Sample records for tetrapyrrole sulfonation metals

  1. Supramolecular metal complex systems based on crown-substituted tetrapyrroles

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    Tsivadze, Aslan Yu [Institute of Physical Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)


    The characteristic features of the structures and properties of crown-substituted porphyrinates and phthalocyaninates are considered. Interactions of these compounds with alkali metal salts yield supramolecular ensembles. The factors determining the architecture of such ensembles are described.

  2. Tetrapyrrole Signaling in Plants

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    Robert M. Larkin


    Full Text Available Tetrapyrroles make critical contributions to a number of important processes in diverse organisms. In plants, tetrapyrroles are essential for light signaling, the detoxification of reactive oxygen species, the assimilation of nitrate and sulfate, respiration, photosynthesis, and programed cell death. Thus, it is not surprising that tetrapyrrole metabolism is strictly regulated and that tetrapyrrole metabolism affects signaling mechanisms that regulate gene expression. In plants and algae, tetrapyrroles are synthesized in plastids and were some of the first plastid signals demonstrated to regulate nuclear gene expression. In plants, the mechanism of tetrapyrrole-dependent plastid-to-nucleus signaling remains poorly understood. Additionally, some of experiments that tested ideas for possible signaling mechanisms appeared to produce conflicting data. In some instances, these conflicts are potentially explained by different experimental conditions. Although the biological function of tetrapyrrole signaling is poorly understood, there is compelling evidence that this signaling is significant. Specifically, this signaling appears to affect the accumulation of starch and may promote abiotic stress tolerance. Tetrapyrrole-dependent plastid-to-nucleus signaling interacts with a distinct plastid-to-nucleus signaling mechanism that depends on GENOMES UNCUOPLED1 (GUN1. GUN1 contributes to a variety of processes, such as chloroplast biogenesis, the circadian rhythm, abiotic stress tolerance, and development. Thus, the contribution of tetrapyrrole signaling to plant function is potentially broader than we currently appreciate. In this review, I discuss these aspects of tetrapyrrole signaling.

  3. Synthesis, Spectral Analysis and Preliminary in Vitro Evaluation of Some Tetrapyrrolic Complexes with 3d Metal Ions

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    Radu Socoteanu


    Full Text Available In this paper, two tetrapyrrolic complexes, Zn(II-5-(3-hydroxyphenyl-10,15,20-tris-(4-acetoxy-3-methoxyphenylporphyrin and Cu(II-5-(3-hydroxyphenyl-10,15,20-tris-(4-acetoxy-3-methoxyphenylporphyrin were synthesized, and characterized from a spectral and biological point of view. The study provided data concerning the behavior of identical external substituents vs. two different core insertions. Some of the properties of the proposed tetrapyrrolic structures were highlighted, having photodynamic therapy of cancer as a targeted biomedical application. Elemental analysis, NMR, FTIR and UV-Vis data in various solvents were provided. A preliminary in vitro study on normal and cancer cultured cells was carried out for biocompatibility assessment in dark conditions. The preliminary in vitro study performed on human peripheral mononuclear cells exposed to tetrapyrrolic compounds (2 µM showed that the proposed compounds had a convenient cytotoxic profile on human normal peripheral blood mononuclear cells under dark conditions. Meanwhile, the investigated compounds reduced the number of metabolically active breast tumor MCF-7 cells, with the exception of Zn(II complex-containing a symmetrical ligand. Accordingly, preliminary in vitro data suggest that the proposed tetrapyrrolic compounds are good candidates for PDT, as they limit tumor expansion even under dark conditions, whilst sparing normal cells.

  4. Prevention of poxvirus infection by tetrapyrroles

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    Marzilli Luigi G


    Full Text Available Abstract Background Prevention of poxvirus infection is a topic of great current interest. We report inhibition of vaccinia virus in cell culture by porphyrins and phthalocyanines. Most previous work on the inhibition of viruses with tetrapyrroles has involved photodynamic mechanisms. The current study, however, investigates light-independent inhibition activity. Methods The Western Reserve (WR and International Health Department-J (IHD-J strains of vaccinia virus were used. Virucidal and antiviral activities as well as the cytotoxicity of test compounds were determined. Results Examples of active compounds include zinc protoporphyrin, copper hematoporphyrin, meso(2,6-dihydroxyphenylporphyrin, the sulfonated tetra-1-naphthyl and tetra-1-anthracenylporphyrins, selected sulfonated derivatives of halogenated tetraphenyl porphyrins and the copper chelate of tetrasulfonated phthalocyanine. EC50 values for the most active compounds are as low as 0.05 µg/mL (40 nM. One of the most active compounds was the neutral meso(2,6-dihydroxyphenylporphyrin, indicating that the compounds do not have to be negatively charged to be active. Conclusions Porphyrins and phthalocyanines have been found to be potent inhibitors of infection by vaccinia virus in cell culture. These tetrapyrroles were found to be active against two different virus strains, and against both enveloped and non-enveloped forms of the virus, indicating that these compounds may be broadly effective in their ability to inhibit poxvirus infection.

  5. Efficient and selective adsorption of multi-metal ions using sulfonated cellulose as adsorbent. (United States)

    Dong, Cuihua; Zhang, Fulong; Pang, Zhiqiang; Yang, Guihua


    Contamination of heavy metal in wastewater has caused great concerns on human life and health. Developing an efficient material to eliminate the heavy metal ions has been a popular topic in recent years. In this work, sulfonated cellulose (SC) was explored as efficient adsorbent for metal ions in solution. Thermo gravimetric analyzer (TGA), X-ray diffraction (XRD) and Fourier-transform infrared spectrometer (FTIR) first analyzed the characterizations of SC. Subsequently, effects of solution pH, adsorbent loading, temperature and initial metal ion concentration on adsorption performance were investigated. The results showed that sulfonated modification of cellulose could decrease the crystallinity and thermostability of cellulose. Due to its excellent performance of adsorption to metal ions, SC could reach adsorption equilibrium status within as short as 2min. In multi-component solution, SC can orderly removes Fe(3+), Pb(2+) and Cu(2+) with excellent selectivity and high efficiency. In addition, SC is a kind of green and renewable adsorbent because it can be easily regenerated by treatment with acid or chelating liquors. The mechanism study shows that the sulfonic group play a major role in the adsorption process. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Syntheses, crystal structures and characterization of divalent transition metal sulfonate complexes with o-phenanthroline (United States)

    Yang, Jin; Ma, Jian-Fang; Wu, Dong-Mei; Guo, Li-Ping; Liu, Jing-Fu


    Three new complexes, namely [Cu(phen)(L)(H 2O) 2]L·H 2O 1, [M(phen) 2(H 2O) 2]2L·6H 2O [M=Co( 2), Ni( 3)], where, HL=4-methylbenzenesulfonic acid and phen= o-phenanthroline, have been synthesized. The crystal structures were determined by X-ray diffraction method and refined by full-matrix least-squares methods to R=0.0535 and wR=0.1492 using 3567 reflections with I>2 σ( I) for 1; R=0.0388 and wR=0.1223 using 3844 reflections with I>2 σ( I) for 2; and R=0.0401 and wR=0.1222 using 3425 reflections with I>2 σ( I) for 3. 1 Consists of cationic species [Cu(phen)(L)(H 2O) 2] +, in which Cu(II) ion is five-coordinated by two nitrogen atoms of o-phenanthroline, two water molecules and one sulfonate oxygen atom. The cations and the non-coordinating sulfonate anions are linked by hydrogen bonds to form infinite chains. Complexes 2 and 3 are isostructral compounds. Each of them consists of cationic species [M(phen) 2(H 2O) 2] 2+, in which metal ion is six-coordinated by four nitrogen atoms from two o-phenanthroline molecules and two water oxygen atoms. The sulfonate ions do not coordinate to metal ion. The cations, non-coordinating sulfonate ions and lattice water molecules are linked by hydrogen bonds to form infinite zigzag chains. CV, FT-IR, UV-Vis and TGA were also used to characterize these compounds.

  7. Ion-Selective Ionic Polymer Metal Composite (IPMC) Actuator Based on Crown Ether Containing Sulfonated Poly(Arylene Ether Ketone)

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    Tas, Sinem; Zoetebier, Bram; Sardan Sukas, Ö.; Bayraktar, Muharrem; Hempenius, Mark A.; Vancso, Gyula J.; Nijmeijer, Dorothea C.

    This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane

  8. Removal of textile dyes and metallic ions using polyelectrolytes and macroelectrolytes containing sulfonic acid groups. (United States)

    Caldera Villalobos, M; Peláez Cid, A A; Herrera González, Ana M


    This work reports the removal of textile dyes and metallic ions by means of adsorption and coagulation-flocculation using two polyelectrolytes and two macroelectrolytes containing sulfonic acid groups. The adsorption of textile dyes was studied in aqueous solutions containing cationic dyes and in wastewater containing a vat dye. Also, removal of vat and naphthol dyes was studied using the process of coagulation-flocculation. The results show these materials possess elevated adsorption capacity, and they accomplished removal rates above 97% in aqueous solutions. The removal of the vat dye improved the quality of the wastewater notably, and an uncolored effluent was obtained at the end of the treatment. The treatment using adsorption decreased the values for coloration, conductivity, suspended solids, and pH. The removal of vat and naphthol dyes by means of coagulation-flocculation was studied as well, and removal rates of 90% were obtained. The polyelectrolytes and macroelectrolytes also proved effective in the adsorption of metallic ions in wastewater. The treatment using adsorption accomplished high removal rates of metallic ions, and it showed greater selectivity towards Cu(2+), Fe(3+) and Pb(2+). A decrease in the content of solids as well as the values for COD and conductivity was observed in the wastewater as well. The analyses of FT-IR indicated that cationic dyes and metallic ions were chemisorbed by means of ionic exchange. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Electro-active Polymer Actuator Based on Sulfonated Polyimide with Highly Conductive Silver Electrodes Via Self-metallization. (United States)

    Song, Jiangxuan; Jeon, Jin-Han; Oh, Il-Kwon; Park, K C


    We report here a facile synthesis of high performance electro-active polymer actuator based on a sulfonated polyimide with well-defined silver electrodes via self-metallization. The proposed method greatly reduces fabrication time and cost, and obviates a cation exchange process required in the fabrication of ionic polymer-metal composite actuators. Also, the self-metallized silver electrodes exhibit outstanding metal-polymer adhesion with high conductivity, resulting in substantially larger tip displacements compared with Nafion-based actuators. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Sulfonate Functionalisation of Transition Metal Complexes: A Versatile Tool Towards Catalyst Recovery

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    Virboul, M.A.N.|info:eu-repo/dai/nl/304837709


    This thesis describes the synthesis and application of sulfonate-functionalised ligands in organometallic chemistry and (aqueous) catalysis. Due to their ability to trigger specific solubility, different NHC ligand precursors bearing a butyl-sulfonate chain were synthesised. The formation of

  11. Fast microwave-assisted solvothermal synthesis of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated MWCNTs: Pd-based bimetallic catalysts for ethanol oxidation in alkaline medium

    CSIR Research Space (South Africa)

    Ramulifho, T


    Full Text Available The preparation of metal nanoparticles (Pd, Ni, Sn) supported on sulfonated multi-walled carbon nanotubes (SF-MWCNTs) using a very rapid microwave-assisted solvothermal strategy has been described. Electrocatalytic behaviour of the SF...

  12. Tetrapyrrole pigments in the geologic record

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    Louda, J.W.; Baker, E.W.


    This paper is a synthesis of our ongoing studies on the fossilization of biotic tetrapyrrole pigments and is directed at revealing the utility of such study in assessing pre-, syn- and post-depositional processes. Diagenesis is found to become fated during oxic or anoxic deposition as to pigment destruction or fossilization, respectively. The progress of organic maturation has been followed in suited of oceanic sediments as well as shales and petroleum crudes from various basins in the US and Canada. Early catagenesis is witnessed by the release (ex kerogen.) of large quantities, re bitumen, of C28 to C34 V=O porphyrins. As catagenesis continues pigment concentration decreases, due to dilution, and higher C number porphyrins (C34-C45+) are added. Once the source is depleted or divorced from the bitumen, maturation leads to dealkylation which ends in the destruction of all tetrapyrrole structure. These changes are in concert with a shift from DPEP to ETIO dominance and parallel overall organic maturation in strict fashions. Organic source and paleoenvironment may also be addressed through porphyrin studies. Patterns of tetrapyrroles can differentiate the more allochthonous nature of black shale OM in the N. Atlantic from the autochthonous materials in these sequences in the margins of N.W. Africa and the S. Atlantic (high yield, DPEP).

  13. Polystyrene Sulfonate Threaded through a Metal-Organic Framework Membrane for Fast and Selective Lithium-Ion Separation. (United States)

    Guo, Yi; Ying, Yulong; Mao, Yiyin; Peng, Xinsheng; Chen, Banglin


    Extraction of lithium ions from salt-lake brines is very important to produce lithium compounds. Herein, we report a new approach to construct polystyrene sulfonate (PSS) threaded HKUST-1 metal-organic framework (MOF) membranes through an in situ confinement conversion process. The resulting membrane PSS@HKUST-1-6.7, with unique anchored three-dimensional sulfonate networks, shows a very high Li(+) conductivity of 5.53×10(-4)  S cm(-1) at 25 °C, 1.89×10(-3)  S cm(-1) at 70 °C, and Li(+) flux of 6.75 mol m(-2)  h(-1) , which are five orders higher than that of the pristine HKUST-1 membrane. Attributed to the different size sieving effects and the affinity differences of the Li(+) , Na(+) , K(+) , and Mg(2+) ions to the sulfonate groups, the PSS@HKUST-1-6.7 membrane exhibits ideal selectivities of 78, 99, and 10296 for Li(+) /Na(+) , Li(+) /K(+) , Li(+) /Mg(2+) and real binary ion selectivities of 35, 67, and 1815, respectively, the highest ever reported among ionic conductors and Li(+) extraction membranes. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Regulation and function of tetrapyrrole biosynthesis in plants and algae. (United States)

    Brzezowski, Pawel; Richter, Andreas S; Grimm, Bernhard


    Tetrapyrroles are macrocyclic molecules with various structural variants and multiple functions in Prokaryotes and Eukaryotes. Present knowledge about the metabolism of tetrapyrroles reflects the complex evolution of the pathway in different kingdoms of organisms, the complexity of structural and enzymatic variations of enzymatic steps, as well as a wide range of regulatory mechanisms, which ensure adequate synthesis of tetrapyrrole end-products at any time of development and environmental condition. This review intends to highlight new findings of research on tetrapyrrole biosynthesis in plants and algae. In the course of the heme and chlorophyll synthesis in these photosynthetic organisms, glutamate, one of the central and abundant metabolites, is converted into highly photoreactive tetrapyrrole intermediates. Thereby, several mechanisms of posttranslational control are thought to be essential for a tight regulation of each enzymatic step. Finally, we wish to discuss the potential role of tetrapyrroles in retrograde signaling and point out perspectives of the formation of macromolecular protein complexes in tetrapyrrole biosynthesis as an efficient mechanism to ensure a fine-tuned metabolic flow in the pathway. This article is part of a Special Issue entitled: Chloroplast Biogenesis. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Sulfonated Polyaniline Coated Mercury Film Electrodes for Voltammetric Analysis of Metals in Water

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    Denise Alves Fungaro


    Full Text Available The electrochemical polymerization of 2-aminobenzenesulfonic acid with and without aniline has been carried by cyclic potencial sweep in sulfuric acid solution at the glassy carbon electrode. The polymer and copolymer formed have been characterized voltammetrically. The sulfonated polyaniline coated mercury thin-film electrodes have been evaluated for use with anodic stripping voltammetry. The electrodes were tested and compared with a conventional thin-film mercury electrode. Calibration plots showed linearity up to 10-7 mol L-1. Detection limits for zinc, lead and cadmium test species are very similar at around 12 nmol L-1. Applications to analysis of waters samples are demonstrated.

