClkg(-1) soil), Nanyu-1 grew well with no significant alteration of dry matter distribution to stems and tubers. In contrast, under moderate salt stress (2.7gNaClkg(-1) soil), the distribution to stem decreased and to tubers decreased significantly. Mild salt stress induced sugar accumulation in tubers at the beginning of the tuber-expansion period, but significantly inhibited (i) transfer of non-reducing sugars to tubers, and (ii) polymerization and accumulation of fructan during the tuber-expansion stage. Under different salinity stress, before the stolon growth, the ratio of IAA/ABA in leaves increased significantly and that of GA3/ABA increased slightly; during tuber development, these ratios continued to decrease and reached the minimum late in the tuber-expansion period. While, salt stress inhibited (i) underground dry matter accumulation, (ii) tuber dry matter accumulation efficiency, (iii) transport of non-reducing sugars to tubers, and (iv) fructan accumulation efficiency during the tuber-expansion period; these effects were accompanied by significantly decreased tuber yield with an increase in salinity. With soil salinity increasing, the synthesis of IAA and GA3 was inhibited in leaves and tubers, while ABA synthesis was stimulated. In brief, tuber yield would significantly decreased with the increase of salinity

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

    PubMed

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

    2018-02-01

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

  9. Water purification using organic salts

    DOEpatents

    Currier, Robert P.

    2004-11-23

    Water purification using organic salts. Feed water is mixed with at least one organic salt at a temperature sufficiently low to form organic salt hydrate crystals and brine. The crystals are separated from the brine, rinsed, and melted to form an aqueous solution of organic salt. Some of the water is removed from the aqueous organic salt solution. The purified water is collected, and the remaining more concentrated aqueous organic salt solution is reused.

  10. Detecting Levels of Polyquaternium-10 (PQ-10) via Potentiometric Titration with Dextran Sulphate and Monitoring the Equivalence Point with a Polymeric Membrane-Based Polyion Sensor.

    PubMed

    Ferguson, Stephen A; Wang, Xuewei; Meyerhoff, Mark E

    2016-08-07

    Polymeric quaternary ammonium salts (polyquaterniums) have found increasing use in industrial and cosmetic applications in recent years. More specifically, polyquaternium-10 (PQ-10) is routinely used in cosmetic applications as a conditioner in personal care product formulations. Herein, we demonstrate the use of potentiometric polyion-sensitive polymeric membrane-based electrodes to quantify PQ-10 levels. Mixtures containing both PQ-10 and sodium lauryl sulfate (SLS) are used as model samples to illustrate this new method. SLS is often present in cosmetic samples that contain PQ-10 (e.g., shampoos, etc.) and this surfactant species interferes with the polyion sensor detection chemistry. However, it is shown here that SLS can be readily separated from the PQ-10/SLS mixture by use of an anion-exchange resin and that the PQ-10 can then be titrated with dextran sulphate (DS). This titration is monitored by potentiometric polyanion sensors to provide equivalence points that are directly proportional to PQ-10 concentrations.

  11. 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.

  12. Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates and Method Relating Thereto

    NASA Technical Reports Server (NTRS)

    Simpson, Joycelyn O. (Inventor); St.Claire, Terry L. (Inventor)

    2002-01-01

    A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared, This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches. adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrates; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

  13. A universal salt model based on under-ground precipitation of solid salts due to supercritical water `out-salting'

    NASA Astrophysics Data System (ADS)

    Rueslåtten, H.; Hovland, M. T.

    2010-12-01

    One of the common characteristics of planets Earth and Mars is that both host water (H2O) and large accumulations of salt. Whereas Earth’s surface-environment can be regarded as ‘water-friendly’ and ‘salt hostile’, the reverse can be said for the surface of Mars. This is because liquid water is stable on Earth, and the atmosphere transports humidity around the globe, whereas on planet Mars, liquid water is unstable, rendering the atmosphere dry and, therefore, ‘salt-friendly’. The riddle as to how the salt accumulated in various locations on those two planets, is one of long-lasting and great debate. The salt accumulations on Earth are traditionally termed ‘evaporites’, meaning that they formed as a consequence of the evaporation of large masses of seawater. How the accumulations on Mars formed is much harder to explain, as an ocean only existed briefly. Although water molecules and OH-groups may exist in abundance in bound form (crystal water, adsorbed water, etc.), the only place where free water is expected to be stable on Mars is within underground faults, fractures, and crevices. Here it likely occurs as brine or in the form of ice. Based on these conditions, a key to understanding the accumulation of large deposits of salt on both planets is linked to how brines behave in the subsurface when pressurized and heated beyond their supercritical point. At depths greater than about 3 km (P>300 bars) water will no longer boil in a steam phase. Rather, it becomes supercritical and will attain the phase of supercritical water vapor (SCRIW) with a specific gravity of typically 0.3 g/cm3. An important characteristic of SCRIW is its inability to dissolve the common sea salts. The salt dissolved in the brines will therefore precipitate as solid particles when brines (seawater on the Earth) move into the supercritical P&T-domain (T>400°C, P>300 bars). Numerical modeling of a hydrothermal system in the Atlantis II Deep of the Red Sea indicates that a

  14. Polymeric Coatings for Combating Biocorrosion

    NASA Astrophysics Data System (ADS)

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

    2018-03-01

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

  15. Salt Stability - The Effect of pHmax on Salt to Free Base Conversion.

    PubMed

    Hsieh, Yi-Ling; Merritt, Jeremy M; Yu, Weili; Taylor, Lynne S

    2015-09-01

    The aim of this study was to investigate how the disproportionation process can be impacted by the properties of the salt, specifically pHmax. Five miconazole salts and four sertraline salts were selected for this study. The extent of conversion was quantified using Raman spectroscopy. A mathematical model was utilized to estimate the theoretical amount of conversion. A trend was observed that for a given series of salts of a particular basic compound (both sertraline and miconazole are bases), the extent of disproportionation increases as pHmax decreases. Miconazole phosphate monohydrate and sertraline mesylate, although exhibiting significantly different pHmax values (more than 2 units apart), underwent a similar extent of disproportionation, which may be attributed to the lower buffering capacity of sertraline salts. This work shows that the disproportionation tendency can be influenced by pHmax and buffering capacity and thus highlights the importance of selecting the appropriate salt form during the screening process in order to avoid salt-to-free form conversion.

  16. Separation and characterization of allergic polymerized impurities in cephalosporins by 2D-HPSEC×LC-IT-TOF MS.

    PubMed

    Xu, Yu; Wang, DanDan; Tang, Lan; Wang, Jian

    2017-10-25

    Eleven unknown allergic impurities in cefodizime, cefmenoxime and cefonicid were separated and characterized by a trap-free two-dimensional high performance size exclusion chromatography (HPSEC) and reversed phase liquid chromatography (RP-HPLC) coupled to high resolution ion trap/time-of-flight mass spectrometry (2D-HPSEC×LC-IT-TOF MS) with positive and negative modes of electrospray ionization method. Separation and characterization the allergic polymerized impurities in β-lactam antibiotics were on the basis of column-switching technique which effectively combined the advantages of HPSEC and the ability of RP-HPLC to identify the special impurities. In the first dimension HPSEC, the column was Xtimate SEC-120 analytical column (7.8mm×30cm, 5μm), and the gradient elution used pH 7.0 buffer-acetonitrile as mobile phase And the second dimension analytical column was ZORBAX SB-C18 (4.6×150mm, 3.5μm) with ammonium formate solution (10mM) and ammonium formate (8mM) in [acetonitrile-water (4:1, v/v)] solution as mobile phase. Structures of eleven unknown impurities were deduced based on the high resolution MS n data with both positive and negative modes, in which nine impurities were polymerized impurities. The forming mechanism of β-lactam antibiotic polymerization in cephalosporins was also studied. The question on incompatibility between non-volatile salt mobile phase and mass spectrometry was solved completely by multidimensional heart-cutting approaches and online demineralization technique, which was worthy of widespread use and application for the advantages of stability and repeatability. Copyright © 2017. Published by Elsevier B.V.

  17. Polymersome nanoreactors for enzymatic ring-opening polymerization.

    PubMed

    Nallani, Madhavan; de Hoog, Hans-Peter M; Cornelissen, Jeroen J L M; Palmans, Anja R A; van Hest, Jan C M; Nolte, Roeland J M

    2007-12-01

    Polystyrene-polyisocyanopeptide (PS-PIAT) polymersomes containing CALB in two different locations, one in the aqueous inner compartment and one in the bilayer, were investigated for enzymatic ring-opening polymerization of lactones in water. It is shown that the monomers 8-octanolactone and dodecalactone yield oligomers with this polymersome system. It is also observed that the polymerization activity is dependent on the position of the enzyme in the polymersome. SEM investigations show that the polymersome structures were destabilized during the polymerization. Further investigations show that the vesicular morphology of the polymersomes was destabilized only in the case of polymer product formation.

  18. Salt forms of the pharmaceutical amide dihydrocarbamazepine.

    PubMed

    Buist, Amanda R; Kennedy, Alan R

    2016-02-01

    Carbamazepine (CBZ) is well known as a model active pharmaceutical ingredient used in the study of polymorphism and the generation and comparison of cocrystal forms. The pharmaceutical amide dihydrocarbamazepine (DCBZ) is a less well known material and is largely of interest here as a structural congener of CBZ. Reaction of DCBZ with strong acids results in protonation of the amide functionality at the O atom and gives the salt forms dihydrocarbamazepine hydrochloride {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride, C15H15N2O(+)·Cl(-)}, dihydrocarbamazepine hydrochloride monohydrate {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride monohydrate, C15H15N2O(+)·Cl(-)·H2O} and dihydrocarbamazepine hydrobromide monohydrate {systematic name: [(10,11-dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium bromide monohydrate, C15H15N2O(+)·Br(-)·H2O}. The anhydrous hydrochloride has a structure with two crystallographically independent ion pairs (Z' = 2), wherein both cations adopt syn conformations, whilst the two hydrated species are mutually isostructural and have cations with anti conformations. Compared to neutral dihydrocarbamazepine structures, protonation of the amide group is shown to cause changes to both the molecular (C=O bond lengthening and C-N bond shortening) and the supramolecular structures. The amide-to-amide and dimeric hydrogen-bonding motifs seen for neutral polymorphs and cocrystalline species are replaced here by one-dimensional polymeric constructs with no direct amide-to-amide bonds. The structures are also compared with, and shown to be closely related to, those of the salt forms of the structurally similar pharmaceutical carbamazepine.