  16. 2010 Tetrapyrroles, Chemistry & Biology of Gordon Research Conference

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    Angela Wilks


    The objective of the Chemistry & Biology of Tetrapyrroles Gordon Conference is to bring together researchers from diverse disciplines that otherwise would not interact. By bringing biologists, chemists, engineers and clinicians with a common interest in tetrapyrroles the conference provides a forum for cross-disciplinary ideas and collaboration. The perspective provided by biologists, chemists, and clinicians working in fields such as newly discovered defects in human porphyrin metabolism, the myriad of strategies for light harvesting in photosynthetic organisms, novel tetrapyrroles that serve as auxiliary chromophores or enzyme cofactors, synthetic strategies in the design of novel tetrapyrrole scaffolds, and tetrapyrrole based cell signaling and regulatory systems, makes this conference unique in the field. Over the years the growing evidence for the role of tetrapyrroles and their reactive intermediates in cell signaling and regulation has been of increasing importance at this conference. The 2010 conference on Chemistry & Biology of Tetrapyrroles will focus on many of these new frontiers as outlined in the preliminary program listed. Speakers will emphasize unpublished results and new findings in the field. The oral sessions will be followed by the highly interactive afternoon poster sessions. The poster sessions provide all conferees with the opportunity to present their latest research and to exchange ideas in a more informal setting. As in the past, this opportunity will continue during the nightly social gathering that takes place in the poster hall following the evening lectures. All conferees are encouraged to submit and present posters. At the conference the best poster in the areas of biology, chemistry and medicine will be selected by a panel of previous conference chairs.

  17. A flexible metal-organic framework with a high density of sulfonic acid sites for proton conduction (United States)

    Yang, Fan; Xu, Gang; Dou, Yibo; Wang, Bin; Zhang, Heng; Wu, Hui; Zhou, Wei; Li, Jian-Rong; Chen, Banglin


    The design of stable electrolyte materials with high proton conductivity for use in proton exchange membrane fuel cells remains a challenge. Most of the materials explored have good conductivity at high relative humidity (RH), but significantly decreased conductivity at reduced RH. Here we report a chemically stable and structurally flexible metal-organic framework (MOF), BUT-8(Cr)A, possessing a three-dimensional framework structure with one-dimensional channels, in which high-density sulfonic acid (-SO3H) sites arrange on channel surfaces for proton conduction. We propose that its flexible nature, together with its -SO3H sites, could allow BUT-8(Cr)A to self-adapt its framework under different humid environments to ensure smooth proton conduction pathways mediated by water molecules. Relative to other MOFs, BUT-8(Cr)A not only has a high proton conductivity of 1.27 × 10-1 S cm-1 at 100% RH and 80 °C but also maintains moderately high proton conductivity at a wide range of RH and temperature.

  18. Novel nanofiltration membranes consisting of a sulfonated pentablock copolymer rejection layer for heavy metal removal. (United States)

    Thong, Zhiwei; Han, Gang; Cui, Yue; Gao, Jie; Chung, Tai-Shung; Chan, Sui Yung; Wei, Shawn


    Facing stringent regulations on wastewater discharge containing heavy metal ions, various industries are demanding more efficient and effective treatment methods. Among the methods available, nanofiltration (NF) is a feasible and promising option. However, the development of new membrane materials is constantly required for the advancement of this technology. This is a report of the first attempt to develop a composite NF membrane comprising a molecularly designed pentablock copolymer selective layer for the removal of heavy metal ions. The resultant NF membrane has a mean effective pore diameter of 0.50 nm, a molecular weight cutoff of 255 Da, and a reasonably high pure water permeability (A) of 2.4 LMH/bar. The newly developed NF membrane can effectively remove heavy metal cations such as Pb(2+), Cd(2+), Zn(2+), and Ni(2+) with a rejection of >98.0%. On the other hand, the membrane also shows reasonably high rejections toward anions such as HAsO4(2-) (99.9%) and HCrO4(-) (92.3%). This performance can be attributed to (1) the pentablock copolymer's unique ability to form a continuous water transport passageway with a defined pore size and (2) the incorporation of polyethylenimine as a gutter layer between the selective layer and the substrate. To the best of our knowledge, this is the first reported NF membrane comprising this pentablock copolymer as the selective material. The promising preliminary results achieved in this study provide a useful platform for the development of new NF membranes for heavy metal removal.

  19. A series of phenyl sulfonate metal coordination polymers as catalysts for one-pot Biginelli reactions under solvent-free conditions. (United States)

    Wang, Jin-Hua; Tang, Gui-Mei; Wang, Yong-Tao; Cui, Yue-Zhi; Wang, Jun-Jie; Ng, Seik Weng


    Three new metal coordination polymers, namely, [Co(DPP)2(H2O)2]·(BS)2·2H2O (1), [Co(DPP)2(H2O)2]·(ABS)2·2H2O (2) and [Co(DPP)2(MBS)2] (3) [DPP = 1,3-di(pyridin-4-yl)propane, BS = phenyl sulfonic acid, ABS = p-aminobenzene sulfonic acid, MBS = p-methylbenzene sulfonic acid] were obtained under hydrothermal conditions. Complexes 1-3 were structurally characterized using X-ray single-crystal diffraction, XRD and IR spectroscopy. Both complexes 1 and 2 display a 1D tape structure. Meanwhile, complex 3 exhibits a 2D layer and further stacks via C-Hπ interactions to generate a three-dimensional supramolecular architecture. These three metal coordination polymers have been applied as catalysts for the green synthesis of a variety of 3,4-dihydropyrimidin-2(1H)-ones under solvent-free conditions through the Biginelli reaction. Interestingly, the catalysis products have been obtained in high yields under eco-friendly synthesis conditions.

  20. DFT Study of Binding and Electron Transfer from a Metal-Free Dye with Carboxyl, Hydroxyl, and Sulfonic Anchors to a Titanium Dioxide Nanocluster

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    Corneliu I. Oprea


    Full Text Available We report results of density functional theory (DFT calculations of a metal-free dye, 5-(4-sulfophenylazosalicylic acid disodium salt, known as Mordant Yellow 10 (MY-10, used as sensitizer for TiO2 dye-sensitized solar cells (DSSCs. Given the need to better understand the behavior of the dyes adsorbed on the TiO2 nanoparticle, we studied various single and double deprotonated forms of the dye bound to a TiO2 cluster, taking advantage of the presence of the carboxyl, hydroxyl, and sulfonic groups as possible anchors. We discuss various binding configurations to the TiO2 substrate and the charge transfer from the pigment to the oxide by means of DFT calculations. In agreement with other reports, we find that the carboxyl group tends to bind in bidentate bridging configurations. The salicylate uses both the carboxyl and hydroxyl substituent groups for either a tridentate binding to adjacent Ti(IV ions or a bidentate Ti-O binding together with an O-H-O binding, due to the rotation of the carboxyl group out of the plane of the dye. The sulfonic group prefers a tridentate binding. We analyze the propensity for electron transfer of the various dyes and find that for MY-10, as a function of the anchor group, the DSSC performance decreases in the order hydroxyl + carboxyl > carboxyl > sulfonate.

  1. Design features for optimization of tetrapyrrole macrocycles as antimicrobial and anticancer photosensitizers. (United States)

    Martinez De Pinillos Bayona, Alejandra; Mroz, Pawel; Thunshelle, Connor; Hamblin, Michael R


    Photodynamic therapy (PDT) uses non-toxic dyes called photosensitizers (PS) and harmless visible light that combine to form highly toxic reactive oxygen species that kill cells. Originally, a cancer therapy, PDT, now includes applications for infections. The most widely studied PS are tetrapyrrole macrocycles including porphyrins, chlorins, bacteriochlorins, and phthalocyanines. The present review covers the design features in PS that can work together to maximize the PDT activity for various disease targets. Photophysical and photochemical properties include the wavelength and size of the long-wavelength absorption peak (for good light penetration into tissue), the triplet quantum yield and lifetime, and the propensity to undergo type I (electron transfer) or type II (energy transfer) photochemical mechanisms. The central metal in the tetrapyrrole macrocycle has a strong influence on the PDT activity. Hydrophobicity and charge are important factors that govern interactions with various types of cells (cancer and microbial) in vitro and the pharmacokinetics and biodistribution in vivo. Hydrophobic structures tend to be water insoluble and require a drug delivery vehicle for maximal activity. Molecular asymmetry and amphiphilicity are also important for high activity. In vivo some structures possess the ability to selectively accumulate in tumors and to localize in the tumor microvasculature producing vascular shutdown after illumination. © 2017 John Wiley & Sons A/S.

  2. Transcriptional regulation of tetrapyrrole biosynthesis in Arabidopsis thaliana

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    Koichi Kobayashi


    Full Text Available Biosynthesis of chlorophyll (Chl involves many enzymatic reactions that share several first steps for biosynthesis of other tetrapyrroles such as heme, siroheme and phycobilins. Chl allows photosynthetic organisms to capture light energy for photosynthesis but with simultaneous threat of photooxidative damage to cells. To prevent photodamage by Chl and its highly photoreactive intermediates, photosynthetic organisms have developed multiple levels of regulatory mechanisms to coordinate tetrapyrrole biosynthesis (TPB with the formation of photosynthetic and photoprotective systems and to fine-tune the metabolic flow with the varying needs of Chl and other tetrapyrroles under various developmental and environmental conditions. Among a wide range of regulatory mechanisms of TPB, this review summarizes transcriptional regulation of TPB genes during plant development,with focusing on several transcription factors characterized in Arabidopsis thaliana.Key TPB genes are tightly coexpressed with other photosynthesis-associated nuclear genes and are induced by light, oscillate in a diurnal and circadian manner, are coordinated with developmental and nutritional status, and are strongly downregulated in response to arrested chloroplast biogenesis. LONG HYPOCOTYL 5 and PHYTOCHROME-INTERACTING FACTORs, which are positive and negative transcription factors with a wide range of light signaling, respectively, target many TPB genes for light and circadian regulation. GOLDEN2-LIKE transcription factors directly regulate key TPB genes to fine-tune the formation of the photosynthetic apparatus with chloroplast functionality. Some transcription factors such as FAR-RED ELONGATED HYPOCOTYL3, REVEILLE1, and scarecrow-like transcription factors may directly regulate some specific TPB genes, whereas other factors such as GATA transcription factors are likely to regulate TPB genes in an indirect manner. Comprehensive transcriptional analyses of TPB genes and detailed

  3. Tetrapyrroles as Endogenous TSPO Ligands in Eukaryotes and Prokaryotes: Comparisons with Synthetic Ligands

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    Leo Veenman


    Full Text Available The 18 kDa translocator protein (TSPO is highly 0conserved in eukaryotes and prokaryotes. Since its discovery in 1977, numerous studies established the TSPO’s importance for life essential functions. For these studies, synthetic TSPO ligands typically are applied. Tetrapyrroles present endogenous ligands for the TSPO. Tetrapyrroles are also evolutionarily conserved and regulate multiple functions. TSPO and tetrapyrroles regulate each other. In animals TSPO-tetrapyrrole interactions range from effects on embryonic development to metabolism, programmed cell death, response to stress, injury and disease, and even to life span extension. In animals TSPOs are primarily located in mitochondria. In plants TSPOs are also present in plastids, the nuclear fraction, the endoplasmic reticulum, and Golgi stacks. This may contribute to translocation of tetrapyrrole intermediates across organelles’ membranes. As in animals, plant TSPO binds heme and protoporphyrin IX. TSPO-tetrapyrrole interactions in plants appear to relate to development as well as stress conditions, including salt tolerance, abscisic acid-induced stress, reactive oxygen species homeostasis, and finally cell death regulation. In bacteria, TSPO is important for switching from aerobic to anaerobic metabolism, including the regulation of photosynthesis. As in mitochondria, in bacteria TSPO is located in the outer membrane. TSPO-tetrapyrrole interactions may be part of the establishment of the bacterial-eukaryote relationships, i.e., mitochondrial-eukaryote and plastid-plant endosymbiotic relationships.

  4. Sodium dodecyl benzene sulfonate functionalized graphene for confined electrochemical growth of metal/oxide nanocomposites for sensing application. (United States)

    Zhou, Shenghai; Wei, Donglei; Shi, Hongyan; Feng, Xun; Xue, Kaiwen; Zhang, Feng; Song, Wenbo


    The electrochemical fructose sensor attracts considerable attention in the food industry and for clinical applications. Here, a novel fructose biosensor was developed based on immobilization of highly dispersed CuO-Cu nanocomposites on Graphene that was non-covalently functionalized by sodium dodecyl benzene sulfonate (SDBS) (denoted briefly as SDBS/GR/CuO-Cu). The structure and morphology of SDBS/GR/CuO-Cu were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemistry and electrocatalysis were evaluated by cyclic voltammetry (CV). The fructose sensing performances were evaluated by chronoamperometry (i-t). Those properties were also compared with that of CuO-Cu. Results revealed the distinctly enhanced sensing properties of SDBS/GR/CuOCu towards fructose, showing significantly lowered overpotential of +0.40V, ultrafast (<1s) and ultra-sensitive current response (932 μAm M(-1)cm(-2)) in a wide linear range of 3-1000 μM, with satisfactory reproducibility and stability. Those could be ascribed to the good electrical conductivity, large specific surface area, high dispersing ability and chemical stability of GR upon being functionalized non-covalently by SDBS, as well as the outstanding cation anchoring ability of SDBS on GR to resist aggregation among Cu-based nanoparticles during electro-reduction. More importantly, an improved selectivity in fructose detection was achieved. SDBS/GR/CuO-Cu is one of the promising electrode materials for electrochemical detection of fructose. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Catalyst-free synthesis of 3-sulfone nitrile from sulfonyl hydrazides and acrylonitrile in water. (United States)

    Li, Wei; Gao, Lingfeng; Zhuge, Wenyun; Sun, Xu; Zheng, Gengxiu


    A novel catalyst-free sulfonation reaction for synthesizing 3-sulfone nitrile compounds from sulfonyl hydrazides and acrylonitriles in water, without any metal catalyst, ligand or organic solvent, was demonstrated. This catalyst-free protocol provides a new synthetic method for the construction of 3-sulfone nitrile compounds with excellent yields. The D2O experiment adequately proved that the catalyst-free sulfonation reaction occurs via a Michael addition mechanism and that the hydrogen of 3-sulfone nitrile comes from water.

  6. Magnetic and dielectric properties of sulfonated (S) poly[(styrene)-(ethylene-co-butylene)]-styrene (SEBS) block copolymer/magnetic metal oxide nanocomposites synthesized via an in-situ precipitation method (United States)

    Peddini, Sateesh Kumar

    Block copolymer/magnetic metal oxide nanocomposites were synthesized by growing metal oxide nanoparticles (cobalt ferrite, CoFe2O 4 and iron oxide, alpha-Fe2O3) in sulfonated (s) poly (styrene) (PS) block domains of sulfonated poly [(styrene)-(ethylene-co-butylene)-(styrene)] (SEBS) BCP preformed films via an in-situ precipitation method by dissolving the salts of respective metal chloride (s) in a suitable solvent that selectively swells the sPS regions. Inorganic uptake was determined using thermogravimetric analysis (TGA), and it was observed that none of the samples incorporated more than 5 wt % of the inorganic component. Dynamical mechanical analysis was used to observe the changes in the glass transition temperatures (T g) in both blocks of the BCP by plotting tan delta vs. temperature responses in tensile mode on all samples. The results showed that the T g of the sPS block domains increased with sulfonation level and further increased with the incorporation of both nanoparticles in the same blocks, indicating that growth of nanoparticles takes place only in sPS blocks. The crystalline structure of the nanoparticles was observed using wide angle X-ray diffractometry (WAXD), and it was determined that cobalt iron oxide nanoparticles in 20 mole % sulfonated SEBS exhibited an inverse spinel structure confirming the structure to be CoFe2O4. And with iron oxide nanoparticles in 10 mole % sulfonated SEBS exhibiting a hematite (alpha-Fe2O 3) phase. Transmission electron microscopy (TEM) was used to investigate the particle size and distribution of nanoparticles in sBCP matrices at all sulfonation levels. Select area electron diffraction in TEM was used to determine crystalline structures of individual nanoparticles to compare with the structure observed from WAXD. The changes in thickness of interfaces between the individual PS and EB block domains with increase in sulfonation of PS blocks were investigated semi-quantitatively using tapping mode atomic force

  7. Spectroscopic Behavior of Some A3B Type Tetrapyrrolic Complexes in Several Organic Solvents and Micellar Media

    Directory of Open Access Journals (Sweden)

    Radu Socoteanu


    Full Text Available The paper presents spectral studies of some unsymmetrical A3B tetrapyrrolic, porphyrin-type complexes with Cu(II and Zn(II in different solvents and micellar media aimed at estimating their properties in connection with the living cell. The results indicate that the position of the absorption and emission peaks is mostly influenced by the central metal ion and less by the environmental polarity or the peripheric substituents of the porphyrinic core. The comparison between the overall absorption and emission spectra of the compounds in methanol or cyclohexane vs. direct and reverse Triton X micellar systems, respectively, suggests for all compounds the localization at the interface between the polyethylene oxide chains and the tert-octyl-phenyl etheric residue of the Triton X-100 molecules. These findings could be important when testing the compounds embedded in liposomes or other delivery systems to the targeted cell.

  8. Enhanced Proton Conductivity of Sulfonated Hybrid Poly(arylene ether ketone) Membranes by Incorporating an Amino-Sulfo Bifunctionalized Metal-Organic Framework for Direct Methanol Fuel Cells. (United States)

    Ru, Chunyu; Li, Zhenhua; Zhao, Chengji; Duan, Yuting; Zhuang, Zhuang; Bu, Fanzhe; Na, Hui


    Novel side-chain-type sulfonated poly(arylene ether ketone) (SNF-PAEK) containing naphthalene and fluorine moieties on the main chain was prepared in this work, and a new amino-sulfo-bifunctionalized metal-organic framework (MNS, short for MIL-101-NH 2 -SO 3 H) was synthesized via a hydrothermal technology and postmodification. Then, MNS was incorporated into a SNF-PAEK matrix as an inorganic nanofiller to prepare a series of organic-inorganic hybrid membranes (MNS@SNF-PAEK-XX). The mechanical property, methanol resistance, electrochemistry, and other properties of MNS@SNF-PAEK-XX hybrid membranes were characterized in detail. We found that the mechanical strength and methanol resistances of these hybrid membranes were improved by the formation of an ionic cross-linking structure between -NH 2 of MNS and -SO 3 H on the side chain of SNF-PAEK. Particularly, the proton conductivity of these hybrid membranes increased obviously after the addition of MNS. MNS@SNF-PAEK-3% exhibited the proton conductivity of 0.192 S·cm -1 , which was much higher than those of the pristine membrane (0.145 S·cm -1 ) and recast Nafion (0.134 S·cm -1 ) at 80 °C. This result indicated that bifunctionalized MNS rearranged the microstructure of hybrid membranes, which could accelerate the transfer of protons. The hybrid membrane (MNS@SNF-PAEK-3%) showed a better direct methanol fuel cell performance with a higher peak power density of 125.7 mW/cm 2 at 80 °C and a higher open-circuit voltage (0.839 V) than the pristine membrane.

  9. Interdependence of tetrapyrrole metabolism, the generation of oxidative stress and the mitigative oxidative stress response

    Directory of Open Access Journals (Sweden)

    Andrea W.U. Busch


    Full Text Available Tetrapyrroles are involved in light harvesting and light perception, electron-transfer reactions, and as co-factors for key enzymes and sensory proteins. Under conditions in which cells exhibit stress-induced imbalances of photosynthetic reactions, or light absorption exceeds the ability of the cell to use photoexcitation energy in synthesis reactions, redox imbalance can occur in photosynthetic cells. Such conditions can lead to the generation of reactive oxygen species (ROS associated with alterations in tetrapyrrole homeostasis. ROS accumulation can result in cellular damage and detrimental effects on organismal fitness, or ROS molecules can serve as signals to induce a protective or damage-mitigating oxidative stress signaling response in cells. Induced oxidative stress responses include tetrapyrrole-dependent and -independent mechanisms for mitigating ROS generation and/or accumulation. Thus, tetrapyrroles can be contributors to oxidative stress, but are also essential in the oxidative stress response to protect cells by contributing to detoxification of ROS. In this review, we highlight the interconnection and interdependence of tetrapyrrole metabolism with the occurrence of oxidative stress and protective oxidative stress signaling responses in photosynthetic organisms.

  10. Recent overview of the Mg branch of the tetrapyrrole biosynthesis leading to chlorophylls. (United States)

    Masuda, Tatsuru


    In plants, chlorophylls (chlorophyll a and chlorophyll b) are the most abundant tetrapyrrole molecules and are essential for photosynthesis. The first committed step of chlorophyll biosynthesis is the insertion of Mg(2+) into protoporphyrin IX, and thus subsequent steps of the biosynthesis are called the Mg branch. As the Mg branch in higher plants is complex, it was not until the last decade--after many years of intensive research--that most of the genes encoding the enzymes for the pathway were identified. Biochemical and molecular genetic analyses have certainly modified the classic metabolic map of tetrapyrrole biosynthesis, and only recently have the molecular mechanisms of regulatory pathways governing chlorophyll metabolism been elucidated. As a result, novel functions of tetrapyrroles and biosynthetic enzymes have been proposed. In this review, I summarize the recent findings on enzymes involved in the Mg branch, mainly in higher plants.

  11. 9th International Conference on Tetrapyrrole Photoreceptors of Photosynthetic Organisms (ICTPPO 2009): Meeting Proceedings

    Energy Technology Data Exchange (ETDEWEB)

    Lagarias, J. Clark


    Tetrapyrroles are strongly pigmented heterocyclic molecules that play key roles in the harvesting of light and in its efficient conversion into chemical energy by photosynthetic organisms, including agronomically important plant species. This grant provided financial support for the International Conference on Tetrapyrrole Photoreceptors of Photosynthetic Organisms (ICTPPO 2009), the ninth in the series of ad hoc biennial conferences focused on the structure, function and biotechnological applications of tetrapyrrole photoreceptors, held at Asilomar Conference Center, Monterey CA from July 26 to July 31, 2009. The goal of this meeting was to bring together leading experts in the field of tetrapyrrole photoreceptors and from associated fields with new investigators, to provide critical analyses of the current state of their fields, the challenges and opportunities therein and their most recent unpublished discoveries to stimulate new approaches to address key issues of agricultural and energy significance. Among the 80 participants included 40 PIs (including one Nobelist in chemistry, two members of the US National Academy of Science, and a recent inductee to the Royal Society), 8 senior scientists, 1 DOE program manager, 12 postdoctoral fellows and 20 graduate students representing 13 countries. One third of the formal lecture program was reserved for discussion, and these sessions particularly well supported the conference objectives. In the spirit of the Gordon Conference format adopted for this meeting, the conference proceedings were documented in a bound document available to all participants but were not distributed to the general public. The major output was the cross-breeding of scientists not previously associated with this meeting, both senior and junior, from the fields of photosynthesis/energy conversion, tetrapyrrole metabolism and bioinspired, tetrapyrrole-based light harvesting systems.

  12. Comparative Study of the Optical and Textural Properties of Tetrapyrrole Macrocycles Trapped Within ZrO₂, TiO₂, and SiO₂ Translucent Xerogels. (United States)

    Salas-Bañales, Eduardo; Quiroz-Segoviano, R Iris Y; Díaz-Alejo, Luis Antonio; Rojas-González, Fernando; Estrella-González, Alberto; Campero, Antonio; García-Sánchez, Miguel A


    The entrapping of physicochemical active molecules inside mesoporous networks is an appealing field of research due to the myriad of potential applications in optics, photocatalysis, chemical sensing, and medicine. One of the most important reasons for this success is the possibility of optimizing the properties that a free active species displays in solution but now trapped inside a solid substrate. Additionally it is possible to modulate the textural characteristics of substrates, such as pore size, specific surface area, polarity and chemical affinity of the surface, toward the physical or chemical adhesion of a variety of adsorbates. In the present document, two kinds of non-silicon metal alkoxides, Zr and Ti, are employed to prepare xerogels containing entrapped tetrapyrrolic species that could be inserted beforehand in analogue silica systems. The main goal is to develop efficient methods for trapping or binding tetrapyrrole macrocycles inside TiO₂ and ZrO₂ xerogels, while comparing the properties of these systems against those of the SiO₂ analogues. Once the optimal synthesis conditions for obtaining translucent monolithic xerogels of ZrO₂ and TiO₂ networks were determined, it was confirmed that these substrates allowed the entrapment, in monomeric form, of macrocycles that commonly appear as aggregates within the SiO₂ network. From these experiments, it could be determined that the average pore diameters, specific surface areas, and water sorption capacities depicted by each one of these substrates, are a consequence of their own nature combined with the particular structure of the entrapped tetrapyrrole macrocycle. Furthermore, the establishment of covalent bonds between the intruding species and the pore walls leads to the obtainment of very similar pore sizes in the three different metal oxide (Ti, Zr, and Si) substrates as a consequence of the templating effect of the encapsulated species.

  13. Comparative Study of the Optical and Textural Properties of Tetrapyrrole Macrocycles Trapped Within ZrO2, TiO2, and SiO2 Translucent Xerogels

    Directory of Open Access Journals (Sweden)

    Eduardo Salas-Bañales


    Full Text Available The entrapping of physicochemical active molecules inside mesoporous networks is an appealing field of research due to the myriad of potential applications in optics, photocatalysis, chemical sensing, and medicine. One of the most important reasons for this success is the possibility of optimizing the properties that a free active species displays in solution but now trapped inside a solid substrate. Additionally it is possible to modulate the textural characteristics of substrates, such as pore size, specific surface area, polarity and chemical affinity of the surface, toward the physical or chemical adhesion of a variety of adsorbates. In the present document, two kinds of non-silicon metal alkoxides, Zr and Ti, are employed to prepare xerogels containing entrapped tetrapyrrolic species that could be inserted beforehand in analogue silica systems. The main goal is to develop efficient methods for trapping or binding tetrapyrrole macrocycles inside TiO2 and ZrO2 xerogels, while comparing the properties of these systems against those of the SiO2 analogues. Once the optimal synthesis conditions for obtaining translucent monolithic xerogels of ZrO2 and TiO2 networks were determined, it was confirmed that these substrates allowed the entrapment, in monomeric form, of macrocycles that commonly appear as aggregates within the SiO2 network. From these experiments, it could be determined that the average pore diameters, specific surface areas, and water sorption capacities depicted by each one of these substrates, are a consequence of their own nature combined with the particular structure of the entrapped tetrapyrrole macrocycle. Furthermore, the establishment of covalent bonds between the intruding species and the pore walls leads to the obtainment of very similar pore sizes in the three different metal oxide (Ti, Zr, and Si substrates as a consequence of the templating effect of the encapsulated species.

  14. In vitro antioxidant capacity and antigenotoxic properties of protoporphyrin and structurally related tetrapyrroles. (United States)

    Mölzer, Christine; Huber, Hedwig; Steyrer, Andrea; Ziesel, Gesa; Ertl, Anita; Plavotic, Admira; Wallner, Marlies; Bulmer, Andrew Cameron; Wagner, Karl-Heinz


    The antioxidant properties of protoporphyrin IX and related tetrapyrroles are poorly characterized. Therefore, eight tetrapyrroles, five of which are produced in vivo, were tested to assess their antioxidant capacities in the Salmonella reverse mutation, TEAC, FRAP and ORAC assays. Tertiary-butyl hydroperoxide (tert-BOOH) in the presence or absence of metabolic activation (±S9) was added to Salmonella strain TA102 together with the test compounds. In the absence of metabolic activation, the order of effectiveness was protoporphyrin > biliverdin > bilirubin ditaurate > bilirubin > biliverdin dimethyl ester > stercobilin > bilirubin dimethyl ester > urobilin. In the presence of S9, the effectiveness was reversed, with urobilin > biliverdin dimethyl ester > bilirubin dimethyl ester > stercobilin > biliverdin > bilirubin > bilirubin ditaurate > protoporphyrin. In the antioxidant capacity assays FRAP, TEAC and ORAC, mainly bilirubin, bilirubin ditaurate, biliverdin and protoporphyrin showed antioxidant activity. This study reports that previously untested tetrapyrroles of related structure prevent oxidatively induced genotoxicity, and for some, novel underlying mechanisms of antioxidant action were revealed. These results support the physiological importance and biological relevance of tetrapyrroles including protoporphyrin that might act as antioxidants, protecting from oxidatively induced DNA damage, particularly in the tissues/organs where they accumulate.