  19. Plasma 24,25-dihydroxyvitamin D concentration of Dahl salt-sensitive rats decreases during high salt intake

    NASA Technical Reports Server (NTRS)

    Thierry-Palmer, Myrtle; Tewolde, Teclemicael K.; Forte, Camille; Wang, Min; Bayorh, Mohamed A.; Emmett, Nerimiah L.; White, Jolanda; Griffin, Keri

    2002-01-01

    Dahl salt-sensitive rats, but not salt-resistant rats, develop hypertension in response to high salt intake. We have previously shown an inverse relationship between plasma 25-hydroxyvitamin D (25-OHD) concentration and blood pressure of Dahl salt-sensitive rats during high salt intake. In this study, we report on the relationship between high salt intake and plasma 24,25-dihydroxyvitamin D (24,25-(OH)(2)D) concentration of Dahl salt-sensitive and salt-resistant rats. Rats were fed a high salt diet (8%) and sacrificed at day 2, 7, 14, 21, and 28. Plasma 24,25-(OH)(2)D concentrations of salt-sensitive rats were reduced to 50% of that at baseline at day 2-when blood pressure and plasma 25-OHD concentration were unchanged, but 25-OHD content in the kidney was 81% of that at baseline. Plasma 24,25-(OH)(2)D concentration was reduced further to 10% of that at baseline from day 7 to 14 of high salt intake, a reduction that was prevented in rats switched to a low salt (0.3%) diet at day 7. Exogenous 24,25-dihydroxycholecalciferol (24,25-(OH)(2)D(3)), administered at a level that increased plasma 24,25-(OH)(2)D concentration to five times normal, did not attenuate the salt-induced hypertension of salt-sensitive rats. Plasma 24,25-(OH)(2)D concentration of salt-resistant rats was gradually reduced to 50% of that at baseline at day 14 and returned to baseline value at day 28 of high salt intake. We conclude that the decrease in plasma 24,25-(OH)(2)D concentration in salt-sensitive rats during high salt intake is caused by decreased 25-OHD content in the kidney and also by another unidentified mechanism.

  20. 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.

  1. Comparison of salt taste thresholds and salt usage behaviours between adults in Myanmar and Korea.

    PubMed

    Cho, Hyungjin; Kim, So Mi; Jeong, Seong Su; Kim, Soon Bae

    2016-12-01

    Excessive oral salt intake can induce hypertension. According to previous studies, the prevalence of hypertension is higher in Myanmar than in Korea. We postulated that Myanmar adults had higher salt taste thresholds and eat much saltier food. This study aimed to compare salt taste thresholds and salt usage behaviour scores between adults in Myanmar and Korea. This cross-sectional study enrolled patients who visited volunteer medical service clinics at Ansung in Korea and Hlegu and Bago in Myanmar in August 2014. We measured the vital signs, heights, and weights of each patient and evaluated detection thresholds, recognition thresholds, and salt preferences. All patients underwent urinalysis and spot urine Na tests. Additionally, they each completed a salt usage behaviour questionnaire. A total of 131 patients were enrolled, including 64 Myanmarese patients and 67 Korean patients. Blood pressure was significantly higher in the Myanmarese than in the Koreans. Detection and recognition thresholds, salt preferences, and spot urine sodium and salt usage behaviour scores were also higher in the Myanmarese than in the Korean subjects. We calculated correlation coefficients between systolic blood pressure and parameters that were related to salt intake. The detection and recognition thresholds were significantly correlated with systolic blood pressure. All parameters related to salt intake, including detection and recognition thresholds, salt preference, salt usage behaviour scores and spot urine sodium concentrations, are significantly higher in Myanmarese than in Korean individuals.

  2. Mineral resource of the month: salt

    USGS Publications Warehouse

    Kostick, Dennis S.

    2010-01-01

    The article presents information on various types of salt. Rock salt is either found from underground halite deposits or near the surface. Other types of salt include solar salt, salt brine, and vacuum pan salt. The different uses of salt are also given including its use as a flavor enhancer, as a road deicing agent, and to manufacture sodium hydroxide.

  3. Mechanical stratification of autochthonous salt: Implications from basin-scale numerical models of rifted margin salt tectonics

    NASA Astrophysics Data System (ADS)

    Ings, Steven; Albertz, Markus

    2014-05-01

    Deformation of salt and sediments owing to the flow of weak evaporites is a common phenomenon in sedimentary basins worldwide, and the resulting structures and thermal regimes have a significant impact on hydrocarbon exploration. Evaporite sequences ('salt') of significant thickness (e.g., >1km) are typically deposited in many cycles of seawater inundation and evaporation in restricted basins resulting in layered autochthonous evaporite packages. However, analogue and numerical models of salt tectonics typically treat salt as a homogeneous viscous material, often with properties of halite, the weakest evaporite. In this study, we present results of two-dimensional plane-strain numerical experiments designed to illustrate the effects of variable evaporite viscosity and embedded frictional-plastic ('brittle') sediment layers on the style of salt flow and associated deformation of the sedimentary overburden. Evaporite viscosity is a first-order control on salt flow rate and the style of overburden deformation. Near-complete evacuation of low-viscosity salt occurs beneath expulsion basins, whereas significant salt is trapped when viscosity is high. Embedded frictional-plastic sediment layers (with finite yield strength) partition salt flow and develop transient contractional structures (folds, thrust faults, and folded faults) in a seaward salt-squeeze flow regime. Multiple internal sediment layers reduce the overall seaward salt flow during sediment aggradation, leaving more salt behind to be re-mobilized during subsequent progradation. This produces more seaward extensive allochthonous salt sheets. If there is a density difference between the embedded layers and the surrounding salt, then the embedded layers 'fractionate' during deformation and either float to the surface or sink to the bottom (depending on density), creating a thick zone of pure halite. Such a process of 'buoyancy fractionation' may partially explain the apparent paradox of layered salt in

  4. 238Pu recovery and salt disposition from the molten salt oxidation process

    NASA Astrophysics Data System (ADS)

    Remerowski, M. L.; Stimmel, Jay J.; Wong, Amy S.; Ramsey, Kevin B.

    2000-07-01

    We have begun designing and optimizing our recovery and recycling processes by experimenting with samples of "spent salt" produced by MSO treatment of surrogate waste in the reaction vessel at the Naval Surface Warfare Center-Indian Head. One salt was produced by treating surrogate waste containing pyrolysis ash spiked with cerium. The other salt contains residues from MSO treatment of materials similar to those used in 238Pu processing, e.g., Tygon tubing, PVC bagout bags, HDPE bottles. Using these two salt samples, we will present results from our investigations.

  5. Polyurethane nanofiber strain sensors via in situ polymerization of polypyrrole and application to monitoring joint flexion

    NASA Astrophysics Data System (ADS)

    Kim, Inhwan; Cho, Gilsoo

    2018-07-01

    Strain sensors made of intrinsically conductive polymers (ICPs) and nanofibers were fabricated and tested for suitability for use in wearable technology. The sensors were fabricated and evaluated based on their surface appearances, and electrical, tensile, and chemical/thermal properties. Polypyrrole (PPy) was in situ polymerized onto polyurethane (PU) nanofiber substrates by exposing pyrrole monomers to ammonium persulfate as oxidant and 2,6-naphthalenedisulfonic acid disodium salt as doping agents in an aqueous bath. The PPy treated PU nanofibers were then coated with polydimethylsiloxane (PDMS). Both pyrrole concentrations and layer numbers were significantly related to change in electrical conductivity. Specimen treated with 0.1 M of PPy and having three layered structure showed the best electrical conductivity. Regarding tensile strength, the in situ polymerization process decreased tensile strength because the oxidant chemically degraded the PU fibers. Adding layers and PDMS treatment generally improved tensile properties while adding layers created fracture parts in the stress–strain curves. The treatment condition of 0.1 M of PPy, two layered, and PDMS treated specimen showed the best tensile properties as a strain sensor. The chemical property evaluation with Fourier transform infrared and x-ray photoelectron spectroscopy tests showed successful PPy polymerization and PDMS treatments. The functional groups and chemical bonds in polyol, urethane linkage, backbone ring structure in PPy, silicon-based functional groups in PDMS, and elemental content changes by treatment at each stage were characterized. The real-time data acquired from the dummy and five human subjects with repetition of motion at three different speeds of 0.16, 0.25 and 0.5 Hz generated similar trends and tendencies. The PU nanofiber sensors based on PPy and PDMS treatments in this study point to the possibility of developing textiles based wearable strain sensors developed using ICPs.

  6. Salt Weathering on Mars

    NASA Astrophysics Data System (ADS)

    Jagoutz, E.

    2006-12-01

    Large well rounded boulders and angular rock fragments characterizes the Martian landscape as seen on the recent excellent quality photos. Analyzing the different rock-shapes indicates a time sequence of emplacement, fragmentation and transport of different rocks on Mars, which might give interesting insight into transport and weathering processes. Larger commonly well rounded boulders were emplaced onto gravel plains. After emplacement, these rocks were fragmented and disassembled. Nests of angular rock fragments are marking the locations of preexisting larger rocks. Frequently it is possible to reconstruct larger rounded rocks from smaller angular fragments. In other cases transport after fragmentation obscured the relationship of the fragments. However, a strewn field of fragments is still reminiscent of the preexisting rock. Mechanical salt weathering could be a plausible explanation for the insitu fragmentation of larger rounded blocks into angular fragments. Impact or secondary air fall induced fragmentation produces very different patterns, as observed around impact crates on Earth. Salt weathering of rocks is a common process in terrestrial environments. Salt crystallization in capillaries causes fragmentation of rocks, irrespective of the process of salt transportation and concentration. On Earth significant salt weathering can be observed in different climatic environments: in the transition zone of alluvial aprons and salt playas in desserts and in dry valleys of Antarctica. In terrestrial semi-arid areas the salt is transported by salt solution, which is progressively concentrated by evaporation. In Antarctic dry valleys freeze-thaw cycles causes salt transportation and crystallization resulting in rock fragmentation. This salt induced process can lead to complete destruction of rocks and converts rocks to fine sand. The efficient breakdown of rocks is dominating the landscape in some dry valleys of the Earth but possibly also on Mars. (Malin, 1974

  7. Should we eat less salt?

    PubMed

    Delahaye, François

    2013-05-01

    High blood pressure is a major cardiovascular risk factor. There is overwhelming evidence that high salt consumption is a major cause of increased blood pressure. There is also a link between high salt consumption and risk of stroke, left ventricular hypertrophy, renal disease, obesity, renal stones and stomach cancer. Reducing salt consumption leads to a decrease in blood pressure and the incidence of cardiovascular disease. There are no deleterious effects associated with reducing salt consumption and it is also very cost-effective. Many organizations and state governments have issued recommendations regarding the suitable amount of salt consumption. In France, the objective is a salt consumption<8g/day in men and<6.5g/day in women and children. As 80% of consumed salt comes from manufactured products in developed countries, reduction of salt consumption requires the participation of the food industry. The other tool is consumer information and education. Salt consumption has already decreased in France in recent years, but efforts must continue. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

  8. Actinide removal from spent salts

    DOEpatents

    Hsu, Peter C.; von Holtz, Erica H.; Hipple, David L.; Summers, Leslie J.; Adamson, Martyn G.

    2002-01-01

    A method for removing actinide contaminants (uranium and thorium) from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents are added to precipitate the thorium as thorium oxide and/or the uranium as either uranium oxide or as a diuranate salt. The precipitated materials are filtered, dried and packaged for disposal as radioactive waste. About 90% of the thorium and/or uranium present is removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 0.1 ppm of thorium or uranium.

  9. Power plant I - Fused salt

    NASA Astrophysics Data System (ADS)

    Roche, M.

    A solar thermal power plant using fused salt as the heat transfer fluid for steam power generation is analyzed for the feasibility of economic operation. The salt is also stored in a tank reservoir for maintaining the primary heat loop at temperatures high enough for the salts to remain liquid, and also to provide reserve power for the steam generator. Initial studies were with eutectic (hitec) salt comprising Na, KOH, and nitrites melting at 146 C, and further studies were performed employing draw salt, which has no nitrite, is more stable at high temperature, and melts at 225 C. The use of draw salt was found to allow a 5 percent reduction in storage capacity. Further examinations of the effects of the hitec salts on corrosion and composition degradation at high temperatures are indicated. The molten salt system is projected to offer an efficiency of 26 percent.

  10. 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.

  11. Sequence-Controlled Polymerization on Facially Amphiphilic Templates at Interfaces

    DTIC Science & Technology

    2016-06-14

    controlled chain growth polymerization. We will synthesize a ?- conjugated “parent” polymer by iterative exponential growth (IEG), attach cyclic olefin...template that is programmed to direct sequence- controlled chain growth polymerization. We will synthesize a ?- conjugated “parent” polymer by iterative...polymerization. We will synthesize a π- conjugated “parent” polymer by organometallic iterative exponential growth (IEG),2 attach cyclic olefin “daughter

  12. An insight into polymerization-induced self-assembly by dissipative particle dynamics simulation.

    PubMed

    Huang, Feng; Lv, Yisheng; Wang, Liquan; Xu, Pengxiang; Lin, Jiaping; Lin, Shaoliang

    2016-08-14

    Polymerization-induced self-assembly is a one-pot route to produce concentrated dispersions of block copolymer nano-objects. Herein, dissipative particle dynamics simulations with a reaction model were employed to investigate the behaviors of polymerization-induced self-assembly. The polymerization kinetics in the polymerization-induced self-assembly were analyzed by comparing with solution polymerization. It was found that the polymerization rate enhances in the initial stage and decreases in the later stage. In addition, the effects of polymerization rate, length of macromolecular initiators, and concentration on the aggregate morphologies and formation pathway were studied. The polymerization rate and the length of the macromolecular initiators are found to have a marked influence on the pathway of the aggregate formations and the final structures. Morphology diagrams were mapped correspondingly. A comparison between simulation results and experimental findings is also made and an agreement is shown. This work can enrich our knowledge about polymerization-induced self-assembly.

  13. In Situ Thermal Generation of Silver Nanoparticles in 3D Printed Polymeric Structures

    PubMed Central

    Fantino, Erika; Chiappone, Annalisa; Calignano, Flaviana; Fontana, Marco; Pirri, Fabrizio; Roppolo, Ignazio

    2016-01-01

    Polymer nanocomposites have always attracted the interest of researchers and industry because of their potential combination of properties from both the nanofillers and the hosting matrix. Gathering nanomaterials and 3D printing could offer clear advantages and numerous new opportunities in several application fields. Embedding nanofillers in a polymeric matrix could improve the final material properties but usually the printing process gets more difficult. Considering this drawback, in this paper we propose a method to obtain polymer nanocomposites by in situ generation of nanoparticles after the printing process. 3D structures were fabricated through a Digital Light Processing (DLP) system by disolving metal salts in the starting liquid formulation. The 3D fabrication is followed by a thermal treatment in order to induce in situ generation of metal nanoparticles (NPs) in the polymer matrix. Comprehensive studies were systematically performed on the thermo-mechanical characteristics, morphology and electrical properties of the 3D printed nanocomposites. PMID:28773716

  14. In Situ Thermal Generation of Silver Nanoparticles in 3D Printed Polymeric Structures.

    PubMed

    Fantino, Erika; Chiappone, Annalisa; Calignano, Flaviana; Fontana, Marco; Pirri, Fabrizio; Roppolo, Ignazio

    2016-07-19

    Polymer nanocomposites have always attracted the interest of researchers and industry because of their potential combination of properties from both the nanofillers and the hosting matrix. Gathering nanomaterials and 3D printing could offer clear advantages and numerous new opportunities in several application fields. Embedding nanofillers in a polymeric matrix could improve the final material properties but usually the printing process gets more difficult. Considering this drawback, in this paper we propose a method to obtain polymer nanocomposites by in situ generation of nanoparticles after the printing process. 3D structures were fabricated through a Digital Light Processing (DLP) system by disolving metal salts in the starting liquid formulation. The 3D fabrication is followed by a thermal treatment in order to induce in situ generation of metal nanoparticles (NPs) in the polymer matrix. Comprehensive studies were systematically performed on the thermo-mechanical characteristics, morphology and electrical properties of the 3D printed nanocomposites.

  15. Post polymerization cure shape memory polymers

    DOEpatents

    Wilson, Thomas S.; Hearon, II, Michael Keith; Bearinger, Jane P.

    2017-01-10

    This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

  16. Post polymerization cure shape memory polymers

    DOEpatents

    Wilson, Thomas S; Hearon, Michael Keith; Bearinger, Jane P

    2014-11-11

    This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

  17. Non-equilibrium supramolecular polymerization.

    PubMed

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-09-18

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  18. Salt briquette: the form of salt monopoly in madura, 1883-1911

    NASA Astrophysics Data System (ADS)

    Wisnu; Alrianingrum, S.; Artono; Liana, C.

    2018-01-01

    This study describes the history of the salt monopoly in Indonesia because it is associated with the issue of salt crisis lately, widely reported in various media. This study tried to find answers to the relationship between monopoly and crisis events through the study of history. Monopoly policy by the government of the colonial period is actually an industrial modernization effort, but it turned out another impact. Although the colonial government wanted to issue a policy that ends strengthens the position of the government in the industry, but ultimately backfire and disasters in the salt industry at the time. This article discusses only the focus of the salt monopoly in Madura as a selection of events, arguing the island as a center of salt in Indonesia. The method used in this study using a review of history. Therefore, their explanations using historical sources. Methodologically through the process of collecting historical sources, criticize these sources, synthesize and interpret the analysis in an array of historical writing. In conclusion, although the salt monopoly policy gives a great advantage to the colonial government, but the overall population of Madura remains in a poor state. It is evident that the Madurese to migrate Madurese to various areas outside the island of Madura, to fix the economy.

  19. Dynamics of salt playa polygons

    NASA Astrophysics Data System (ADS)

    Goehring, L.; Fourrière, A.

    2014-12-01

    In natural salt playa or in evaporation pools for the salt extraction industry, one can sometimes see surprising regular structures formed by ridges of salt. These ridges connect together to form a self-organized network of polygons one to two meters in diameter, which we call salt polygons. Here we propose a mechanism based on porous media convection of salty water in soil to explain the formation and the scaling of the salt polygons. Surface evaporation causes a steady upward flow of salty water, which can cause precipitation near the surface. A vertical salt gradient then builds up in the porous soil, with heavy salt-saturated water lying over the less salty source water. This can drive convection when a threshold is reached, given by a critical Rayleigh number of about 7. We suggest that the salt polygons are the surface expression of the porous medium convection, with salt crystallizing along the positions of the convective downwellings. To study this instability directly, we developed a 2D analogue experiment using a Hele-Shaw cell filled with a porous medium saturated with a salt solution and heated from above. We perform a linear stability analysis of this system, and find that it is unstable to convection, with a most unstable wavelength that is set by a balance between salt diffusion and water evaporation. The Rayleigh number in our experiment is controlled by the particle size of our model soil, and the evaporation rate. We obtain results that scale with the observation of natural salt polygons. Using dye, we observe the convective movement of salty water and find downwelling convective plumes underneath the spots where surface salt ridges form, as shown in the attached figure.

  20. Salt and cocrystals of sildenafil with dicarboxylic acids: solubility and pharmacokinetic advantage of the glutarate salt.

    PubMed

    Sanphui, Palash; Tothadi, Srinu; Ganguly, Somnath; Desiraju, Gautam R

    2013-12-02

    Sildenafil is a drug used to treat erectile dysfunction and pulmonary arterial hypertension. Because of poor aqueous solubility of the drug, the citrate salt, with improved solubility and pharmacokinetics, has been marketed. However, the citrate salt requires an hour to reach its peak plasma concentration. Thus, to improve solubility and bioavailability characteristics, cocrystals and salts of the drug have been prepared by treating aliphatic dicarboxylic acids with sildenafil; the N-methylated piperazine of the drug molecule interacts with the carboxyl group of the acid to form a heterosynthon. Salts are formed with oxalic and fumaric acid; salt monoanions are formed with succinic and glutaric acid. Sildenafil forms cocrystals with longer chain dicarboxylic acids such as adipic, pimelic, suberic, and sebacic acids. Auxiliary stabilization via C-H···O interactions is also present in these cocrystals and salts. Solubility experiments of sildenafil cocrystal/salts were carried out in 0.1N HCl aqueous medium and compared with the solubility of the citrate salt. The glutarate salt and pimelic acid cocrystal dissolve faster than the citrate salt in a two hour dissolution experiment. The glutarate salt exhibits improved solubility (3.2-fold) compared to the citrate salt in water. Solubilities of the binary salts follow an inverse correlation with their melting points, while the solubilities of the cocrystals follow solubilities of the coformer. Pharmacokinetic studies on rats showed that the glutarate salt exhibits doubled plasma AUC values in a single dose within an hour compared to the citrate salt. The high solubility of glutaric acid, in part originating from the strained conformation of the molecule and its high permeability, may be the reason for higher plasma levels of the drug.

  1. Metals removal from spent salts

    DOEpatents

    Hsu, Peter C.; Von Holtz, Erica H.; Hipple, David L.; Summers, Leslie J.; Brummond, William A.; Adamson, Martyn G.

    2002-01-01

    A method and apparatus for removing metal contaminants from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents may be added to precipitate the metal oxide and/or the metal as either metal oxide, metal hydroxide, or as a salt. The precipitated materials are filtered, dried and packaged for disposal as waste or can be immobilized as ceramic pellets. More than about 90% of the metals and mineral residues (ashes) present are removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be spray-dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 1.0 ppm of contaminants.

  2. Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  3. Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes.

    PubMed

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

    2015-11-06

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

  4. Water and salt balance of Great Salt Lake, Utah, and simulation of water and salt movement through the causeway

    USGS Publications Warehouse

    Wold, Steven R.; Thomas, Blakemore E.; Waddell, Kidd M.

    1997-01-01

    The water and salt balance of Great Salt Lake primarily depends on the amount of inflow from tributary streams and the conveyance properties of a causeway constructed during 1957-59 that divides the lake into the south and north parts. The conveyance properties of the causeway originally included two culverts, each 15 feet wide, and the permeable rock-fill material.During 1980-86, the salt balance changed as a result of record high inflow that averaged 4,627,000 acre-feet annually and modifications made to the conveyance properties of the causeway that included opening a 300-foot-wide breach. In this study, a model developed in 1973 by Waddell and Bolke to simulate the water and salt balance of the lake was revised to accommodate the high water-surface altitude and modifications made to the causeway. This study, done by the U.S. Geological Survey in cooperation with the Utah Department of Natural Resources, Division of State Lands and Forestry, updates the model with monitoring data collected during 1980-86. This report describes the calibration of the model and presents the results of simulations for three hypothetical 10-year periods.During January 1, 1980, to July 31, 1984, a net load of 0.5 billion tons of dissolved salt flowed from the south to the north part of the lake primarily as a result of record inflows. From August 1, 1984, when the breach was opened, to December 31,1986, a net load of 0.3 billion tons of dissolved salt flowed from the north to the south part of the lake primarily as a result of the breach.For simulated inflow rates during a hypothetical 10-year period resulting in the water-surface altitude decreasing from about 4,200 to 4,192 feet, there was a net movement of about 1.0 billion tons of dissolved salt from the south to the north part, and about 1.7 billion tons of salt precipitated in the north part. For simulated inflow rates during a hypothetical 10-year period resulting in a rise in water-surface altitude from about 4,200 to 4

  5. Salt Reductions in Some Foods in The Netherlands: Monitoring of Food Composition and Salt Intake

    PubMed Central

    Temme, Elisabeth H. M.; Hendriksen, Marieke A. H.; Milder, Ivon E. J.; Toxopeus, Ido B.; Westenbrink, Susanne; Brants, Henny A. M.; van der A, Daphne L.