  15. Sequence Evidence for the Presence of Two Tetrapyrrole Pathways in Euglena gracilis (United States)

    Kořený, Luděk; Oborník, Miroslav


    Abstract Genes encoding enzymes of the tetrapyrrole biosynthetic pathway were searched within Euglena gracilis EST databases and 454 genome reads and their 5' end regions were sequenced when not available. Phylogenetic analyses and protein localization predictions support the hypothesis concerning the presence of two separated tetrapyrrole pathways in E. gracilis. One of these pathways resembles the heme synthesis in primarily heterotrophic eukaryotes and was presumably present in the host cell prior to secondary endosymbiosis with a green alga. The second pathway is similar to the plastid-localized tetrapyrrole syntheses in plants and photosynthetic algae. It appears to be localized to the secondary plastid, presumably derived from an algal endosymbiont and probably serves only for the production of plastidial heme and chlorophyll. Thus, E. gracilis represents an evolutionary intermediate in a metabolic transformation of a primary heterotroph to a photoautotroph through secondary endosymbiosis. We propose here that the tetrapyrrole pathway serves as a highly informative marker for the evolution of plastids and plays a crucial role in the loss of plastids. PMID:21444293

  16. PAPP5 is involved in the tetrapyrrole mediated plastid signalling during chloroplast development.

    Directory of Open Access Journals (Sweden)

    Juan de Dios Barajas-López

    Full Text Available The initiation of chloroplast development in the light is dependent on nuclear encoded components. The nuclear genes encoding key components in the photosynthetic machinery are regulated by signals originating in the plastids. These plastid signals play an essential role in the regulation of photosynthesis associated nuclear genes (PhANGs when proplastids develop into chloroplasts. One of the plastid signals is linked to the tetrapyrrole biosynthesis and accumulation of the intermediates the Mg-ProtoIX and its methyl ester Mg-ProtoIX-ME. Phytochrome-Associated Protein Phosphatase 5 (PAPP5 was isolated in a previous study as a putative Mg-ProtoIX interacting protein. In order to elucidate if there is a biological link between PAPP5 and the tetrapyrrole mediated signal we generated double mutants between the Arabidopsis papp5 and the crd mutants. The crd mutant over-accumulates Mg-ProtoIX and Mg-ProtoIX-ME and the tetrapyrrole accumulation triggers retrograde signalling. The crd mutant exhibits repression of PhANG expression, altered chloroplast morphology and a pale phenotype. However, in the papp5crd double mutant, the crd phenotype is restored and papp5crd accumulated wild type levels of chlorophyll, developed proper chloroplasts and showed normal induction of PhANG expression in response to light. Tetrapyrrole feeding experiments showed that PAPP5 is required to respond correctly to accumulation of tetrapyrroles in the cell and that PAPP5 is most likely a component in the plastid signalling pathway down stream of the tetrapyrrole Mg-ProtoIX/Mg-ProtoIX-ME. Inhibition of phosphatase activity phenocopied the papp5crd phenotype in the crd single mutant demonstrating that PAPP5 phosphatase activity is essential to mediate the retrograde signal and to suppress PhANG expression in the crd mutant. Thus, our results suggest that PAPP5 receives an inbalance in the tetrapyrrole biosynthesis through the accumulation of Mg-ProtoIX and acts as a negative

  17. Analytical methodology for sulfonated lignins

    NARCIS (Netherlands)

    Brudin, S.; Schoenmakers, P.


    There is a significant need to characterize and classify lignins and sulfonated lignins. Lignins have so far received a good deal of attention, whereas this is not true for sulfonated lignins. There is a clear demand for a better understanding of sulfonated lignins on a chemical as well as physical

  18. Combined liquid chromatography/mass spectrometry of tetrapyrroles of sedimentary significance

    Energy Technology Data Exchange (ETDEWEB)

    Eckardt, C.B.; Carter, J.F.; Maxwell, J.R. (Univ. of Bristol (England))

    The on-line coupling of a high-performance liquid chromatograph to a mass spectrometer (LC/MS) has allowed the analysis of a number of tetrapyrrole pigments of sedimentary significance. Mass spectra were obtained under conditions of discharge ionization and are characterized by the presence of protonated ion species (positive-ion mode) or molecular ions (negative-ion mode), respectively. Fragmentation processes were found to be restricted to the periphery of the structures. In the positive-ion mode the extent of fragmentation could be manipulated by alteration of the repeller voltage in the ion source, allowing molecular weight information to be obtained, as well as specific fragmentation patterns. These findings have suggested a number of applications of LC/MS in the investigation of sedimentary tetrapyrrole distributions. In particular, the assignment of individual components in mixtures without resort to their isolation is possible from comparison of mass spectra with those of authentic standards and from coinjection with the standards.

  19. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Norton, C.J.; Falk, D.O.


    An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

  20. Evolution of the Tetrapyrrole Biosynthetic Pathway in Secondary Algae: Conservation, Redundancy and Replacement.

    Directory of Open Access Journals (Sweden)

    Jaromír Cihlář

    Full Text Available Tetrapyrroles such as chlorophyll and heme are indispensable for life because they are involved in energy fixation and consumption, i.e. photosynthesis and oxidative phosphorylation. In eukaryotes, the tetrapyrrole biosynthetic pathway is shaped by past endosymbioses. We investigated the origins and predicted locations of the enzymes of the heme pathway in the chlorarachniophyte Bigelowiella natans, the cryptophyte Guillardia theta, the "green" dinoflagellate Lepidodinium chlorophorum, and three dinoflagellates with diatom endosymbionts ("dinotoms": Durinskia baltica, Glenodinium foliaceum and Kryptoperidinium foliaceum. Bigelowiella natans appears to contain two separate heme pathways analogous to those found in Euglena gracilis; one is predicted to be mitochondrial-cytosolic, while the second is predicted to be plastid-located. In the remaining algae, only plastid-type tetrapyrrole synthesis is present, with a single remnant of the mitochondrial-cytosolic pathway, a ferrochelatase of G. theta putatively located in the mitochondrion. The green dinoflagellate contains a single pathway composed of mostly rhodophyte-origin enzymes, and the dinotoms hold two heme pathways of apparently plastidal origin. We suggest that heme pathway enzymes in B. natans and L. chlorophorum share a predominantly rhodophytic origin. This implies the ancient presence of a rhodophyte-derived plastid in the chlorarachniophyte alga, analogous to the green dinoflagellate, or an exceptionally massive horizontal gene transfer.

  1. Anti-cancer effects of blue-green alga Spirulina platensis, a natural source of bilirubin-like tetrapyrrolic compounds. (United States)

    Koníčková, Renata; Vaňková, Kateřina; Vaníková, Jana; Váňová, Kateřina; Muchová, Lucie; Subhanová, Iva; Zadinová, Marie; Zelenka, Jaroslav; Dvořák, Aleš; Kolář, Michal; Strnad, Hynek; Rimpelová, Silvie; Ruml, Tomáš; J Wong, Ronald; Vítek, Libor


    Spirulina platensis is a blue-green alga used as a dietary supplement because of its hypocholesterolemic properties. Among other bioactive substances, it is also rich in tetrapyrrolic compounds closely related to bilirubin molecule, a potent antioxidant and anti-proliferative agent. The aim of our study was to evaluate possible anticancer effects of S. platensis and S. platensis-derived tetrapyrroles using an experimental model of pancreatic cancer. The anti-proliferative effects of S. platensis and its tetrapyrrolic components [phycocyanobilin (PCB) and chlorophyllin, a surrogate molecule for chlorophyll A] were tested on several human pancreatic cancer cell lines and xenotransplanted nude mice. The effects of experimental therapeutics on mitochondrial reactive oxygen species (ROS) production and glutathione redox status were also evaluated. Compared to untreated cells, experimental therapeutics significantly decreased proliferation of human pancreatic cancer cell lines in vitro in a dose-dependent manner (from 0.16 g•L-1 [S. platensis], 60 μM [PCB], and 125 μM [chlorophyllin], pcancer growth was evidenced since the third day of treatment (p compounds decreased generation of mitochondrial ROS and glutathione redox status (p = 0.0006; 0.016; and 0.006 for S. platensis, PCB, and chlorophyllin, respectively). In conclusion, S. platensis and its tetrapyrrolic components substantially decreased the proliferation of experimental pancreatic cancer. These data support a chemopreventive role of this edible alga. Furthermore, it seems that dietary supplementation with this alga might enhance systemic pool of tetrapyrroles, known to be higher in subjects with Gilbert syndrome.

  2. Virtual libraries of tetrapyrrole macrocycles. Combinatorics, isomers, product distributions, and data mining. (United States)

    Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S


    A software program (PorphyrinViLiGe) has been developed to enumerate the type and relative amounts of substituted tetrapyrrole macrocycles in a virtual library formed by one of four different classes of reactions. The classes include (1) 4-fold reaction of n disubstituted heterocycles (e.g., pyrroles or diiminoisoindolines) to form β-substituted porphyrins, β-substituted tetraazaporphyrins, or α- or β-substituted phthalocyanines; (2) combination of m aminoketones and n diones to form m × n pyrroles, which upon 4-fold reaction give β-substituted porphyrins; (3) derivatization of an 8-point tetrapyrrole scaffold with n reagents, and (4) 4-fold reaction of n aldehydes and pyrrole to form meso-substituted porphyrins. The program accommodates variable ratios of reactants, reversible or irreversible reaction (reaction classes 1 and 2), and degenerate modes of formation. Pólya's theorem (for enumeration of cyclic entities) has also been implemented and provides validation for reaction classes 3 and 4. The output includes the number and identity of distinct reaction-accessible substituent combinations, the number and identity of isomers thereof, and the theoretical mass spectrum. Provisions for data mining enable assessment of the number of products having a chosen pattern of substituents. Examples include derivatization of an octa-substituted phthalocyanine with eight reagents to afford a library of 2,099,728 members (yet only 6435 distinct substituent combinations) and reversible reaction of six distinct disubstituted pyrroles to afford 2649 members (yet only 126 distinct substituent combinations). In general, libraries of substituted tetrapyrrole macrocycles occupy a synthetically accessible region of chemical space that is rich in isomers (>99% or 95% for the two examples, respectively).

  3. 21 CFR 573.600 - Lignin sulfonates. (United States)


    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Lignin sulfonates. 573.600 Section 573.600 Food... Additive Listing § 573.600 Lignin sulfonates. Lignin sulfonates may be safely used in animal feeds in... feeds, as liquid lignin sulfonate, in an amount not to exceed 11 percent of the molasses. (4) As a...

  4. Preliminary UHPLC–PDA–ESI-MS screening of light-accelerated autoxidation products of the tetrapyrrole biliverdin

    NARCIS (Netherlands)

    Weesepoel, Y.J.A.; Gruppen, H.; Vincken, J.P.


    The application of phycobiliproteins, e.g. blue C-phycocyanin, as natural water-soluble food colourants is emerging. The chromophore of these proteins comprises a number of tetrapyrroles (or phycocyanobilins), which have an extensive conjugated system, vulnerable to autoxidation. To assess the

  5. Aspects of γ-radiation induced modification of calf thymus DNA in the presence of sodium 1,4-dihydroxy-9,10-anthraquinone-2-sulfonate and its transition metal complexes with Cu2+ and Ni2+ (United States)

    Guin, Partha Sarathi; Mandal, Parikshit Chandra; Das, Saurabh


    Radiation-induced double-strand modification of DNA was studied in the absence and presence of sodium 1,4-dihydroxy-9,10-anthraquinone-2-sulfonate (NaQSH2) and its metal (Cu2+ and Ni2+) complexes in aerated, de-aerated (Argon saturated) and N2O saturated aqueous media at pH 7.4. Ethidium bromide, an established DNA intercalator was used to estimate DNA remaining after interaction with γ-radiation, by measuring loss of fluorescence of the ethidium bromide-DNA adduct. In de-aerated (Argon saturated) and N2O saturated aqueous media radiation-induced double-strand modification of calf thymus DNA was comparatively less in presence of NaQSH2 and its Ni(II) complex than standard control indicating the compounds behaved as radio-protectors. However, in presence of the Cu(II) complex radiation-induced double-strand modification increased significantly. In N2O saturated medium, double-strand modification of DNA was almost double in all cases than that observed in de-aerated (Argon saturated) medium indicating OH radicals played a major role in modifying DNA. That OH radicals were important was verified by repeating experiments using tertiary-butanol that showed significant decrease in DNA modification. Another important observation was in aerated medium NaQSH2, Ni(II)-NaQSH2 did not show radioprotection while Cu(II)-NaQSH2 was an almost equally effective radiosensitizer as that observed in N2O saturated medium. Role of molecular oxygen as radiosensitizer was thus realized.

  6. Lignin Sulfonation - A different Approach

    DEFF Research Database (Denmark)

    Bjørkmann, Anders


    . It was found that lignin is very reactive, that is why the sulfonation chemistry alone does not necessarily determine its dissolution rate. It became evident that the ultrastructure dispersion of lignin in wood is beneficial for its dissolution. For W, the rate was much higher at pH 1.5 than at 6. MW lignin...... and MWL dissolved (after extraction of the "immediate" lignin) at higher rates than W lignin. For MWL, the rate difference between pH 1.5 and 6 was moderate, compared to W lignin. Borohydride reduction did not affect the lignin dissolution from W, but gave a large decrease of sulfonation rate for MWL...

  7. Fast atom bombardment mass spectrometric and tandem mass spectrometric studies of some functionalized tetrapyrroles derived from chlorophylls a and b

    Energy Technology Data Exchange (ETDEWEB)

    Keely, B.J.; Maxwell, J.R. (Univ. of Bristol (England))

    Fast atom bombardment (FAB) mass spectra of a number of functionalized tetrapyrroles derived from chlorophylls a and b have been obtained and MS/MS studies used to investigate aspects of the fragmentation behavior of some of them. The application of this approach is demonstrated by the assignment of pheophytin b isolated from a lake sediment where the amount and purity were insufficient for {sup 1}H nuclear magnetic resonance spectroscopic studies.

  8. [3,3]-Sigmatropic rearrangement of allenic alcohols: stereoselective synthesis of 1,3-diene-2-ol sulfonates. (United States)

    Zhao, Yuyang; Wang, Yurong; Gu, Zhanshou; Wang, Zhiming


    An efficient synthetic pathway to 1,3-diene-2-ol sulfonates involving the [3,3]-sigmatropic rearrangement of allenic alcohols with sulfonic acids under mild reaction conditions is described. These products can easily undergo reduction or transition-metal catalyzed cross-coupling reactions to yield a series of stereodefined multisubstituted 1,3-dienes.