    2017-01-01

    Background and objectives. High salt intake increases blood pressure and thereby the risk of chronic diseases. Food reformulation (or food product improvement) may lower the dietary intake of salt. This study describes the changes in salt contents of foods in the Dutch market over a five-year period (2011–2016) and differences in estimated salt intake over a 10-year period (2006–2015). Methods. To assess the salt contents of foods; we obtained recent data from chemical analyses and from food labels. Salt content of these foods in 2016 was compared to salt contents in the 2011 version Dutch Food Composition Database (NEVO, version 2011), and statistically tested with General Linear Models. To estimate the daily dietary salt intake in 2006, 2010, and 2015, men and women aged 19 to 70 years were recruited through random population sampling in Doetinchem, a small town located in a rural area in the eastern part of the Netherlands. The characteristics of the study population were in 2006: n = 317, mean age 49 years, 43% men, in 2010: n = 342, mean age 46 years, 45% men, and in 2015: n = 289, mean age 46 years, 47% men. Sodium and potassium excretion was measured in a single 24-h urine sample. All estimates were converted to a common metric: salt intake in grams per day by multiplication of sodium with a factor of 2.54. Results. In 2016 compared to 2011, the salt content in certain types of bread was on average 19 percent lower and certain types of sauce, soup, canned vegetables and legumes, and crisps had a 12 to 26 percent lower salt content. Salt content in other types of foods had not changed significantly. Between 2006, 2010 and 2015 the estimated salt intake among adults in Doetinchem remained unchanged. In 2015, the median estimated salt intake was 9.7 g per day for men and 7.4 g per day for women. As in 2006 and 2010, the estimated salt intake in 2015 exceeded the recommended maximum intake of 6 g per day set by the Dutch Health Council. Conclusion. In the

  6. Salt Reductions in Some Foods in The Netherlands: Monitoring of Food Composition and Salt Intake.

    PubMed

    Temme, Elisabeth H M; Hendriksen, Marieke A H; Milder, Ivon E J; Toxopeus, Ido B; Westenbrink, Susanne; Brants, Henny A M; van der A, Daphne L

    2017-07-22

    High salt intake increases blood pressure and thereby the risk of chronic diseases. Food reformulation (or food product improvement) may lower the dietary intake of salt. This study describes the changes in salt contents of foods in the Dutch market over a five-year period (2011-2016) and differences in estimated salt intake over a 10-year period (2006-2015). To assess the salt contents of foods; we obtained recent data from chemical analyses and from food labels. Salt content of these foods in 2016 was compared to salt contents in the 2011 version Dutch Food Composition Database (NEVO, version 2011), and statistically tested with General Linear Models. To estimate the daily dietary salt intake in 2006, 2010, and 2015, men and women aged 19 to 70 years were recruited through random population sampling in Doetinchem, a small town located in a rural area in the eastern part of the Netherlands. The characteristics of the study population were in 2006: n = 317, mean age 49 years, 43% men, in 2010: n = 342, mean age 46 years, 45% men, and in 2015: n = 289, mean age 46 years, 47% men. Sodium and potassium excretion was measured in a single 24-h urine sample. All estimates were converted to a common metric: salt intake in grams per day by multiplication of sodium with a factor of 2.54. In 2016 compared to 2011, the salt content in certain types of bread was on average 19 percent lower and certain types of sauce, soup, canned vegetables and legumes, and crisps had a 12 to 26 percent lower salt content. Salt content in other types of foods had not changed significantly. Between 2006, 2010 and 2015 the estimated salt intake among adults in Doetinchem remained unchanged. In 2015, the median estimated salt intake was 9.7 g per day for men and 7.4 g per day for women. As in 2006 and 2010, the estimated salt intake in 2015 exceeded the recommended maximum intake of 6 g per day set by the Dutch Health Council. In the Netherlands, the salt content of bread, certain sauces, soups

  7. Photochemical and radiation-chemical aspects of matrix acidity effects on some organic systems

    NASA Astrophysics Data System (ADS)

    Ambroz, H. B.; Przybytniak, G. K.; Wronska, T.; Kemp, T. J.

    The role of matrix effects in radiolysis and photolysis is illustrated using two systems: organosulphur compounds and benzenediazonium salts. Their intermediates as detected by low temperature ESR and optical spectroscopy or FAB-MS give evidence that the main reaction pathways depend strongly on these effects. Changes in matrix acidity can control the formation of neutral radical, ion-radical or ionic species which are crucial to the character of the final products of irradiation of organosulphur compounds, which are of great importance in medicine, biology, ecology and industry. Microenvironmental influences determine whether the triplet aryl cation or radical species are detected as the principal or sole intermediates in the decomposition of diazonium salts, a process leading to different stable products with industrial application.

  8. Self-Healing of biocompatible polymeric nanocomposities

    NASA Astrophysics Data System (ADS)

    Espino, Omar; Chipara, Dorina

    2014-03-01

    Polymers are vulnerable to damage in form of cracks deep within the structure, where detection is difficult and repair is near to impossible. These cracks lead to mechanical degradation of the polymer. A method has been created to solve this problem named polymeric self healing. Self healing capabilities implies the dispersion within the polymeric matrix of microcapsules filled with a monomer and of catalyst. Poly urea-formaldehyde microcapsules used in this method are filled with dicyclopentadiene that is liberated after being ruptured by the crack propagation in the material. Polymerization is assisted by a catalyst FGGC that ignites the self healing process. Nanocomposites, such as titanium oxide, will be used as an integration of these polymers that will be tested by rupturing mechanically slowly. In order to prove the self healing process, Raman spectroscopy, FTIR, and SEM are used.

  9. Simultaneous measurement of polymerization stress and curing kinetics for photo-polymerized composites with high filler contents.

    PubMed

    Wang, Zhengzhi; Landis, Forrest A; Giuseppetti, Anthony A M; Lin-Gibson, Sheng; Chiang, Martin Y M

    2014-12-01

    Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈80% (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. Published by Elsevier Ltd.

  10. Simultaneous Measurement of Polymerization Stress and Curing Kinetics for Photo-polymerized Composites with High Filler Contents

    PubMed Central

    Wang, Zhengzhi; Landis, Forrest A.; Giuseppetti, Anthony A.M.; Lin-Gibson, Sheng; Chiang, Martin Y.M.

    2015-01-01

    Objectives Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Methods Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Results Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈ 80 % (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. Significance The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. PMID:25443160

  11. Plant salt-tolerance mechanisms

    DOE PAGES

    Deinlein, Ulrich; Stephan, Aaron B.; Horie, Tomoaki; ...

    2014-06-01

    Crop performance is severely affected by high salt concentrations in soils. To engineer more salt-tolerant plants it is crucial to unravel the key components of the plant salt-tolerance network. Here we review our understanding of the core salt-tolerance mechanisms in plants. Recent studies have shown that stress sensing and signaling components can play important roles in regulating the plant salinity stress response. We also review key Na+ transport and detoxification pathways and the impact of epigenetic chromatin modifications on salinity tolerance. In addition, we discuss the progress that has been made towards engineering salt tolerance in crops, including marker-assisted selectionmore » and gene stacking techniques. We also identify key open questions that remain to be addressed in the future.« less

  12. Gold nanoparticles modified electrode via simple electrografting of in situ generated mercaptophenyl diazonium cations for development of DNA electrochemical biosensor.

    PubMed

    Li, Feng; Feng, Yan; Dong, Pingjun; Yang, Limin; Tang, Bo

    2011-01-15

    A novel protocol for development of DNA electrochemical biosensor based on gold nanoparticles (AuNPs) modified glassy carbon electrode (GCE) was proposed, which was carried out by the self-assembly of AuNPs on the mercaptophenyl film (MPF) via simple electrografting of in situ generated mercaptophenyl diazonium cations. The resulting MPF was covalently immobilized on GCE surface via C-C bond with high stability, which was desirable in fabrication of excellent performance biosensors. Probe DNA was self-assembled on AuNPs through the well-known Au-thiol binding. The recognition of fabricated DNA electrochemical biosensor toward complementary single-stranded DNA was determined by differential pulse voltammetry with the use of Co(phen)(3)(3+) as the electrochemical indicator. Taking advantage of amplification effects of AuNPs and stability of MPF, the developed biosensor could detect target DNA with the detection limit of 7.2×10(-11) M, which also exhibits good selectivity, stability and regeneration ability for DNA detection. Copyright © 2010 Elsevier B.V. All rights reserved.

  13. 8 Allergenic Composition of Polymerized Allergen Extracts of Betula verrucosa, Dermatophagoides Pteronyssinus and Phleum Pratense

    PubMed Central

    Fernandez-Caldas, Enrique; Cases, Barbara; Tudela, Jose Ignacio; Fernandez, Eva Abel; Casanovas, Miguel; Subiza, Jose Luis

    2012-01-01

    Background Allergoids have been successfully used in the treatment of respiratory allergic diseases. They are modified allergen extracts that allow the administration of high allergen doses, due to their reduced IgE binding capacity.They maintain allergen-specific T-cell recognition. Since they are native allergen extracts that have been polymerized with glutaraldehyde, identification of the allergenic molecules requires more complicated methods. The aim of the study was to determine the qualitative composition of different polymerized extracts and investigate the presence of defined allergenic molecules using Mass spectrometry. Methods Proteomic analysis was carried out at the Proteomics Facility of the Hospital Nacional de Parapléjicos (Toledo, Spain). After reduction and alkylation, proteins were digested with trypsin and the resulting peptides were cleaned using C18 SpinTips Sample Prep Kit; peptides were separated on an Ultimate nano-LC system using a Monolithic C18 column in combination with a precolumn for salt removal. Fractionation of the peptides was performed with a Probot microfraction collector and MS and MS/MS analysis of offline spotted peptide samples were performed using the Applied Biosystems 4800 plus MALDI TOF/TOF Analyzer mass spectrometer. ProteinPilot Software V 2.0.1 and the Paragon algorithm were used for the identification of the proteins. Each MS/MS spectrum was searched against the SwissProt 2010_10 database, Uniprot-Viridiplantae database and Uniprot_Betula database. Results Analysis of the peptides revealed the presence of native allergens in the polymerized extracts: Der p 1, Der p 2, Der p 3, Der p 8 and Der p 11 in D. pteronyssinus; Bet v 2, Bet v 6, Bet v 7 and several Bet v 1 isoforms in B. verrucosa and Phl p 1, Phl p 3, Phl p 5, Phl p 11 and Phl p 12 in P. pratense allergoids. In all cases, potential allergenic proteins were also identified, including ubiquitin, actin, Eenolase, fructose-bisphosphate aldolase, luminal

  14. Early evolution of salt structures in north Louisiana salt basin

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

    Lobao, J.J.; Pilger, R.H. Jr.