  9. Preliminary UHPLC-PDA-ESI-MS screening of light-accelerated autoxidation products of the tetrapyrrole biliverdin. (United States)

    Weesepoel, Yannick; Gruppen, Harry; Vincken, Jean-Paul


    The application of phycobiliproteins, e.g. blue C-phycocyanin, as natural water-soluble food colourants is emerging. The chromophore of these proteins comprises a number of tetrapyrroles (or phycocyanobilins), which have an extensive conjugated system, vulnerable to autoxidation. To assess the autoxidation products, a simplified model system was used in which the free tetrapyrrole biliverdin, instead of phycobiliprotein, was subjected to light-accelerated autoxidation. Degradation products of biliverdin were subsequently annotated by reversed-phase ultra-high performance liquid chromatography with a photo diode array and positive mode in-line electrospray ionization mass spectrometry. To facilitate the analysis of degradation products, autoxidation of the three methine bridges in biliverdin was mimicked in silico. It was found that both the peripheral and central methine bridges of biliverdin were susceptible to light-accelerated autoxidation. Scission products tentatively annotated with MS(2) and MS(3) were propionic acid-containing pyrroles. From this, it can be speculated that tetrapyrroles attached to phycobiliproteins are susceptible to autoxidative degradation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. The tetrapyrrole synthesis pathway as a model of horizontal gene transfer in euglenoids. (United States)

    Lakey, Bryan; Triemer, Richard


    The history of euglenoids may have begun as early as ~2 bya. These early phagotrophs ate cyanobacteria, archaea, and eubacteria, and the subsequent appearance of red algae and chromalveolates provided euglenoids with additional food sources. Following the appearance of green algae, euglenoids acquired a chloroplast via a secondary endosymbiotic event with a green algal ancestor. This endosymbiosis also involved a massive transfer of nuclear-encoded genes from the symbiont nucleus to the host. Expecting these genes to have a green algal origin, this research has shown, through the use of DNA-sequences and the analysis of phylogenetic relationships, that many housekeeping genes have a red algal/chromalveolate ancestry. This suggested that many other endosymbiotic/horizontal gene transfers, which brought genes from chromalveolates to euglenoids, may have been taking place long before the acquisition of the chloroplast. The investigation of the origin of the enzymes involved in the tetrapyrrole synthesis pathway provided insights into horizontal gene transfer in euglenoids and demonstrated that the euglenoid nuclear genome is a mosaic comprised of genes from the ancestral lineage plus genes transferred endosymbiotically/horizontally from green, red, and chromalveolates lineages. © 2016 Phycological Society of America.

  11. A durable alternative for proton-exchange membranes: sulfonated poly(benzoxazole thioether sulfone)s

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dan [Center for Innovative Fuel Cell and Battery Technologies, School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245 (United States); Lab of PEMFC Key Materials and Technologies, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Liaoning, Dalian 116023 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100039 (China); Li, Jinhuan [Center for Innovative Fuel Cell and Battery Technologies, School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245 (United States); College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016 (China); Song, Min-Kyu; Liu, Meilin [Center for Innovative Fuel Cell and Battery Technologies, School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245 (United States); Yi, Baolian; Zhang, Huamin [Lab of PEMFC Key Materials and Technologies, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Liaoning, Dalian 116023 (China)


    To develop a durable proton-exchange membrane (PEM) for fuel-cell applications, a series of sulfonated poly(benzoxazole thioether sulfone)s (SPTESBOs) are designed and synthesized, with anticipated good dimensional stability (via acid-base cross linking), improved oxidative stability against free radicals (via incorporation of thioether groups), and enhanced inherent stability (via elimination of unstable end groups) of the backbone. The structures and the degree of sulfonation of the copolymers are characterized using Fourier-transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy ({sup 1}H NMR and {sup 19}F NMR). The electrochemical stabilities of the monomers are examined using cyclic voltammetry in a typical three-electrode cell configuration. The physicochemical properties of the membranes vital to fuel-cell performance are also carefully evaluated under conditions relevant to fuel-cell operation, including chemical and thermal stability, proton conductivity, solubility in different solvents, water uptake, and swelling ratio. The new membranes exhibit low dimensional change at 25 C to 90 C and excellent thermal stability up to 250 C. Upon elimination of unstable end groups, the co-polymers display enhanced chemical resistance and oxidative stability in Fenton's test. Further, the SPTESBO-HFB-60 (HFB-60=hexafluorobenzene, 60 mol% sulfone) membrane displays comparable fuel-cell performance to that of an NRE 212 membrane at 80 C under fully humidified condition, suggesting that the new membranes have the potential to be more durable but less expensive for fuel-cell applications. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. A Durable Alternative for Proton-Exchange Membranes: Sulfonated Poly(Benzoxazole Thioether Sulfone)s

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dan; Li, Jin Hui; Song, Min Kyu; Yi, Baolian; Zhang, Huamin; Liu, Meilin


    To develop a durable proton-exchange membrane (PEM) for fuel-cell applications, a series of sulfonated poly(benzoxazole thioether sulfone)s ( SPTESBOs) are designed and synthesized, with anticipated good dimensional stability (via acid–base cross linking), improved oxidative stability against free radicals (via incorporation of thioether groups), and enhanced inherent stability (via elimination of unstable end groups) of the backbone. The structures and the degree of sulfonation of the copolymers are characterized using Fourier-transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy ({sup 1}H NMR and {sup 19}F NMR). The electrochemical stabilities of the monomers are examined using cyclic voltammetry in a typical three-electrode cell configuration. The physicochemical properties of the membranes vital to fuel-cell performance are also carefully evaluated under conditions relevant to fuel-cell operation, including chemical and thermal stability, proton conductivity, solubility in different solvents, water uptake, and swelling ratio. The new membranes exhibit low dimensional change at 25°C to 90°C and excellent thermal stability up to 250°C. Upon elimination of unstable end groups, the co-polymers display enhanced chemical resistance and oxidative stability in Fenton's test. Further, the SPTESBO-HFB-60 (HFB-60=hexafluorobenzene, 60 mol% sulfone) membrane displays comparable fuel-cell performance to that of an NRE 212 membrane at 80°C under fully humidified condition, suggesting that the new membranes have the potential to be more durable but less expensive for fuel-cell applications.

  13. Synthesis and characterization of sulfonated cardo poly(arylene ether sulfone)s for fuel cell proton exchange membrane application

    Energy Technology Data Exchange (ETDEWEB)

    Islam, M.M.; Jang, H.H.; Lim, Y.D.; Seo, D.W.; Kim, W.G. [Department of Applied Chemistry, Konkuk University, Chungju, Chungbuk (Korea, Republic of); Kim, T.H.; Hong, Y.T. [Energy Material Research Center, Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Kim, D.M. [Material Engineering and Science, Hongik Univ, Jochiwon-eup, Yeongi-gun, Chungnam (Korea, Republic of)


    Sulfonated cardo poly(arylene ether sulfone)s (SPPA-PES) with various degrees of sulfonation (DS) were prepared by post-sulfonation of synthesized phenolphthalein anilide (PPA; N-phenyl-3,3'-bis(4-hydroxyphenyl)-1-isobenzopyrolidone) poly(arylene ether sulfone)s (PPA-PES) by using concentrated sulfuric acid. PPA-PES copolymers were synthesized by direct polycondensation of PPA with bis-(4-fluorophenyl)-sulfone and 4,4'-sulfonyldiphenol. The DS was varied with different mole ratios of PPA (24, 30, 40, 50 mol.%) in the polymer. The structure of the resulting SPPA-PES copolymers and the different contents of the sulfonated unit were studied by Fourier transform infrared (FT-IR) spectroscopy, {sup 1}H NMR spectroscopy, and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymer with water. The ion exchange capacity (IEC) and proton conductivity of SPPA-PES were evaluated according to the increase of DS. The water uptake (WU) of the resulting SPPA-PES membranes was in the range of 20-72%, compared with 28% for Nafion 211 registered. The SPPA-PES membranes showed proton conductivities of 23-82 mS cm{sup -1}, compared with 194 mS cm{sup -1} for Nafion 211 registered, under 100% relative humidity (RH) at 80 C. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Preparation and characterization of sulfonated amine-poly(ether sulfone)s for proton exchange membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Dong-Wan; Lim, Young-Don; Lee, Soon-Ho; Jeong, Young-Gi; Kim, Whan-Gi [Department of Applied Chemistry/RIC-ReSEM, Konkuk University, Chungju-si, Chungbuk 380-701 (Korea, Republic of); Hong, Tae-Whan [Department of Materials Sci and Engineering/RIC-ReSEM, Chungju National University, Chungju, Chungbuk (Korea, Republic of)


    Sulfonated amine-poly(ether sulfone)s (S-APES)s were prepared by nitration, reduction and sulfonation of poly(ether sulfone) (ultrason {sup registered} -S6010). Poly(ether sulfone) was reacted with ammonium nitrate and trifluoroacetic anhydride to produce the nitrated poly(ether sulfone), and was followed by reduction using tin(II)chloride and sodium iodide as reducing agents to give the amino-poly(ether sulfone). The S-APES was obtained by reaction of 1,3-propanesultone and the amino-poly(ether sulfone) (NH{sub 2}-PES) with sodium methoxide. The different degrees of nitration and reduction of poly(ether sulfone) were successfully synthesized by an optimized process. The reduction of nitro group to amino was done quantitatively, and this controlled the contents of the sulfonic acid group. The films were converted from salt to acid forms with dilute hydrochloric acid. Different contents of sulfonated unit of the S-APES were studied by FT-IR, {sup 1}H NMR spectroscopy, differential scanning calorimetry (DSC), and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The ion exchange capacity (IEC), a measure of proton conductivity, was evaluated. The S-APES membranes exhibit conductivities (25 C) from 1.05 x 10{sup -3} to 4.83 x 10{sup -3} S/cm, water swell from 30.25 to 66.50%, IEC from 0.38 to 0.82 meq/g, and methanol diffusion coefficients from 3.10 x 10{sup -7} to 4.82 x 10{sup -7} cm{sup 2}/S at 25 C. (author)

  15. Ion Exchange Formation via Sulfonated Bicomponent Nonwovens (United States)

    Stoughton, Hannah L.

    For many years ion exchange resins were used to: remove heavy metals from water, recover materials from wastewater, and eliminate harmful gases from the air. While use of these resin beads dominates the ion exchange industry, the beads have limitations that should be considered when decisions are made to employ them. For instance, officials must balance the inherent zero sum surface area and porosity of the materials. This series of studies investigates the use of bicomponent nonwovens as a base substrate for producing high surface area ion exchange materials for the removal of heavy metal ions. Functionalized materials were produced in a two-step process: (1) PET/PE spunbond bicomponent fibers were fractured completely, producing the high surface area nonwoven to be used as the base ion exchange material, and (2) the conditions for functionalizing the PET fibers of the nonwoven webs were investigated where an epoxy containing monomer was grafted to the surface followed by sulfonation of the monomer. The functionalization reactions of the PET fibers were monitored based on: weight gain, FTIR, TOF-SIMS, and SEM. Ion exchange properties were evaluated using titration and copper ion removal capacity from test solutions. The relationship between web structure and removal efficiency of the metal ions was defined through a comparison of the bicomponent and homocomponent nonwovens for copper ion removal efficiency. The investigation revealed that utilizing the high surface area, fractured bicomponent nonwoven ion exchange materials with capacities comparable to commercially available ion exchange resins could be produced.

  16. Properties of polypyrrole doped with alkylbenzene sulfonates

    DEFF Research Database (Denmark)

    Bay, Lasse; Skaarup, Steen; West, Keld


    -standing 10 mu m thick film is prepared electrochemically at a constant current from an aqueous solution of pyrrole and sodium alkylbenzene sulfonate. The mechanical properties of the film (tensile strength and Young's modulus) and the reversible linear elongation between the oxidised and reduced states...... are measured. Alkylbenzene sulfonates with alkyl chain lengths between 1 and 22 carbon atoms are used as dopant anion. The films made with the different anions have highly different properties and are here compared to outline the influence of the size of the anion. A maximum in linear elongation is found for p......-(n-octyl)benzene sulfonate and in conductivity for p-(n-butyl)benzene sulfonate....

  17. Cation permeable membranes from blends of sulfonated poly(ether ether ketone) and poly (ether sulfone)

    NARCIS (Netherlands)

    Wilhelm, F.G.; Punt, Ineke G.M.; van der Vegt, N.F.A.; Strathmann, H.; Wessling, Matthias


    Sulfonated poly(aryl ether ether ketone), S-PEEK, is blended with non-sulfonated poly(ether sulfone) (PES) to adjust the properties of ion permeable and ion selective membranes. In this study, membranes are prepared from blends with (i) a S-PEEK content between 10 and 100 wt.% using one S-PEEK batch

  18. Photoinduced electron transfer at the tetrapyrrole-TiO2 interface: Effect of the energy alignment (United States)

    Nieto-Pescador, Jesus S.

    Photoinduced electron transfer is a ubiquitous process behind several physical, chemical, and biological processes. Its potential applications, ranging from solar cell technologies to photodynamic cancer therapy, require a thorough understanding of the basics of the reaction. This dissertation addresses open questions for a particular case of electron transfer processes: Heterogeneous Electron Transfer (HET). In this process, an electron is transferred between a localized donor and a multitude of delocalized acceptor states. HET between photoexcited tetrapyrroles and colloidal TiO2 has been investigated using femtosecond transient absorption spectroscopy. Specifically, this work explores the not well-understood influence of the availability of states on the HET reaction. This problem is addressed by measuring electron injection times as a function of the energy difference between the LUMO and the conduction band of TiO2. The change in the energy alignment was done using two experimental strategies. The first one employs a recently synthesized phlorin with two different excited states above the conduction band of TiO2. This molecule allows comparing HET rates from two different excited states. The second strategy measures the electron injection rates after exciting the same electronic state of a set of specially designed porphyrins. The novelty of the approach is that the difference in energy alignment is attained by the introduction of dipole groups within the bridge group of the molecule. This strategy generates a difference in energy alignment of up to 200 meV. The reported measurements were carried in a high vacuum environment with an apparatus capable of resolving sub 30 fs processes. Disentanglement of the electron transfer processes was done, after careful study of the relaxation dynamics of the molecules in solution, by monitoring the decay of the excited state absorption and the rise of the cation spectral signatures. Within our time resolution, our results

  19. 4-Aminopyridinium-3-sulfonate monohydrate

    Directory of Open Access Journals (Sweden)

    Zhi-Biao Zhu


    Full Text Available The reaction of 4-aminopyridine and oleum yielded the title hydrated zwitterion, C5H6N2O3S·H2O. There are two formula units in the asymmetric unit. The H and non-H atoms of both zwitterions lie on a mirror plane except for one sulfonate O atom. The water molecules are also situated on a mirror plane. In the crystal, the zwitterions and water molecules are linked by O—H...O and N—H...O hydrogen bonds, generating a three-dimensional network.

  20. High performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry for V and Ni quantification as tetrapyrroles

    Energy Technology Data Exchange (ETDEWEB)

    Duyck, Christiane Beatrice, E-mail: [Pontificia Universidade Catolica do Rio de Janeiro (PUC-Rio), R. Marques de Sao Vicente, 225, Gavea, Rio de Janeiro, RJ, 22451-900 (Brazil); Universidade Federal Fluminense (UFF), Campus do Valonguinho, Outeiro de Sao Joao Batista, s/no, 24020-150, Niteroi, RJ (Brazil); Saint' Pierre, Tatiana Dillenburg; Miekeley, Norbert [Pontificia Universidade Catolica do Rio de Janeiro (PUC-Rio), R. Marques de Sao Vicente, 225, Gavea, Rio de Janeiro, RJ, 22451-900 (Brazil); Oliveira da Fonseca, Teresa Cristina; Szatmari, Peter [Centro de Pesquisas Leopoldo A. Miguez de Mello da Petrobras (CENPES), Av. Horacio Macedo, 950, Cidade Universitaria, Rio de Janeiro, RJ, 21941-915 (Brazil)


    A method was developed for the determination of V and Ni as tetrapyrroles by High Performance Liquid Chromatography hyphenated to Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) using reversed phase and elution gradient. Chlorinated solvents and tetrahydrofuran were investigated as regard to separation time and ICP-MS detection efficiencies. The final elution gradient program started from pure methanol to a mixture of 20:80 (v/v) chloroform:methanol. External quantification of V and Ni with inorganic standards by flow injection ICP-MS, used online with HPLC, resulted in 95% of recoveries. The Limits of Detection for V during methanol elution and for Ni during the 20% chloroform gradient elution were evaluated by their minimum detectable concentrations, which were, respectively, 5 {mu}g L{sup -1} and 8 {mu}g L{sup -1}. The methodology was applied to polar and resin fractions separated from a Brazilian crude oil and a sediment extract from an oil-polluted area in the Guanabara Bay, Rio de Janeiro, Brazil. Vanadium as tetrapyrroles represented the totality of V content in the polar fraction, whereas Ni was in different polar forms in the resin and sediment extract.

  1. Octahedral molybdenum cluster complexes with aromatic sulfonate ligands


    Efremova, Olga A.; Vorotnikov, Yuri A.; Brylev, Konstantin A.; Vorotnikova, Natalya A.; Novozhilov, Igor N.; Kuratieva, Natalia V.; Edeleva, Mariya V.; Benoit, David M.; Kitamura, Noboru; Mironov, Yuri V.; Shestopalov, Michael A.; Sutherland, Andrew J.


    This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>...

  2. Poly(arylene sulfide sulfone) polymer containing ether groups

    Energy Technology Data Exchange (ETDEWEB)

    Edmonds, J.T. Jr.; Geibel, J.; Bobsein, R.L.; Straw, J.J.


    This patent describes a process comprising: (a) reacting in an organic solvent a dihalo aromatic sulfone with an aromatic diphenol at a mole ratio of about 8/1 to about 20/1 in the presence of an alkali metal base to form a mixture comprising dihalo-terminated oligomers, and subsequently (b) adding a sulfur source selected from the group consisting of hydrogen sulfide, alkali metal hydrosulfides, alkali metal sulfides, acyclic and cyclic thioamides and mixtures, thereof, to the mixture resulting from (a) and continuing the reaction at a temperature and for a sufficient time to form a recoverable polymeric solid, characterized as having a polymer melt temperature in excess of 250/sup 0/C.

  3. Antimalarial effects of vinyl sulfone cysteine proteinase inhibitors.


    Rosenthal, P J; Olson, J E; Lee, G K; Palmer, J T; Klaus, J L; Rasnick, D


    We evaluated the antimalarial effects of vinyl sulfone cysteine proteinase inhibitors. A number of vinyl sulfones strongly inhibited falcipain, a Plasmodium falciparum cysteine proteinase that is a critical hemoglobinase. In studies of cultured parasites, nanomolar concentrations of three vinyl sulfones inhibited parasite hemoglobin degradation, metabolic activity, and development. The antimalarial effects correlated with the inhibition of falcipain. Our results suggest that vinyl sulfones or...

  4. Crossed and Linked Histories of Tetrapyrrolic Macrocycles and Their Use for Engineering Pores within Sol-Gel Matrices

    Directory of Open Access Journals (Sweden)

    Miguel A. García-Sánchez


    Full Text Available The crossed and linked histories of tetrapyrrolic macrocycles, interwoven with new research discoveries, suggest that Nature has found in these structures a way to ensure the continuity of life. For diverse applications porphyrins or phthalocyanines must be trapped inside solid networks, but due to their nature, these compounds cannot be introduced by thermal diffusion; the sol-gel method makes possible this insertion through a soft chemical process. The methodologies for trapping or bonding macrocycles inside pristine or organo-modified silica or inside ZrO2 xerogels were developed by using phthalocyanines and porphyrins as molecular probes. The sizes of the pores formed depend on the structure, the cation nature, and the identities and positions of peripheral substituents of the macrocycle. The interactions of the macrocyclic molecule and surface Si-OH groups inhibit the efficient displaying of the macrocycle properties and to avoid this undesirable event, strategies such as situating the macrocycle far from the pore walls or to exchange the Si-OH species by alkyl or aryl groups have been proposed. Spectroscopic properties are better preserved when long unions are established between the macrocycle and the pore walls, or when oligomeric macrocyclic species are trapped inside each pore. When macrocycles are trapped inside organo-modified silica, their properties result similar to those displayed in solution and their intensities depend on the length of the alkyl chain attached to the matrix. These results support the prospect of tuning up the pore size, surface area, and polarity inside the pore cavities in order to prepare efficient catalytic, optical, sensoring, and medical systems. The most important feature is that research would confirm again that tetrapyrrolic macrocycles can help in the development of the authentic pore engineering in materials science.

  5. Cadmium ion sorption onto lignocellulosic biosorbent modified by sulfonation : the origin of sorption capacity improvement (United States)

    Eun Woo Shin; Roger M. Rowell


    Juniper (Juniperus monosperma), a small-diameter underutilized material, has been studied as a lignocellulosic bio-sorbent for removing heavy metals from water. In this study, juniper wood was modified by sulfonation to enhance sorption capacity for cadmium in water. The origin of the enhancement was investigated by observing the sorption behaviors and the change in...

  6. Chlorine resistant desalination membranes based on directly sulfonated poly(arylene ether sulfone) copolymers (United States)

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


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

  7. Enhancement of proton conductivity of sulfonated polystyrene ...

    Indian Academy of Sciences (India)

    Enhancement of proton conductivity of sulfonated polystyrene membrane prepared by plasma polymerization process. BHABESH KUMAR NATH, AZIZ KHAN, JOYANTI CHUTIA. ∗. , ARUP RATAN PAL,. HEREMBA BAILUNG, NEELOTPAL SEN SARMA, DEVASISH CHOWDHURY and NIRAB CHANDRA ADHIKARY.

  8. Sulfonated 1,3-bis(4-pyridylpropane

    Directory of Open Access Journals (Sweden)

    Ore Kuyinu


    Full Text Available In the title compound, 4-[3-(3-sulfonatopyridin-1-ium-4-ylpropyl]pyridin-1-ium-3-sulfonate, C13H14N2O6S2, the molecule is zwitterionic, with the sulfonic acid proton transfered to the basic pyridine N atom. Also, the structure adopts a butterfly-like conformation with the sulfonate groups on opposite sides of the `wings'. The dihedral angle between the two pyridinium rings is 83.56 (7°, and this results in the molecule having a chiral conformation and packing. There is strong intermolecular hydrogen bonding between the pyridinium H and sulfonate O atoms of adjoining molecules. In addition, there are weaker intermolecular C—H...O interactions.

  9. Novel proton exchange membranes based on cardo poly(arylene ether sulfone/nitrile)s with perfluoroalkyl sulfonic acid moieties for passive direct methanol fuel cells (United States)

    Zheng, Jifu; He, Qingyi; Gao, Nian; Yuan, Ting; Zhang, Suobo; Yang, Hui


    A new series of cardo poly(arylene ether sulfone/nitrile)s FSPES-x with perfluoroalkyl sulfonic acid groups have been successfully prepared by the perfluorosulfonic acid lactone ring-opening reaction without using any metal or base catalysts. These materials have been characterized by IR, NMR and TGA. The results indicate that this simple and metal-free method of preparation is highly efficient for controlling both the degree of perfluorosulfonation and the position of the sulfonate group and no side reactions such as crosslinking is observed. The FSPES-x membranes (IEC = 1.17-1.64 m equiv g-1) show the desired characteristics such as good film-forming ability, excellent thermal and mechanical properties, low methanol permeability, high conductivity (up to 0.083 S cm-1 at room temperature), as well as appropriate cell performance compared to Nafion®117. With these properties, such fluorinated sulfonic acid side-chain-type polymers are promising PEM materials for application in fuel cells.

  10. Sulfonation of vulcanized ethylene-propylene-diene terpolymer membranes

    Energy Technology Data Exchange (ETDEWEB)

    Barroso-Bujans, F. [Instituto de Ciencia y Tecnologia de Polimeros, CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)], E-mail:; Verdejo, R.; Lozano, A. [Instituto de Ciencia y Tecnologia de Polimeros, CSIC, Juan de la Cierva 3, 28006 Madrid (Spain); Fierro, J.L.G. [Instituto de Catalisis y Petroleoquimica, CSIC, Marie Curie 2, Cantoblanco, 28049 Madrid (Spain); Lopez-Manchado, M.A. [Instituto de Ciencia y Tecnologia de Polimeros, CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)


    In the present work, sulfonation of previously vulcanized ethylene propylene diene terpolymer (EPDM) membranes was developed in a swelling solvent with acetyl sulfate. This procedure avoids the need to pre-dissolve the raw polymer. The reaction conditions were optimized in terms of solvent type, reaction time, acetyl sulfate concentration and film thickness to obtain the maximum degree of sulfonation of the polymer. The sulfonation procedure presented in this study yields a degree of sulfonation comparable to the chlorosulfonic acid procedure. Sulfonic acid groups were detected by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy, and quantified by titrations. Proton conductivity and water uptake were measured by means of impedance spectroscopy and swelling measurements, respectively, and were correlated with the degree of sulfonation. Tensile strength and Young's modulus of sulfonated EPDM increased with the degree of sulfonation, while elongation at break remained constant. Thermal stability of the sulfonated EPDM was studied by simultaneous thermogravimetry-mass spectroscopy.

  11. Preparation of Sulfonated PVA-TMSP Membranes for Direct Methanol Fuel Cell

    Directory of Open Access Journals (Sweden)



    Full Text Available Novel preparation and characterization of sulfonated polyvinyl alcohol (PVA–trimethoxysilyl propanethiol (TMSP membranes for direct methanol fuel cell (DMFC application have been investigated. Preparation of sulfonated PVA-TMSP membrane was conducted by crosslinking steps using sol-gel method and a catalyst of concentrated HCl. TMSP concentrations were varied from 1% to 3%. The gel solution was cast on to the membrane metal plate to obtain membrane sheets. The membrane was then oxidized in H2O2 concentrations of (10-30% to convert the mercapto groups into sulfonate group. Investigations of the cross-linking process and the existence of sulfonate group were conducted by infrared spectroscopy as shown for frequencies at 1140–1200/cm and 1200–1145/cm respectively. The scanning electron microscope–energy dispersive X-rays (SEM–EDX of the membranes indicated that the distribution of silica particles from sol–gel reaction products was uneven due to the fast exchange rate of condensation. The degree of swelling decreased as methanol concentrations increase for sulfonated PVA–TMSP membrane which opposed toward the value of commercial Nafion membrane. The maximum value of ion exchange capacity of the membrane was 1.82 mmol/g whereas the highest proton conductivity was 3.9 x 10-4 S/cm. Therefore it can be concluded that the membrane was a potential candidate for application in DMFC.

  12. The expression of Arabidopsis glutamate dehydrogenase gene gdh2 is induced under the influence of tetrapyrrole synthesis inhibitor norflurazon

    Directory of Open Access Journals (Sweden)

    E.Yu. Garnik


    Full Text Available The gdh2 gene encoding beta-subunit of glutamate dehydrogenase in Arabidopsis belongs to diurnal-regulated genes. Its expression is highly increased in the dark and reduced to minimal rates at the day light. Some sugar-responsive regulatory pathways are known to be involved in the gdh2 light repression, but the specific mechanisms of this regulation are unknown. In our experiments expression of gdh2 gene increased 6-11 fold in Arabidopsis seedlings grown in presence of the tetrapyrrole synthesis inhibitor norflurazon. The increasing rate depended on the light intensity and did not correlate with the induction of ROS marker genes. This observation can be explained by both a low glucose level in the cells treated with norflurazon and absence of repression by the chloroplast-to-nucleus retrograde pathways because of chloroplast dysfunction. We assume that the diurnal regulation of gdh2 gene expression involves not only sugar-dependent, but also chloroplast-to-nucleus regulatory signals.

  13. Anaerobic degradation of linear alkylbenzene sulfonate

    DEFF Research Database (Denmark)

    Mogensen, Anders Skibsted; Haagensen, Frank; Ahring, Birgitte Kiær


    Linear alkylbenzene sulfonate (LAS) found in wastewater is removed in the wastewater treatment facilities by sorption and aerobic biodegradation. The anaerobic digestion of sewage sludge has not been shown to contribute to the removal. The concentration of LAS based on dry matter typically...... increases during anaerobic stabilization due to transformation of easily degradable organic matter. Hence, LAS is regarded as resistant to biodegradation under anaerobic conditions. We present data from a lab-scale semi-continuously stirred tank reactor (CSTR) spiked with linear dodecylbenzene sulfonate (C...

  14. An investigation of proton conductivity of binary matrices sulfonated ...

    Indian Academy of Sciences (India)

    SPSU) and polyvinyl triazole were studied as binary matrices. The sulfonation of polysulfone was performed with trimethylsilylchlorosulfonate and high degree of sulfonation (140%) was obtained. Ion exchange capacity of SPSU was determined ...

  15. An investigation of proton conductivity of binary matrices sulfonated ...

    Indian Academy of Sciences (India)

    The polymer electrolyte membranes were prepared by blending of sulfonated polysulfone with polyvinyl triazole and phosphoric acid. Fourier transform infrared spectroscopy confirmed the sulfonation of the polysulfone and the ionic interaction between sulfonic acid and triazole units. Thermogravimetric analysis showed ...