    1986-05-01

    Several salt diapirs and pillows in southern and central north Louisiana have been studied using approximately 355 mi (570 km) of seismic reflection data and information from 57 deep well holes. Using seismic profiles with deep well-hole data is the most advantageous method to document regional salt tectonism through time. The following conclusions were reached on diapirism in the North Louisiana Salt basin. (1) The diapiric event began early (early Coahuilan) in the southern and central part of the basin, and later (late Coahuilan to Comanchean) in the northern part. (2) The initial diapiric event is much more abrupt andmore » intense in the southern and central diapirs when compared with the later diapiric event in the northern diapirs. (3) Regional depocenter shifting, relative sea level, local erosion with salt extrusion, and rapid depositional loading of sediments are the major controls on diapirism in the basin.« less

  15. Salt weathering on Mars

    NASA Astrophysics Data System (ADS)

    Jagoutz, E.

    Large well rounded boulders and angular rock fragments characterizes the Martian landscape as seen on the recent excellent quality photos. Analyzing the different rock-shapes indicates a time sequence of emplacement, fragmentation and transport of different rocks on Mars, which might give interesting insight into transport and weathering processes. Larger commonly well rounded boulders were emplaced onto gravel plains. After emplacement, these rocks were fragmented and disassembled. Nests of angular rock fragments are marking the locations of preexisting larger rocks. Frequently it is possible to reconstruct larger rounded rocks from smaller angular fragments. In other cases transport after fragmentation obscured the relationship of the fragments. However, a strewn field of fragments is still reminiscent of the preexisting rock. Mechanical salt weathering could be a plausible explanation for the insitu fragmentation of larger rounded blocks into angular fragments. Impact or secondary air fall induced fragmentation produces very different patterns, as observed around impact crates on Earth. Salt weathering of rocks is a common process in terrestrial environments. Salt crystallization in capillaries causes fragmentation of rocks, irrespective of the process of salt transportation and concentration. On Earth significant salt weathering can be observed in different climatic environments: in the transition zone of alluvial aprons and salt playas in desserts and in dry valleys of Antarctica. In terrestrial semi-arid areas the salt is transported by salt solution, which is progressively concentrated by evaporation. In Antarctic dry valleys freeze-thaw cycles causes salt transportation and crystallization resulting in rock fragmentation. This salt induced process can lead to complete destruction of rocks and converts rocks to fine sand. The efficient breakdown of rocks is dominating the landscape in some dry valleys of the Earth but possibly also on Mars. (Malin, 1974

  16. 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.

  17. Chimeric protein identification of dystrophic, Pierson and other laminin polymerization residues

    PubMed Central

    McKee, Karen K.; Aleksandrova, Maya; Yurchenco, Peter D.

    2018-01-01

    Laminin polymerization is a key step of basement membrane self-assembly that depends on the binding of the three different N-terminal globular LN domains. Several mutations in the LN domains cause LAMA2-deficient muscular dystrophy and LAMB2-deficient Pierson syndrome. These mutations may affect polymerization. A novel approach to identify the amino acid residues required for polymerization has been applied to an analysis of these and other laminin LN mutations. The approach utilizes laminin-nidogen chimeric fusion proteins that bind to recombinant non-polymerizing laminins to provide a missing functional LN domain. Single amino acid substitutions introduced into these chimeras were tested to determine if polymerization activity and the ability to assemble on cell surfaces were lost. Several laminin-deficient muscular dystrophy mutations, renal Pierson syndrome mutations, and Drosophila mutations causing defects of heart development were identified as ones causing loss of laminin polymerization. In addition, two novel residues required for polymerization were identified in the laminin γ1 LN domain. PMID:29408412

  18. Preparation of polymeric diacetylene thin films for nonlinear optical applications

    NASA Technical Reports Server (NTRS)

    Frazier, Donald O. (Inventor); Mcmanus, Samuel P. (Inventor); Paley, Mark S. (Inventor); Donovan, David N. (Inventor)

    1995-01-01

    A method for producing polymeric diacetylene thin films having desirable nonlinear optical characteristics has been achieved by producing amorphous diacetylene polymeric films by simultaneous polymerization of diacetylene monomers in solution and deposition of polymerized diacetylenes on to the surface of a transparent substrate through which ultraviolet light has been transmitted. These amorphous polydiacetylene films produced by photo-deposition from solution possess very high optical quality and exhibit large third order nonlinear optical susceptibilities, such properties being suitable for nonlinear optical devices such as waveguides and integrated optics.

  19. Applications of polymeric micelles with tumor targeted in chemotherapy

    NASA Astrophysics Data System (ADS)

    Ding, Hui; Wang, Xiaojun; Zhang, Song; Liu, Xinli

    2012-11-01

    Polymeric micelles (PMs) have gained more progress as a carrier system with the quick development of biological and nanoparticle techniques. In particular, PMs with smart targeting can deliver anti-cancer drugs directly into tumor cells at a sustained rate. PMs with core-shell structure (with diameters of 10 100 nm) have been prepared by a variety of biodegradable and biocompatible polymers via a self-assembly process. The preparation of polymeric micelles with stimuli-responsive block copolymers or modification of target molecules on polymeric micelles' surface are able to significantly improve the efficiency of drug delivery. Polymeric micelles, which have been considered as a novel promising drug carrier for cancer therapeutics, are rapidly evolving and being introduced in an attempt to overcome several limitations of traditional chemotherapeutics, including water solubility, tumor-specific accumulation, anti-tumor efficacy, and non-specific toxicity. This review describes the preparation of polymeric micelles and the targeted modification which greatly enhance the effects of chemotherapeutic agents.

  20. Cooperative polymerization of α-helices induced by macromolecular architecture

    NASA Astrophysics Data System (ADS)

    Baumgartner, Ryan; Fu, Hailin; Song, Ziyuan; Lin, Yao; Cheng, Jianjun

    2017-07-01

    Catalysis observed in enzymatic processes and protein polymerizations often relies on the use of supramolecular interactions and the organization of functional elements in order to gain control over the spatial and temporal elements of fundamental cellular processes. Harnessing these cooperative interactions to catalyse reactions in synthetic systems, however, remains challenging due to the difficulty in creating structurally controlled macromolecules. Here, we report a polypeptide-based macromolecule with spatially organized α-helices that can catalyse its own formation. The system consists of a linear polymeric scaffold containing a high density of initiating groups from which polypeptides are grown, forming a brush polymer. The folding of polypeptide side chains into α-helices dramatically enhances the polymerization rate due to cooperative interactions of macrodipoles between neighbouring α-helices. The parameters that affect the rate are elucidated by a two-stage kinetic model using principles from nucleation-controlled protein polymerizations; the key difference being the irreversible nature of this polymerization.

  1. Combinations of fluorinated solvents with imide salts or methide salts for electrolytes

    DOEpatents

    Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Lei, Norman; Guerrero-Zavala, Guillermo; Kwong, Kristie W

    2015-11-10

    Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include imide salts and/or methide salts as well as fluorinated solvents capable of maintaining single phase solutions at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and improve safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Linear and cyclic imide salts, such as LiN(SO.sub.2CF.sub.2CF.sub.3).sub.2, and LiN(SO.sub.2CF.sub.3).sub.2, as well as methide salts, such as LiC(SO.sub.2CF.sub.3).sub.3 and LiC(SO.sub.2CF.sub.2CF.sub.3).sub.3, may be used in these electrolytes. Fluorinated alkyl groups enhance solubility of these salts in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene, and/or one or more ionic liquids.

  2. Self-Propagating Frontal Polymerization in Water at Ambient Pressure

    NASA Technical Reports Server (NTRS)

    Olten, Nesrin; Kraigsley, Alison; Ronney, Paul D.

    2003-01-01

    Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High

  3. Salt fluoridation and oral health.

    PubMed

    Marthaler, Thomas M

    2013-11-01

    The aim of this paper is to make known the potential of fluoridated salt in community oral health programs, particularly in South Eastern Europe. Since 1922, the addition of iodine to salt has been successful in Switzerland. Goiter is virtually extinct. By 1945, the caries-protective effect of fluorides was well established. Based on the success of water fluoridation, a gynecologist started adding of fluoride to salt. The sale of fluoridated salt began in 1956 in the Swiss Canton of Zurich, and several other cantons followed suit. Studies initiated in the early seventies showed that fluoride, when added to salt, inhibits dental caries. The addition of fluoride to salt for human consumption was officially authorized in 1980-82. In Switzerland 85% of domestic salt consumed is fluoridated and 67% in Germany. Salt fluoridation schemes are reaching more than one hundred million in Mexico, Colombia, Peru and Cuba. The cost of salt fluoridation is very low, within 0.02 and 0.05 € per year and capita. Children and adults of the low socio-economic strata tend to have substantially more untreated caries than higher strata. Salt fluoridation is by far the cheapest method for improving oral health. Salt fluoridation has cariostatic potential like water fluoridation (caries reductions up to 50%). In Europe, meaningful percentages of users have been attained only in Germany (67%) and Switzerland (85%). In Latin America, there are more than 100 million users, and several countries have arrived at coverage of 90 to 99%. Salt fluoridation is by far the cheapest method of caries prevention, and billions of people throughout the world could benefit from this method. Copyright © 2013 by Academy of Sciences and Arts of Bosnia and Herzegovina.

  4. Heterofunctional Glycopolypeptides by Combination of Thiol-Ene Chemistry and NCA Polymerization.

    PubMed

    Krannig, Kai-Steffen; Schlaad, Helmut

    2016-01-01

    Glycopolypeptides are prepared either by the polymerization of glycosylated amino acid N-carboxyanhydrides (NCAs) or by the post-polymerization functionalization of polypeptides with suitable functional groups. Here we present a method for the in-situ functionalization and (co-) polymerization of allylglycine N-carboxyanhydride in a facile one-pot procedure, combining radical thiol-ene photochemistry and nucleophilic ring-opening polymerization techniques, to yield well-defined heterofunctional glycopolypeptides.

  5. Polymerization Initiated at the Sidewalls of Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Tour, James M.; Hudson, Jared L.

    2011-01-01

    A process has been developed for growing polymer chains via anionic, cationic, or radical polymerization from the side walls of functionalized carbon nanotubes, which will facilitate greater dispersion in polymer matrices, and will greatly enhance reinforcement ability in polymeric material.

  6. Physiological responses to salt stress of salt-adapted and directly salt (NaCl and NaCl+Na2SO4 mixture)-stressed cyanobacterium Anabaena fertilissima.

    PubMed

    Swapnil, Prashant; Rai, Ashwani K

    2018-05-01

    Soil salinity in nature is generally mixed type; however, most of the studies on salt toxicity are performed with NaCl and little is known about sulfur type of salinity (Na 2 SO 4 ). Present study discerns the physiologic mechanisms responsible for salt tolerance in salt-adapted Anabaena fertilissima, and responses of directly stressed parent cells to NaCl and NaCl+Na 2 SO 4 mixture. NaCl at 500 mM was lethal to the cyanobacterium, whereas salt-adapted cells grew luxuriantly. Salinity impaired gross photosynthesis, electron transport activities, and respiration in parent cells, but not in the salt-adapted cells, except a marginal increase in PSI activity. Despite higher Na + concentration in the salt mixture, equimolar NaCl appeared more inhibitive to growth. Sucrose and trehalose content and antioxidant activities were maximal in 250 mM NaCl-treated cells, followed by salt mixture and was almost identical in salt-adapted (exposed to 500 mm NaCl) and control cells, except a marginal increase in ascorbate peroxidase activity and an additional fourth superoxide dismutase isoform. Catalase isoform of 63 kDa was induced only in salt-stressed cells. Salinity increased the uptake of intracellular Na + and Ca 2+ and leakage of K + in parent cells, while cation level in salt-adapted cells was comparable to control. Though there was differential increase in intracellular Ca 2+ under different salt treatments, ratio of Ca 2+ /Na + remained the same. It is inferred that stepwise increment in the salt concentration enabled the cyanobacterium to undergo priming effect and acquire robust and efficient defense system involving the least energy.

  7. Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives

    PubMed Central

    Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

    2013-01-01

    The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022–0.088 mmol/g). HAp (2–8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. PMID:23910263

  8. A review of polymeric membranes and processes for potable water reuse

    PubMed Central

    Warsinger, David M.; Chakraborty, Sudip; Tow, Emily W.; Plumlee, Megan H.; Bellona, Christopher; Loutatidou, Savvina; Karimi, Leila; Mikelonis, Anne M.; Achilli, Andrea; Ghassemi, Abbas; Padhye, Lokesh P.; Snyder, Shane A.; Curcio, Stefano; Vecitis, Chad; Arafat, Hassan A.; Lienhard, John H.

    2018-01-01

    Conventional water resources in many regions are insufficient to meet the water needs of growing populations, thus reuse is gaining acceptance as a method of water supply augmentation. Recent advancements in membrane technology have allowed for the reclamation of municipal wastewater for the production of drinking water, i.e., potable reuse. Although public perception can be a challenge, potable reuse is often the least energy-intensive method of providing additional drinking water to water stressed regions. A variety of membranes have been developed that can remove water contaminants ranging from particles and pathogens to dissolved organic compounds and salts. Typically, potable reuse treatment plants use polymeric membranes for microfiltration or ultrafiltration in conjunction with reverse osmosis and, in some cases, nanofiltration. Membrane properties, including pore size, wettability, surface charge, roughness, thermal resistance, chemical stability, permeability, thickness and mechanical strength, vary between membranes and applications. Advancements in membrane technology including new membrane materials, coatings, and manufacturing methods, as well as emerging membrane processes such as membrane bioreactors, electrodialysis, and forward osmosis have been developed to improve selectivity, energy consumption, fouling resistance, and/or capital cost. The purpose of this review is to provide a comprehensive summary of the role of polymeric membranes in the treatment of wastewater to potable water quality and highlight recent advancements in separation processes. Beyond membranes themselves, this review covers the background and history of potable reuse, and commonly used potable reuse process chains, pretreatment steps, and advanced oxidation processes. Key trends in membrane technology include novel configurations, materials and fouling prevention techniques. Challenges still facing membrane-based potable reuse applications, including chemical and biological

  9. Electrolyte salts for nonaqueous electrolytes

    DOEpatents

    Amine, Khalil; Zhang, Zhengcheng; Chen, Zonghai

    2012-10-09

    Metal complex salts may be used in lithium ion batteries. Such metal complex salts not only perform as an electrolyte salt in a lithium ion batteries with high solubility and conductivity, but also can act as redox shuttles that provide overcharge protection of individual cells in a battery pack and/or as electrolyte additives to provide other mechanisms to provide overcharge protection to lithium ion batteries. The metal complex salts have at least one aromatic ring. The aromatic moiety may be reversibly oxidized/reduced at a potential slightly higher than the working potential of the positive electrode in the lithium ion battery. The metal complex salts may also be known as overcharge protection salts.

  10. ADR salt pill design and crystal growth process for hydrated magnetic salts

    NASA Technical Reports Server (NTRS)

    Shirron, Peter J. (Inventor); DiPirro, Michael J. (Inventor); Canavan, Edgar R. (Inventor)

    2013-01-01

    A process is provided for producing a salt pill for use in very low temperature adiabatic demagnetization refrigerators (ADRs). The method can include providing a thermal bus in a housing. The thermal bus can include an array of thermally conductive metal conductors. A hydrated salt can be grown on the array of thermally conductive metal conductors. Thermal conductance can be provided to the hydrated salt.

  11. Highly sensitive electrochemical biosensor for bisphenol A detection based on a diazonium-functionalized boron-doped diamond electrode modified with a multi-walled carbon nanotube-tyrosinase hybrid film.

    PubMed

    Zehani, Nedjla; Fortgang, Philippe; Saddek Lachgar, Mohamed; Baraket, Abdoullatif; Arab, Madjid; Dzyadevych, Sergei V; Kherrat, Rochdi; Jaffrezic-Renault, Nicole

    2015-12-15

    A highly sensitive electrochemical biosensor for the detection of Bisphenol A (BPA) in water has been developed by immobilizing tyrosinase onto a diazonium-functionalized boron doped diamond electrode (BDD) modified with multi-walled carbon nanotubes (MWCNTs). The fabricated biosensor exhibits excellent electroactivity towards o-quinone, a product of this enzymatic reaction of BPA oxidation catalyzed by tyrosinase. The developed BPA biosensor displays a large linear range from 0.01 nM to 100 nM, with a detection limit (LOD) of 10 pM. The feasibility of the proposed biosensor has been demonstrated on BPA spiked water river samples. Therefore, it could be a promising and reliable analytical tool for on-site monitoring of BPA in waste water. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Reconsolidated Salt as a Geotechnical Barrier

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

    Hansen, Francis D.; Gadbury, Casey

    Salt as a geologic medium has several attributes favorable to long-term isolation of waste placed in mined openings. Salt formations are largely impermeable and induced fractures heal as stress returns to equilibrium. Permanent isolation also depends upon the ability to construct geotechnical barriers that achieve nearly the same high-performance characteristics attributed to the native salt formation. Salt repository seal concepts often include elements of reconstituted granular salt. As a specific case in point, the Waste Isolation Pilot Plant recently received regulatory approval to change the disposal panel closure design from an engineered barrier constructed of a salt-based concrete to onemore » that employs simple run-of-mine salt and temporary bulkheads for isolation from ventilation. The Waste Isolation Pilot Plant is a radioactive waste disposal repository for defense-related transuranic elements mined from the Permian evaporite salt beds in southeast New Mexico. Its approved shaft seal design incorporates barrier components comprising salt-based concrete, bentonite, and substantial depths of crushed salt compacted to enhance reconsolidation. This paper will focus on crushed salt behavior when applied as drift closures to isolate disposal rooms during operations. Scientific aspects of salt reconsolidation have been studied extensively. The technical basis for geotechnical barrier performance has been strengthened by recent experimental findings and analogue comparisons. The panel closure change was accompanied by recognition that granular salt will return to a physical state similar to the halite surrounding it. Use of run-of-mine salt ensures physical and chemical compatibility with the repository environment and simplifies ongoing disposal operations. Our current knowledge and expected outcome of research can be assimilated with lessons learned to put forward designs and operational concepts for the next generation of salt repositories. Mined salt

  13. Pathophysiology of salt sensitivity hypertension.

    PubMed

    Ando, Katsuyuki; Fujita, Toshiro

    2012-06-01

    Dietary salt intake is the most important factor contributing to hypertension, but the salt susceptibility of blood pressure (BP) is different in individual subjects. Although the pathogenesis of salt-sensitive hypertension is heterogeneous, it is mainly attributable to an impaired renal capacity to excrete sodium (Na(+) ). We recently identified two novel mechanisms that impair renal Na(+) -excreting function and result in an increase in BP. First, mineralocorticoid receptor (MR) activation in the kidney, which facilitates distal Na(+) reabsorption through epithelial Na(+) channel activation, causes salt-sensitive hypertension. This mechanism exists not only in models of high-aldosterone hypertension as seen in conditions of obesity or metabolic syndrome, but also in normal- or low-aldosterone type of salt-sensitive hypertension. In the latter, Rac1 activation by salt excess causes MR stimulation. Second, renospecific sympathoactivation may cause an increase in BP under conditions of salt excess. Renal beta2 adrenoceptor stimulation in the kidney leads to decreased transcription of the gene encoding WNK4, a negative regulator of Na(+) reabsorption through Na(+) -Cl (-) cotransporter in the distal convoluted tubules, resulting in salt-dependent hypertension. Abnormalities identified in these two pathways of Na(+) reabsorption in the distal nephron may present therapeutic targets for the treatment of salt-sensitive hypertension.

  14. Photocatalytic surface patterning of cellulose using diazonium salts and visible light.

    PubMed

    Schroll, Peter; Fehl, Charlie; Dankesreiter, Stephan; König, Burkhard

    2013-10-14

    Coumarin-functionalized cellulose sheets were chemically modified using a visible light catalyzed "Photo-Meerwein" arylation. Use of a photomask to pattern the surface resulted in directly visible images.

  15. Photocatalytic Surface Patterning of Cellulose using Diazonium Salts and Visible Light

    PubMed Central

    Schroll, Peter; Fehl, Charlie; Dankesreiter, Stephan

    2013-01-01

    Coumarin-functionalized cellulose sheets were chemically modified using a visible light catalyzed “Photo-Meerwein” arylation. Use of a photomask to pattern the surface resulted in directly visible images. PMID:23963264

  16. Free heme and sickle hemoglobin polymerization

    NASA Astrophysics Data System (ADS)

    Uzunova, Veselina V.

    This work investigates further the mechanism of one of the most interesting of the protein self-assembly systems---the polymerization of sickle hemoglobin and the role of free heme in it. Polymerization of sickle hemoglobin is the primary event in the pathology of a chronic hemolytic condition called sickle cell anemia with complex pathogenesis, unexplained variability and symptomatic treatment. Auto-oxidation develops in hemoglobin solutions exposed to room temperature and causes release of ferriheme. The composition of such solutions is investigated by mass spectrometry. Heme dimers whose amount corresponds to the initial amounts of heme released from the protein are followed. Differences in the dimer peak height are established for hemoglobin variants A, S and C and depending on the exposure duration. The effects of free heme on polymerization kinetics are studied. Growth rates and two characteristic parameters of nucleation are measured for stored Hb S. After dialysis of polymerizing solutions, no spherulites are detected at moderately high supersaturation and prolonged exposure times. The addition of 0.16-0.26 mM amounts of heme to dialyzed solutions leads to restoration of polymerization. The measured kinetic parameters have higher values compared to the ones before dialysis. The amount of heme in non-dialyzed aged solution is characterized using spectrophotometry. Three methods are used: difference in absorbance of dialyzed and non-dialyzed solutions, characteristic absorbance of heme-albumin complex and absorbance of non-dialyzed solutions with added potassium cyanide. The various approaches suggest the presence of 0.12 to 0.18 mM of free ferriheme in such solutions. Open questions are whether the same amounts of free heme are present in vivo and whether the same mechanism operates intracellulary. If the answer to those questions is positive, then removal of free heme from erythrocytes can influence their readiness to sickle.