  16. Sulfonated graphenes catalyzed synthesis of expanded porphyrins ...

    Indian Academy of Sciences (India)

    A newer synthesis of sulfonic acid functionalized graphenes have been developed, which have been characterized, examined as heterogeneous solid acid carbocatalyst in the synthesis of selected expanded porphyrins in different reaction conditions. This environment-friendly catalyst avoids the use of toxic catalysts and ...

  17. Sulfonated graphenes catalyzed synthesis of expanded porphyrins ...

    Indian Academy of Sciences (India)

    Abstract. A newer synthesis of sulfonic acid functionalized graphenes have been developed, which have been characterized, examined as heterogeneous solid acid carbocatalyst in the synthesis of selected expanded porphyrins in different reaction conditions. This environment-friendly catalyst avoids the use of toxic ...

  18. Enhancement of proton conductivity of sulfonated polystyrene ...

    Indian Academy of Sciences (India)

    ... water uptake, sulfonation rate, ion exchange capacity and thermal behaviour. The proton conductivity of the membranes is achieved up to 0.6 Scm-1, measured with the help of potentiostat/galvanostat. The thermogravimetric study of the plasma polymerized membrane shows the thermal stability up to 140 °C temperature.

  19. Synthesis, Characterization, and Catalytic Activity of Sulfonated Carbon-Based Catalysts Derived From Rubber Tree Leaves and Pulp and Paper Mill Waste (United States)

    Janaun, J.; Sinin, E.; Hiew, S. F.; Kong, A. M. T.; Lahin, F. A.


    Sulfonated carbon-based catalysts derived from rubber tree leaves, and pulp and paper mill waste were synthesized and characterized. Three types of catalyst synthesized were sulfonated rubber tree leaves (S-RTL), pyrolysed sludge char (P-SC) and sulfonated sludge char (S-SC). Sulfonated rubber tree leaves (S-RTL) and sulfonated sludge char (S-SC) were prepared through pyrolysis followed by functionalization via sulfonation process whereas, P- SC was only pyrolyzed without sulfonation. The characterization results indicated sulfonic acids, hydroxyl, and carboxyl moieties were detected in S-RTL and S-SC, but no sulfonic acid was detected in P-SC. Total acidity test showed S-RTL had the highest value followed by S-SC and P-SC. The thermal stability of S-RTL and S-SC were up to 230oC as the loss was associated with the decomposition of sulfonic acid group, whereas, P-SC showed higher stability than the S-RTL and S-SC. Morphology analysis showed that S-RTL consisted of an amorphous carbon structure, and a crystalline structure for P-SC and S-SC. Furthermore, traces of metal components were also detected on all of the catalysts. The catalyst catalytic activity was tested through esterification of oleic acid with methanol. The results showed that the reaction using S-RTL catalyst produced the highest conversion (99.9%) followed by P-SC (88.4%) and lastly S-SC (82.7%). The synthesized catalysts showed high potential to be used in biodiesel production.

  20. A diastereoselective unique route to cyclopropanes functionalized at all three ring carbon atoms from acyclic vinyl sulfone-modified carbohydrates. (United States)

    Atta, Ananta Kumar; Pathak, Tanmaya


    In a departure from the current trend of using metal-catalyzed routes to cyclopropanation, pentosyl and hexosyl vinyl sulfone-modified carbohydrates having the terminal double bond and a suitably positioned leaving group are reacted in a stereoselective fashion with a series of nucleophiles to yield a myriad of cyclopropanes substituted at all three ring carbon atoms.

  1. The Arabidopsis translocator protein (AtTSPO is regulated at multiple levels in response to salt stress and perturbations in tetrapyrrole metabolism

    Directory of Open Access Journals (Sweden)

    Umen James G


    Full Text Available Abstract Background The translocator protein 18 kDa (TSPO, previously known as the peripheral-type benzodiazepine receptor (PBR, is important for many cellular functions in mammals and bacteria, such as steroid biosynthesis, cellular respiration, cell proliferation, apoptosis, immunomodulation, transport of porphyrins and anions. Arabidopsis thaliana contains a single TSPO/PBR-related gene with a 40 amino acid N-terminal extension compared to its homologs in bacteria or mammals suggesting it might be chloroplast or mitochondrial localized. Results To test if the TSPO N-terminal extension targets it to organelles, we fused three potential translational start sites in the TSPO cDNA to the N-terminus of GFP (AtTSPO:eGFP. The location of the AtTSPO:eGFP fusion protein was found to depend on the translational start position and the conditions under which plants were grown. Full-length AtTSPO:eGFP fusion protein was found in the endoplasmic reticulum and in vesicles of unknown identity when plants were grown in standard conditions. However, full length AtTSPO:eGFP localized to chloroplasts when grown in the presence of 150 mM NaCl, conditions of salt stress. In contrast, when AtTSPO:eGFP was truncated to the second or third start codon at amino acid position 21 or 42, the fusion protein co-localized with a mitochondrial marker in standard conditions. Using promoter GUS fusions, qRT-PCR, fluorescent protein tagging, and chloroplast fractionation approaches, we demonstrate that AtTSPO levels are regulated at the transcriptional, post-transcriptional and post-translational levels in response to abiotic stress conditions. Salt-responsive genes are increased in a tspo-1 knock-down mutant compared to wild type under conditions of salt stress, while they are decreased when AtTSPO is overexpressed. Mutations in tetrapyrrole biosynthesis genes and the application of chlorophyll or carotenoid biosynthesis inhibitors also affect AtTSPO expression. Conclusion Our

  2. Detection, quantifications and pharmacokinetics of toltrazuril sulfone (Ponazuril) in cattle. (United States)

    Dirikolu, L; Yohn, R; Garrett, E F; Chakkath, T; Ferguson, D C


    Toltrazuril sulfone (Ponazuril) is a triazine-based anti-protozoal agent with highly specific actions against apicomplexan group of organisms, which are undergoing intensive investigation. Toltrazuril sulfone may have clinical application in the treatment of Neospora. caninum and other protozoal infections in cattle. To evaluate absorption, distribution, and elimination characteristics of toltrazuril sulfone in cattle, a sensitive validated quantitative high-pressure liquid chromatography method for toltrazuril sulfone in bovine biological fluids was developed. After a single oral dose of toltrazuril sulfone at 5 mg/kg (as 150 mg/g of Marquis; Bayer HealthCare, Shawnee Mission, KS, USA), samples from six cows showed good plasma concentrations of toltrazuril sulfone, which peaked at 4821 ng/mL +/- 916 (SD) at 48 h postadministration. Thereafter, plasma concentration declined to 1950 ng/mL +/- 184 (SD) at 192 h after administration with an average plasma elimination half-life of approximately 58 h. Following oral dose of toltrazuril sulfone, the observed peak plasma concentrations were in relatively close agreement ranging from the lowest 3925 ng/mL to the highest of 6285 ng/mL with the mean peak plasma concentration being 4821 ng/mL. This study shows that toltrazuril sulfone is relatively well absorbed after oral dose in cattle. These results are therefore entirely consistent with and support the reported clinical efficacy of toltrazuril sulfone in the treatment of experimentally induced clinical cases of N. caninum and other protozoal-mediated bovine diseases.

  3. Thermal and Dielectric Behavior Studies of Poly(Arylene Ether Sulfones with Sulfonated and Phosphonated Pendants

    Directory of Open Access Journals (Sweden)

    Shimoga D. Ganesh


    Full Text Available The present paper discusses the aspects of the synthesizing valeric acid based poly(ether sulfones with active carboxylic acid pendants (VALPSU from solution polymerization technique via nucleophilic displacement polycondensation reaction among 4,4′-dichlorodiphenyl sulfone (DCDPS and 4,4′-bis(4-hydroxyphenyl valeric acid (BHPA. The conditions necessary to synthesize and purify the polymer were investigated in some detail. The synthesized poly(ether sulfones comprise sulfone and ether linkages in addition to reactive carboxylic acid functionality; these active carboxylic acid functional groups were exploited to hold the phenyl sulphonic acid and phenyl phosphonic acid pendants. The phenyl sulphonic acid pendants in VALPSU were easily constructed by altering active carboxylic acid moieties by sulfanilic acid using N,N′-dicyclohexylcarbodiimide (DCC mediated mild synthetic route, whereas the latter one was built in two steps. Initially, polyphosphoric acid condensation with VALPSU by 4-bromoaniline and next straightforward palladium catalyzed synthetic route, in both of which acidic pendants are clenched by polymer backbone via amide linkage. Without impairing the primary polymeric backbone modified polymers were prepared by varying the stoichiometric ratios of respective combinations. All the polymers were physicochemically characterized and pressed into tablets; electrical contacts were established to study the dielectric properties. Finally, the influence of the acidic pendants on the dielectric properties was examined.

  4. Synthesis and characterization of sulfonated poly(ether sulfone) copolymer membranes for fuel cell applications (United States)

    Krishnan, N. N.; Kim, H.-J.; Prasanna, M.; Cho, E.; Shin, E.-M.; Lee, S.-Y.; Oh, I.-H.; Hong, S.-A.; Lim, T.-H.

    Sulfonated poly(ether sulfone) copolymers (PESs) are synthesized using hydroquinone 2-potassium sulfonate (HPS) with other monomers (bisphenol A and 4-fluorophenyl sulfone). A series of PESs with different mol% of hydrophilic group is prepared by changing the mole ratio of HPS in the polymerization reaction. The chemical structure and thermal stability of the polymers are characterized by using 1H NMR, FT-IR and TGA techniques. The PES 60 membrane, which has 60 mol% of HPS unit in the polymer backbone, has a proton conductivity of 0.091 S cm -1 and good insolubility in boiling water. The TGA showed that PES 60 is stable up to 272 °C with a char yield of about 29% at 900 °C under a nitrogen atmosphere. To investigate single-cell performance, a catalyst-coated PES 60 membrane is used together with hydrogen and oxygen as the fuel and the oxidant, respectively. Cell performance is enhanced by increasing the temperature. A current density of 1400 mA cm -2 at 0.60 V is obtained at 70 °C.

  5. Production and Application of Lignosulfonates and Sulfonated Lignin. (United States)

    Aro, Thomas; Fatehi, Pedram


    Lignin is the largest reservoir of aromatic compounds on earth and has great potential to be used in many industrial applications. Alternative methods to produce lignosulfonates from spent sulfite pulping liquors and kraft lignin from black liquor of kraft pulping process are critically reviewed herein. Furthermore, options to increase the sulfonate contents of lignin-based products are outlined and the industrial attractiveness of them is evaluated. This evaluation includes sulfonation and sulfomethylation of lignin. To increase the sulfomethylation efficiency of lignin, various scenarios, including hydrolysis, oxidation, and hydroxymethylation, were compared. The application of sulfonated lignin-based products is assessed and the impact of the properties of these products on the characteristics of their end-use application is critically evaluated. Sulfonated lignin-based products have been used as dispersants in cement admixtures and dye solutions more than other applications, and their molecular weight and degree of sulfonation were crucial in determining their efficiency. The use of lignin-based sulfonated products in composites may result in an increase in the hydrophilicity of some composites, but the sulfonated products may need to be desulfonated with an alkali and/or oxygen prior to their use in composites. To be used as a flocculant, sulfonated lignin-based products may need to be cross-linked to increase their molecular weight. The challenges associated with the use of lignin-based products in these applications are comprehensively discussed herein. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Preparation and Characterization of Sulfonated Poly (ether ether ...

    African Journals Online (AJOL)

    Proton-conducting membranes of organic–inorganic (sulfonated poly (ether ether ketone)/phosphated zirconia nanoparticles) composite were prepared by incorporating various ratios of phosphated zirconia nanoparticles (ZP) in sulfonated poly (ether ether ketone) (SPEEK). SPEEK/ZP showed an improvement of ...

  7. Metals and metal complexes in coal

    Energy Technology Data Exchange (ETDEWEB)

    Bonnett, R.; Czechowski, F. (Queen Mary College, London, UK)


    Some of the metal compounds that occur in coal are soluble in organic solvents and are extracted in coal liquefaction processes. The material made by the extraction of coal with hydrogenated anthracene oil has been fractionated by sequential Soxhlet extraction with low-boiling solvents, and the distribution of the metallic elements in the various fractions has been determined. Extraction of Daw Mill coal (92 kg) with acidic methanol furnishes 17.8 mg of a mixture of gallium complexes of homologous porphyrins (C$SUB$2$SUB$7-C$SUB$3$SUB$2). Similar metallo-porphyrin concentrates are obtained from a variety of British bituminous coals, the amount detected being about 1MUg/g, but falling off as coal rank increases. Various lignites and a range of Polish coals have also been surveyed: here, iron porphyrins and (in one case) manganese porphyrins have been observed. The iron porphyrins tend to be confined to coals of lower rank: in the lignites, metal-free tetrapyrroles are also detected. The metalloporphyrins are thought to be derived from the chlorophylls and haems of the biological precursors. Indeed, it is possible that the iron porphyrins are derived directly (i.e. without demetallation-metallation) from biological and microbiological haem compounds. (21 refs.)

  8. Fe–Co/sulfonated polystyrene as an efficient and selective catalyst in heterogeneous Baeyer–Villiger oxidation reaction of cyclic ketones

    Directory of Open Access Journals (Sweden)

    Yingting Wang


    Full Text Available A highly efficient catalyst Fe–Co/sulfonated polystyrene (Fe–Co/SPS was introduced and synthesized, which catalyzed BV oxidation of ketones with aqueous hydrogen peroxide to give the corresponding lactones in high yield and selectivity. Solid acid catalyst of Fe–Co/SPS has been prepared by using the 98-wt% sulfuric acid as the sulfonating agent and CoCl2 combined FeCl3 as sources of metal ions. Various physical–chemical characterizations including FT-IR, XRD, SEM and TGA, revealed that bimetallic ions Fe3+–Co2+ species in the sulfonated polystyrene framework were responsible for the catalytic activities. The BV reaction catalyzed by Fe–Co/SPS highlighted the special effects between metal ions and protonic acids as well as solvent-free heterogeneous catalytic oxidation with excellent conversion.