  17. Microbial Successions and Metabolite Changes during Fermentation of Salted Shrimp (Saeu-Jeot) with Different Salt Concentrations

    PubMed Central

    Lee, Se Hee; Jung, Ji Young; Jeon, Che Ok

    2014-01-01

    To investigate the effects of salt concentration on saeu-jeot (salted shrimp) fermentation, four sets of saeu-jeot samples with 20%, 24%, 28%, and 32% salt concentrations were prepared, and the pH, bacterial and archaeal abundances, bacterial communities, and metabolites were monitored during the entire fermentation period. Quantitative PCR showed that Bacteria were much more abundant than Archaea in all saeu-jeot samples, suggesting that bacterial populations play more important roles than archaeal populations even in highly salted samples. Community analysis indicated that Vibrio, Photobacterium, Psychrobacter, Pseudoalteromonas, and Enterovibrio were identified as the initially dominant genera, and the bacterial successions were significantly different depending on the salt concentration. During the early fermentation period, Salinivibrio predominated in the 20% salted samples, whereas Staphylococcus, Halomonas, and Salimicrobium predominated in the 24% salted samples; eventually, Halanaerobium predominated in the 20% and 24% salted samples. The initially dominant genera gradually decreased as the fermentation progressed in the 28% and 32% salted samples, and eventually Salimicrobium became predominant in the 28% salted samples. However, the initially dominant genera still remained until the end of fermentation in the 32% salted samples. Metabolite analysis showed that the amino acid profile and the initial glycerol increase were similar in all saeu-jeot samples regardless of the salt concentration. After 30–80 days of fermentation, the levels of acetate, butyrate, and methylamines in the 20% and 24% salted samples increased with the growth of Halanaerobium, even though the amino acid concentrations steadily increased until approximately 80–107 days of fermentation. This study suggests that a range of 24–28% salt concentration in saeu-jeot fermentation is appropriate for the production of safe and tasty saeu-jeot. PMID:24587230

  18. Kinematics and dynamics of salt movement driven by sub-salt normal faulting and supra-salt sediment accumulation - combined analogue experiments and analytical calculations

    NASA Astrophysics Data System (ADS)

    Warsitzka, Michael; Kukowski, Nina; Kley, Jonas

    2017-04-01

    In extensional sedimentary basins, the movement of ductile salt is mainly controlled by the vertical displacement of the salt layer, differential loading due to syn-kinematic deposition, and tectonic shearing at the top and the base of the salt layer. During basement normal faulting, salt either tends to flow downward to the basin centre driven by its own weight or it is squeezed upward due to differential loading. In analogue experiments and analytical models, we address the interplay between normal faulting of the sub-salt basement, compaction and density inversion of the supra-salt cover and the kinematic response of the ductile salt layer. The analogue experiments consist of a ductile substratum (silicone putty) beneath a denser cover layer (sand mixture). Both layers are displaced by normal faults mimicked through a downward moving block within the rigid base of the experimental apparatus and the resulting flow patterns in the ductile layer are monitored and analysed. In the computational models using an analytical approximative solution of the Navier-Stokes equation, the steady-state flow velocity in an idealized natural salt layer is calculated in order to evaluate how flow patterns observed in the analogue experiments can be translated to nature. The analytical calculations provide estimations of the prevailing direction and velocity of salt flow above a sub-salt normal fault. The results of both modelling approaches show that under most geological conditions salt moves downwards to the hanging wall side as long as vertical offset and compaction of the cover layer are small. As soon as an effective average density of the cover is exceeded, the direction of the flow velocity reverses and the viscous material is squeezed towards the elevated footwall side. The analytical models reveal that upward flow occurs even if the average density of the overburden does not exceed the density of salt. By testing various scenarios with different layer thicknesses

  19. Measuring salt retention.

    DOT National Transportation Integrated Search

    2013-03-01

    This research developed and completed a field evaluation of salt distribution equipment. The evaluation provides a direct comparison of three different types of salt spreaders at three different truck speeds and brine rates. A rubber mat was divided ...

  20. Non-equilibrium supramolecular polymerization

    PubMed Central

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J.

    2017-01-01

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term “non-equilibrium self-assembly” by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization. PMID:28349143

  1. Polymerization of the tubulin-colchicine complex: relation to microtubule assembly.

    PubMed

    Andreu, J M; Wagenknecht, T; Timasheff, S N

    1983-03-29

    The polymerization of purified tubulin-colchicine complex, which results in polymers different from microtubules under microtubule-promoting conditions, has been characterized. It proceeds as a nucleated condensation polymerization, requires Mg2+, and is inhibited by small concentrations of Ca2+. Polymerization requires GTP binding, but GDP is inhibitory. The GTPase activity proceeds, but it is unlinked to polymerization. The thermodynamic characteristics of the growth reaction, namely, the apparent changes of free energy, enthalpy, entropy, heat capacity, and preferential interaction with H+ and Mg2+, are very similar to those of microtubule assembly. It is proposed that the interactions responsible for the two types of polymerization are very similar and that the molecular mechanism of microtubule inhibition by colchicine may consist in a drug-induced distortion of the normal protomer bonding geometry.

  2. Unlocking the Structure and Dynamics of Thin Polymeric Films

    DTIC Science & Technology

    2016-11-13

    AFRL-AFOSR-JP-TR-2016-0092 Unlocking the Structure and Dynamics of Thin Polymeric Films Andrew Whittaker THE UNIVERSITY OF QUEENSLAND Final Report 11...Final 3. DATES COVERED (From - To)  15 Jun 2015 to 16 Jun 2016 4. TITLE AND SUBTITLE Unlocking the Structure and Dynamics of Thin Polymeric Films 5a...the interfacial structure that are inherent in thin films affects how polymers behave. A number of technically relevant polymeric systems were

  3. Fetal bile salt metabolism

    PubMed Central

    Smallwood, R. A.; Lester, R.; Piasecki, G. J.; Klein, P. D.; Greco, R.; Jackson, B. T.

    1972-01-01

    Bile salt metabolism was studied in fetal dogs 1 wk before term. The size and distribution of the fetal bile salt pool were measured, and individual bile salts were identified. The hepatic excretion of endogenous bile salts was studied in bile fistula fetuses, and the capacity of this excretory mechanism was investigated by the i.v. infusion of a load of sodium taurocholate-14C up to 20 times the endogenous pool size. The total fetal bile salt pool was 30.9±2.7 μmoles, of which two-thirds was in the fetal gallbladder. Expressed on a body weight basis, this was equal to approximately one-half the estimated pool size in the adult dog (119.2±11.3 vs. 247.5±33.1 μmoles/kg body wt). Measurable quantities of bile salt were found in small bowel (6.0±1.8 μmoles), large bowel (1.1±0.3 μmoles), liver (1.2±0.5 μmoles), and plasma (0.1±0.03 μmoles). Plasma bile salt levels were significantly greater in fetal than in maternal plasma (1.01±0.24 μg/ml vs. 0.36±0.06 μg/ml; P < 0.05). Fetal hepatic bile salt excretion showed a fall over the period of study from 2.04±0.34 to 0.30±0.07 μmoles/hr. The maximal endogenous bile salt concentration in fetal hepatic bile was 18.7±1.5 μmoles/ml. The concentration in fetal gallbladder bile was 73.9±8.6 μmoles/ml; and, in those studies in which hepatic and gallbladder bile could be compared directly, the gallbladder appeared to concentrate bile four- to fivefold. Taurocholate, taurochenodeoxycholate, and taurodeoxycholate were present in fetal bile, but no free bile salts were identified. The presence of deoxycholate was confirmed by thin-layer chromatography and gas liquid chromatography, and the absence of microorganisms in fetal gut suggests that it was probably transferred from the maternal circulation. After infusion of a taurocholate load, fetal hepatic bile salt excretion increased 30-fold, so that 85-95% of the dose was excreted by the fetal liver during the period of observation. Placental transfer accounted

  4. Rheological stratification of the Hormuz Salt Formation in Iran - microstructural study of the dirty and pure rock salts from the Kuh-e-Namak (Dashti) salt diapir

    NASA Astrophysics Data System (ADS)

    Závada, Prokop; Desbois, Guillaume; Urai, Janos; Schulmann, Karel; Rahmati, Mahmoud; Lexa, Ondrej; Wollenberg, Uwe

    2014-05-01

    Significant viscosity contrasts displayed in flow structures of a mountain namakier (Kuh-e-Namak - Dashti), between 'weak' terrestrial debris bearing rock salt types and 'strong' pure rock salt types are questioned for deformation mechanisms using detailed quantitative microstructural study including crystallographic preferred orientation (CPO) mapping of halite grains. While the solid impurity rich ("dirty") rock salts contain disaggregated siltstone and dolomite interlayers, "clean" salts (debris free) reveal microscopic hematite and remnants of abundant fluid inclusions in non-recrystallized cores of porphyroclasts. Although flow in both, the recrystallized dirty and clean salt types is accommodated by combined mechanisms of pressure-solution creep (PS), grain boundary sliding (GBS) and dislocation creep accommodated grain boundary migration (GBM), their viscosity contrasts are explained by significantly slower rates of intergranular diffusion and piling up of dislocations at hematite inclusions in clean salt types. Porphyroclasts of clean salts deform by semi-brittle and plastic mechanisms with intra-crystalline damage being induced also by fluid inclusions that explode in the crystals at high fluid pressures. Boudins of clean salt types with coarse grained and original sedimentary microstructure suggest that clean rock salts are associated with dislocation creep dominated power law flow in the source layer and the diapiric stem. Rheological contrasts between both rock salt classes apply in general for the variegated and terrestrial debris rich ("dirty") Lower Hormuz and the "clean" rock salt forming the Upper Hormuz, respectively, and suggest that large strain rate gradients likely exist along horizons of mobilized salt types of different composition and microstructure.

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

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin; Sengel, Sultan Butun

    2016-12-01

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

  6. Dosimetry using silver salts

    DOEpatents

    Warner, Benjamin P.

    2003-06-24

    The present invention provides a method for detecting ionizing radiation. Exposure of silver salt AgX to ionizing radiation results in the partial reduction of the salt to a mixture of silver salt and silver metal. The mixture is further reduced by a reducing agent, which causes the production of acid (HX) and the oxidized form of the reducing agent (R). Detection of HX indicates that the silver salt has been exposed to ionizing radiation. The oxidized form of the reducing agent (R) may also be detected. The invention also includes dosimeters employing the above method for detecting ionizing radiation.

  7. Bioactive Polymeric Materials for Tissue Repair

    PubMed Central

    Bienek, Diane R.; Tutak, Wojtek; Skrtic, Drago

    2017-01-01

    Bioactive polymeric materials based on calcium phosphates have tremendous appeal for hard tissue repair because of their well-documented biocompatibility. Amorphous calcium phosphate (ACP)-based ones additionally protect against unwanted demineralization and actively support regeneration of hard tissue minerals. Our group has been investigating the structure/composition/property relationships of ACP polymeric composites for the last two decades. Here, we present ACP’s dispersion in a polymer matrix and the fine-tuning of the resin affects the physicochemical, mechanical, and biological properties of ACP polymeric composites. These studies illustrate how the filler/resin interface and monomer/polymer molecular structure affect the material’s critical properties, such as ion release and mechanical strength. We also present evidence of the remineralization efficacy of ACP composites when exposed to accelerated acidic challenges representative of oral environment conditions. The utility of ACP has recently been extended to include airbrushing as a platform technology for fabrication of nanofiber scaffolds. These studies, focused on assessing the feasibility of incorporating ACP into various polymer fibers, also included the release kinetics of bioactive calcium and phosphate ions from nanofibers and evaluate the biorelevance of the polymeric ACP fiber networks. We also discuss the potential for future integration of the existing ACP scaffolds into therapeutic delivery systems used in the precision medicine field. PMID:28134776

  8. Unlocking the energy capabilities of micron-sized LiFePO4.

    PubMed

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G; Peng, Zhangquan

    2015-08-03

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a 'carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.

  9. Unlocking the energy capabilities of micron-sized LiFePO4

    PubMed Central

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

    2015-01-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a ‘carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations. PMID:26235395

  10. Unlocking the energy capabilities of micron-sized LiFePO4

    NASA Astrophysics Data System (ADS)

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

    2015-08-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a `carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.

  11. The use of Trametes versicolor laccase for the polymerization of aniline in the presence of vesicles as templates.

    PubMed

    Junker, Katja; Kissner, Reinhard; Rakvin, Boris; Guo, Zengwei; Willeke, Martin; Busato, Stephan; Weber, Thomas; Walde, Peter

    2014-02-05

    The enzymatic polymerization of aniline to polyaniline (PANI) with Trametes versicolor laccase (TvL) as catalyst and dioxygen (O₂) as oxidant was investigated in an aqueous medium containing unilamellar vesicles with an average diameter of about 80 nm formed from AOT (=sodium bis(2-ethylhexyl) sulfosuccinate). Compared to the same reaction carried out with horseradish peroxidase isoenzyme C (HRPC) as catalyst and hydrogen peroxide (H₂O₂) as oxidant, notable differences were found in the kinetics of the reaction, as well as in the characteristics of the PANI obtained. Under comparable optimal conditions, which are pH 3.5 for TvL/O₂ and pH 4.3 for HRPC/H₂O₂, the reaction with TvL/O₂ was much slower than with HRPC/H₂O₂, i.e. ≈27 days vs. 1 day reaction time to reach equilibrium with >90% yield at 25 °C. Although in both cases, aniline monomer coupling occurred mainly via the carbon atom in para position of aniline, UV-vis-NIR absorption and EPR measurements indicate that the reaction with TvL/O₂ yielded mainly overoxidized products (with λ(max)=730 nm). These products had a lower amount of unpaired electrons if compared with the products obtained with HRPC/H₂O₂ (with λ(max)≈1000 nm, which is characteristic for the polaron state of PANI-ES, the emeraldine salt form of PANI). Similarly to previous findings with HRPC/H₂O₂, enzyme inactivation occurred during the polymerization also in the case of TvL/O₂. Since the aqueous PANI-vesicle suspensions obtained are of high colloidal stability, they can be used directly as ink in a conventional thermal inkjet printer for printing on paper or on surface treated polyimide films. Printed PANI-ES patterns on paper changed colour from green (emeraldine salt) to blue (emeraldine base) upon exposure to ammonia gas, demonstrating the expected ammonia sensing properties. Copyright © 2013 Elsevier Inc. All rights reserved.

  12. Determination of discretionary salt intake in rural Guatemala and Benin to determine the iodine fortification of salt required to control iodine deficiency disorders: studies using lithium-labeled salt.

    PubMed

    Melse-Boonstra, A; Rozendaal, M; Rexwinkel, H; Gerichhausen, M J; van den Briel, T; Bulux, J; Solomons, N W; West, C E

    1998-09-01

    The use of discretionary salt, which is salt added during cooking and at the table, as a suitable vehicle for iodine intake was assessed by measuring salt consumption using the lithium-marker technique in rural areas of Guatemala and Benin. In both countries, we studied boys aged 6-12 y and their mothers. Subjects used lithium-labeled salt after all unlabeled salt was removed from their households. In Guatemala, 24-h urine samples for 9 mother-son pairs were collected at baseline and on days 7, 8, and 9 during the use of lithium-labeled salt. Total maternal salt intake averaged 5.2 +/- 1.7 g/d (mean +/- SD), of which 77 +/- 24% came from discretionary sources, whereas Guatemalan boys consumed 1.8 +/- 0.6 g salt/d, of which 72 +/- 12% came from discretionary sources. In Benin, urine collection from 13 mother-son pairs took place at baseline and on days 5 and 7. Beninese mothers had a total salt intake of 9.0 +/- 2.9 g/d and their sons had an intake of 5.7 +/- 2.8 g/d; discretionary salt contributed 52 +/- 14% and 50 +/- 13%, respectively, of total salt consumed. Therefore, fortification of household salt appears to be an appropriate method of controlling iodine deficiency in both countries, although fortification of other salt sources could be considered in Benin.

  13. Cellulose biogenesis: Polymerization and crystallization are coupled processes in Acetobacter xylinum.

    PubMed

    Benziman, M; Haigler, C H; Brown, R M; White, A R; Cooper, K M

    1980-11-01

    Calcofluor White ST, stilbene derivative used commerically as an optical brightener for cellulose, increased the rate of glucose polymerization into cellulose by resting cells of the gram-negative bacterium Acetobacter xylinum. This bacterium normally produces a ribbon of cellulose that is a composite of crystalline microfibrils. In concentrations above 0.1 mM, Calcofluor disrupts the assembly of crystalline cellulose I microfibrils and their integration into a composite ribbon by stoichiometric binding to glucose residues of newly polymerized glucan chains. Under these conditions, the rate of glucose polymerization increases up to 4 times the control rate, whereas oxygen uptake increases only 10-15%. These observed effects are readily reversible. If free Calcofluor is washed away or depleted below the threshold value by binding to cellulose as polymerization continues, ribbon production and the normal rate of polymerization resume. It is concluded that polymerization and crystallization are cell-directed, coupled processes and that the rate of crystallization determines the rate of polymerization. It is suggested that coupling must be maintained for biogenesis of crystalline cellulose I.

  14. Cyclopropenimine superbases: Competitive initiation processes in lactide polymerization

    DOE PAGES

    Stukenbroeker, Tyler S.; Bandar, Jeffrey S.; Zhang, Xiangyi; ...

    2015-07-30

    Cyclopropenimine superbases were employed in this study to catalyze the ring-opening polymerization of lactide. Polymerization occurred readily in the presence and absence of alcohol initiators. Polymerizations in the absence of alcohol initiators revealed a competitive initiation mechanism involving deprotonation of lactide by the cyclopropenimine to generate an enolate. NMR and MALDI-TOF analysis of the poly(lactides) generated from cyclopropenimines in the absence of alcohol initiators showed acylated lactide and hydroxyl end groups. Finally, model studies and comparative experiments with guanidine and phosphazene catalysts revealed the subtle influence of the nature of the superbase on competitive initiation processes.

  15. Hydroxyapatite induces spontaneous polymerization of model self-etch dental adhesives.

    PubMed

    Zhang, Ying; Wu, Ningjing; Bai, Xinyan; Xu, Changqi; Liu, Yi; Wang, Yong

    2013-10-01

    The objective of this study is to report for the first time the spontaneous polymerization phenomenon of self-etch dental adhesives induced by hydroxylapatite (HAp). Model self-etch adhesives were prepared by using a monomer mixture of bis[2-(methacryloyloxy)ethyl] phosphate (2MP) with 2-hydroxyethyl methacrylate (HEMA). The initiator system consisted of camphorquinone (CQ, 0.022 mmol/g) and ethyl 4-dimethylaminobenzoate (4E, 0.022-0.088 mmol/g). HAp (2-8 wt.%) was added to the neat model adhesive. In a dark environment, the polymerization was monitored in-situ using ATR/FT-IR, and the mechanical properties of the polymerized adhesives were evaluated using nanoindentation technique. Results indicated that spontaneous polymerization was not observed in the absence of HAp. However, as different amounts of HAp were incorporated into the adhesives, spontaneous polymerization was induced. Higher HAp content led to higher degree of conversion (DC), higher rate of polymerization (RP) and shorter induction period (IP). In addition, higher 4E content also elevated DC and RP and reduced IP of the adhesives. Nanoindentation result suggested that the Young's modulus of the polymerized adhesives showed similar dependence on HAp and 4E contents. In summary, interaction with HAp could induce spontaneous polymerization of the model self-etch adhesives. This result provides important information for understanding the initiation mechanism of the self-etch adhesives, and may be of clinical significance to strengthen the adhesive/dentin interface based on the finding. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Synthesis and characterization of Cu(II), Co(II) and Ni(II) complexes of a number of sulfadrug azodyes and their application for wastewater treatment

    NASA Astrophysics Data System (ADS)

    El-Baradie, K.; El-Sharkawy, R.; El-Ghamry, H.; Sakai, K.

    2014-03-01

    The azodye ligand (HL1) was synthesized from the coupling of sulfaguanidine diazonium salt with 2,4-dihydroxy-benzaldehyde while the two ligands, HL2 and HL3, were prepared by the coupling of sulfadiazine diazonium salt with salicylaldehyde (HL2) and 2,4-dihydroxy-benzaldehyde (HL3). The prepared ligands were characterized by elemental analysis, IR, 1H NMR and mass spectra. Cu(II), Co(II) and Ni(II) complexes of the prepared ligands have been synthesized and characterized by various spectroscopic techniques like IR, UV-Visible as well as magnetic and thermal (TG and DTA) measurements. It was found that all the ligands behave as a monobasic bidentate which coordinated to the metal center through the azo nitrogen and α-hydroxy oxygen atoms in the case of HL1 and HL3. HL2 coordinated to the metal center through sulfonamide oxygen and pyrimidine nitrogen. The applications of the prepared complexes in the oxidative degradation of indigo carmine dye exhibited good catalytic activity in the presence of H2O2 as an oxidant. The reactions followed first-order kinetics and the rate constants were determined. The degradation reaction involved the catalytic action of the azo-dye complexes toward H2O2 decomposition, which can lead to the generation of HOrad radicals as a highly efficient oxidant attacking the target dye. The detailed kinetic studies and the mechanism of these catalytic reactions are under consideration in our group.

  17. Dietary Salt Intake and Hypertension

    PubMed Central

    2014-01-01

    Over the past century, salt has been the subject of intense scientific research related to blood pressure elevation and cardiovascular mortalities. Moderate reduction of dietary salt intake is generally an effective measure to reduce blood pressure. However, recently some in the academic society and lay media dispute the benefits of salt restriction, pointing to inconsistent outcomes noted in some observational studies. A reduction in dietary salt from the current intake of 9-12 g/day to the recommended level of less than 5-6 g/day will have major beneficial effects on cardiovascular health along with major healthcare cost savings around the world. The World Health Organization (WHO) strongly recommended to reduce dietary salt intake as one of the top priority actions to tackle the global non-communicable disease crisis and has urged member nations to take action to reduce population wide dietary salt intake to decrease the number of deaths from hypertension, cardiovascular disease and stroke. However, some scientists still advocate the possibility of increased risk of CVD morbidity and mortality at extremes of low salt intake. Future research may inform the optimal sodium reduction strategies and intake targets for general populations. Until then, we have to continue to build consensus around the greatest benefits of salt reduction for CVD prevention, and dietary salt intake reduction strategies must remain at the top of the public health agenda. PMID:25061468

  18. 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.

  19. 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.

  20. Preparation of polymeric Janus particles by directional UV-induced reactions.

    PubMed

    Liu, Lianying; Ren, Mingwei; Yang, Wantai

    2009-09-15

    Polymeric Janus particles are obtained by UV-induced selective surface grafting polymerizations and coupling reactions, in virtue of the light-absorption of photoreactive materials such as the immobilized photoinitiator and spread photoinitiator solution on the surfaces exposed to UV light and the sheltering of densely arrayed immovable particles from light. Varying the monomers or macromolecules applied in photografting polymerization or coupling reaction, and choosing diverse polymeric particles of various size, bicolor and amphiphilic Janus particles could be successfully achieved. Observations by fluorescence microscope, scanning electron microscope ,and transmission electron microscope confirmed the asymmetrical morphology of the resultant Janus particles.