  9. Synthesis and characterization of polymer blends of sulfonated polyethersulfone and sulfonated polyethersulfone octylsulfonamide for PEMFC applications

    Energy Technology Data Exchange (ETDEWEB)

    Mabrouk, W. [ERAS Labo, St Nazaire Les Eymes, Grenoble (France); Laboratoire des Materiaux Industriels, Conservatoire National des Arts et Metiers de Paris, 75003 Paris (France); Laboratoire de Chimie Analytique et Electrochimie, Faculte des Sciences de Tunis, Campus Universitaire, 1092 Tunis (Tunisia); Ogier, L.; Vidal, S. [ERAS Labo, St Nazaire Les Eymes, Grenoble (France); Sollogoub, C.; Fauvarque, J.F. [Laboratoire des Materiaux Industriels, Conservatoire National des Arts et Metiers de Paris, 75003 Paris (France); Matoussi, F.; Dachraoui, M. [Laboratoire de Chimie Analytique et Electrochimie, Faculte des Sciences de Tunis, Campus Universitaire, 1092 Tunis (Tunisia)


    Our goal in the present work was to synthesize a new proton exchange membrane that could be used in proton exchange membrane fuel cell (PEMFC), based on a blend of sulfonated polyethersulfone (S-PES) and sulfonated polyethersulfone octylsulfonamide (S-PESOS). Five blends, using S-PESOS with different grafting ratios of sulfonamide groups, have been elaborated, characterized, and tested in a PEMFC. The similar chemical structure between these two polymers favored their compatibility. The synthesized membranes showed a high water swelling capacity and an ionic conductivity equivalent to that of Nafion registered (0.1 S cm{sup -1}) in the same conditions. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. 4-(4-Aminophenylsulfonylanilinium toluene-4-sulfonate

    Directory of Open Access Journals (Sweden)

    Graham Smith


    Full Text Available In the title p-toluenesulfonate salt of the drug dapsone, C12H13N2O2S+·C7H7O3S−, the dihedral angle between the two aromatic rings of the dapsone monocation is 70.19 (17° and those between these rings and that of the p-toluenesulfonate anion are 72.34 (17 and 46.43 (17°. All amine and aminium H atoms are involved in intermolecular N—H...O hydrogen-bonding associations with sulfonyl O-atom acceptors as well as one of the sulfone O atoms, giving a three-dimensional structure.

  11. Preparation of new proton exchange membranes using sulfonated poly(ether sulfone) modified by octylamine (SPESOS)

    Energy Technology Data Exchange (ETDEWEB)

    Mabrouk, W. [Societe ERAS Labo, 222 RN 90, 38330, St Nazaire Les Eymes, Grenoble (France); Laboratoire des Materiaux Industriels, Conservatoire National des Arts et Metiers de Paris 75003, Paris (France); Laboratoire de Chimie Analytique et Electrochimie, Faculte des Sciences de Tunis, Campus Universitaire 1092, Tunis (Tunisia); Ogier, L. [Societe ERAS Labo, 222 RN 90, 38330, St Nazaire Les Eymes, Grenoble (France); Matoussi, F. [Laboratoire de Chimie Analytique et Electrochimie, Faculte des Sciences de Tunis, Campus Universitaire 1092, Tunis (Tunisia); Sollogoub, C., E-mail: [Laboratoire des Materiaux Industriels, Conservatoire National des Arts et Metiers de Paris 75003, Paris (France); Vidal, S. [Societe ERAS Labo, 222 RN 90, 38330, St Nazaire Les Eymes, Grenoble (France); Dachraoui, M. [Laboratoire de Chimie Analytique et Electrochimie, Faculte des Sciences de Tunis, Campus Universitaire 1092, Tunis (Tunisia); Fauvarque, J.F. [Laboratoire des Materiaux Industriels, Conservatoire National des Arts et Metiers de Paris 75003, Paris (France)


    Highlights: {yields} New, simple and cheap way to synthesize a membrane. {yields} The membranes combine good proton conductivities with good mechanical properties. {yields} The membrane performances in a fuel cell are similar to the Nafion 117. - Abstract: Sulfonated poly(arylene ether sulfone) (SPES) has received considerable attention in membrane preparation for proton exchange membrane fuel cell (PEMFC). But such membranes are brittle and difficult to handle in operation. We investigated new membranes using SPES grafted with various degrees of octylamine. Five new materials made from sulfonated polyethersulfone sulfonamide (SPESOS) were synthetized with different grades of grafting. They were made from SPES, with initially an ionic exchange capacity (IEC) of 2.4 meq g{sup -1} (1.3 H{sup +} per monomer unit). Pristine SPES with that IEC is water swelling and becomes soluble at 80 deg. C, its proton conductivity is in the range of 0.1 S cm{sup -1} at room temperature in aqueous H{sub 2}SO{sub 4} 1 M, similar to that of Nafion. After grafting with various amounts of octylamine, the material is water insoluble; membranes are less brittle and show sufficient ionic conductivity. Proton transport numbers were measured close to 1.

  12. Electrical conductivity of sulfonated poly(ether ether ketone) based composite membranes containing sulfonated polyhedral oligosilsesquioxane (United States)

    Celso, Fabricio; Mikhailenko, Serguei D.; Rodrigues, Marco A. S.; Mauler, Raquel S.; Kaliaguine, Serge


    Composite proton exchange membranes (PEMs) intended for fuel cell applications were prepared by embedding of various amounts of dispersed tri-sulfonic acid ethyl POSS (S-Et-POSS) and tri-sulfonic acid butyl POSS (S-Bu-POSS) in thin films of sulfonated poly ether-ether ketone. The electrical properties of the PEMs were studied by Impedance spectroscopy and it was found that their conductivity σ changes with the filler content following a curve with a maximum. The water uptake of these PEMs showed the same dependence. The investigation of initial isolated S-POSS substances revealed the properties of typical electrolytes, which however in both cases possessed low conductivities of 1. 17 × 10-5 S cm-1 (S-Et-POSS) and 3.52 × 10-5 S cm-1 (S-Bu-POSS). At the same time, the insoluble in water S-POSS was found forming highly conductive interface layer when wetted with liquid water and hence producing a strong positive impact on the conductivity of the composite PEM. Electrical properties of the composites were analysed within the frameworks of effective medium theory and bounding models, allowing to evaluate analytically the range of possible conductivity values. It was found that these approaches produced quite good approximation of the experimental data and constituted a fair basis for interpretation of the observed relationship.

  13. Hydroquinone based sulfonated poly (arylene ether sulfone copolymer as proton exchange membrane for fuel cell applications

    Directory of Open Access Journals (Sweden)

    V. Kiran


    Full Text Available Synthesis of sulfonated poly (arylene ether sulfone copolymer by direct copolymerization of 4,4'-bis(4-hydroxyphenyl valeric acid, benzene 1,4-diol and synthesized sulfonated 4,4'-difluorodiphenylsulfone and its characterization by using FTIR (Fourier Transform Infrared and NMR (Nuclear Magnetic Resonance spectroscopic techniques have been performed. The copolymer was subsequently cross-linked with 4, 4!(hexafluoroisopropylidenediphenol epoxy resin by thermal curing reaction to synthesize crosslinked membranes. The evaluation of properties showed reduction in water and methanol uptake, ion exchange capacity, proton conductivity with simultaneous enhancement in oxidative stability of the crosslinked membranes as compared to pristine membrane. The performance of the membranes has also been evaluated in terms of thermal stability, morphology, mechanical strength and methanol permeability by using Thermo gravimetric analyzer, Differential scanning calorimetery, Atomic force microscopy, XPERT-PRO diffractometer, universal testing machine and diffusion cell, respectively. The results demonstrated that the crosslinked membranes exhibited high thermal stability with phase separation, restrained crystallinity, acceptable mechanical properties and methanol permeability. Therefore, these can serve as promising proton exchange membranes for fuel cell applications.

  14. Fully Aromatic Block Copolymers for Fuel Cell Membranes with Densely Sulfonated Nanophase Domains

    DEFF Research Database (Denmark)

    Takamuku, Shogo; Jannasch, Patrick; Lund, Peter Brilner

    Two multiblock copoly(arylene ether sulfone)s with similar block lengths and ion exchange capacities (IECs) were prepared by a coupling reaction between a non-sulfonated precursor block and a highly sulfonated precursor block containing either fully disulfonated diarylsulfone or fully...... tetrasulfonated tetraaryldisulfone segments. The latter two precursor blocks were sulfonated via lithiation-sulfination reactions whereby the sulfonic acid groups were exclu- sively placed in ortho positions to the many sulfone bridges, giving these locks IECs of 4.1 and 4.6 meqg1, respectively. Copolymer...

  15. Room temperature synthesis of biodiesel using sulfonated graphitic carbon nitride (United States)

    Sulfonation of graphitic carbon nitride (g-CN) affords a polar and strongly acidic catalyst, Sg-CN, which displays unprecedented reactivity and selectivity in biodiesel synthesis and esterification reactions at room temperature.

  16. Sulfonated hydrocarbon graft architectures for cation exchange membranes

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller; Jankova Atanasova, Katja; Hvilsted, Søren


    A synthetic strategy to hydrocarbon graft architectures prepared from a commercial polysulfone and aimed as ion exchange membrane material is proposed. Polystyrene is grafted from a polysulfone macroinitiator by atom transfer radical polymerization, and subsequently sulfonated with acetyl sulfate...

  17. Amperometric urea biosensors based on sulfonated graphene/polyaniline nanocomposite


    Das G.; Yoon HH


    Gautam Das, Hyon Hee Yoon Department of Chemical and Biological Engineering, Gachon University, Seongnam, Gyeonggi-do, South Korea Abstract: An electrochemical biosensor based on sulfonated graphene/polyaniline nanocomposite was developed for urea analysis. Oxidative polymerization of aniline in the presence of sulfonated graphene oxide was carried out by electrochemical methods in an aqueous environment. The structural properties of the nanocomposite were characterized by Fourier-transform...

  18. Characterization of a sulfonated polycarbonate resistive humidity sensor. (United States)

    Rubinger, Carla P L; Calado, Hallen D R; Rubinger, Rero M; Oliveira, Henrique; Donnici, Claudio L


    In this work; resistive moisture sensors were obtained by dip coating sulfonated polycarbonate (SPC) onto silver interdigitated electrodes. Commercial polycarbonate was sulfonated with acetyl sulphate at two different sulfonation degrees corresponding to 9.0 and 18.0 mole %. Impedance spectroscopy was used to investigate the humidity sensing properties at controlled relative humidity (RH%) environments generated from standard saline solutions in the range of 11-90 RH%. For the highest sulfonated sample; in the RH% range investigated (11 to 90%); the sensor impedance changed from 4.7 MΩ to 18 kΩ. Humidity sensors made from sulfonated polycarbonate showed exponential decay behavior of the impedance at constant frequency with the environmental relative humidity. Sample 9SPC presented dielectric relaxation response for environmental humidity between 58 and 90 RH% while sample 18SPC presented dielectric relaxation response for the entire measured range between 11 and 90 RH%. Sulfonated polycarbonate could be a promising material for the fabrication of simple and cheap humidity-sensing sensors for the assessment of relative humidity of the surrounding environment, as suggested by experimental results.

  19. Multiblock copolymers with highly sulfonated blocks containing di- and tetrasulfonated arylene sulfone segments for proton exchange membrane fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Takamuku, Shogo; Jannasch, Patric [Polymer and Materials Chemistry, Department of Chemistry, Lund University (Sweden)


    Multiblock copoly(arylene ether sulfone)s with different block lengths and ionic contents are tailored for durable and proton-conducting electrolyte membranes. Two series of fully aromatic copolymers are prepared by coupling reactions between non-sulfonated hydrophobic precursor blocks and highly sulfonated hydrophilic precursor blocks containing either fully disulfonated diarylsulfone or fully tetrasulfonated tetraaryldisulfone segments. The sulfonic acid groups are exclusively introduced in ortho positions to the sulfone bridges to impede desulfonation reactions and give the blocks ion exchange capacities (IECs) of 4.1 and 4.6 meq. g{sup -1}, respectively. Solvent cast block copolymer membranes show well-connected hydrophilic nanophase domains for proton transport and high decomposition temperatures above 310 C under air. Despite higher IEC values, membranes containing tetrasulfonated tetraaryldisulfone segments display a markedly lower water uptake than the corresponding ones with disulfonated diarylsulfone segments when immersed in water at 100 C, presumably because of the much higher chain stiffness and glass transition temperature of the former segments. The former membranes have proton conductivities in level of a perfluorosulfonic acid membrane (NRE212) under fully humidified conditions. A membrane with an IEC of 1.83 meq. g{sup -1} reaches above 6 mS cm{sup -1} under 30% relative humidity at 80 C, to be compared with 10 mS cm{sup -1} for NRE212 under the same conditions. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Synthesis in pilot plant scale and physical properties of sulfonated polystyrene

    Directory of Open Access Journals (Sweden)

    Martins Cristiane R.


    Full Text Available The homogenous sulfonation of polystyrene was developed in a pilot plant scale producing polymers with different sulfonation degrees (18 to 22 mole % of sulfonated styrene units. The reaction yield depends chiefly on the concentration ratio of acetyl sulfate and polystyrene. The morphological and thermal properties of the sulfonated polystyrene obtained by homogeneous sulfonation were studied by means of scanning electron microscopy, differential scanning calorimetry and thermogravimetry. The glass transition temperature of sulfonated polystyrene increases in relation to pure polystyrene and DCp was evaluated in order to confirm the strong interactions among the ~SO3H groups.

  1. Synthesis and characterization of sulfonated poly (arylene ether sulfone) copolymers via direct copolymerization: Candidates for proton exchange membrane fuel cells (United States)

    Harrison, William Lamont

    A designed series of directly copolymerized homo- and disulfonated copolymers containing controlled degrees of pendant sulfonic acid groups have been synthesized via nucleophilic step polymerization. Novel sulfonated poly (arylene ether sulfone) copolymers using 4,4'-bisphenol A, 4,4'-biphenol, hexafluorinated (6F) bisphenol AF, and hydroquinone, respectively, with dichlorodiphenyl sulfone (DCDPS) and 3,3'-disodiumsulfonyl-4,4'-dichlorodiphenylsulfone (SDCDPS) were investigated. Molar ratios of DCDPS and SDCDPS were systematically varied to produce copolymers of controlled compositions, which contained up to 70 mol% of disulfonic acid moiety. The goal is to identify thermally, hydrolytically, and oxidatively stable high molecular weight, film-forming, ductile ion conducting copolymers, which had properties desirable for proton exchange membranes (PEM) in fuel cells. Commercially available bisphenols were selected to produce cost effective alternative PEMs. Partially aliphatic bisphenol A and hexafluorinated (6F) bisphenol AF produced amorphous copolymers with different thermal oxidative and surface properties. Biphenol and hydroquinone was utilized to produce wholly aromatic copolymers. The sulfonated copolymers were prepared in the sodium-salt form and converted to the acid moiety via two different methodologies and subsequently investigated as proton exchange membranes for fuel cells. Hydrophilicity increased with the level of disulfonation, as expected. Moreover, water sorption increased with increasing mole percent incorporation of SDCDPS. The copolymers' water uptake was a function of both bisphenol structure and degree of disulfonation. Furthermore, the acidification procedures were shown to influence the Tg values, water uptake, and conductivity of the copolymers. Atomic force microscopy (AFM) in the tapping mode confirmed that the morphology of the copolymers could be designed to display nanophase separation in the hydrophobic and hydrophilic (sulfonated

  2. Inhibition of the anaerobic digestion process by linear alkylbenzene sulfonates

    DEFF Research Database (Denmark)

    Gavala, Hariklia N.; Ahring, Birgitte Kiær


    Linear Alkylbenzene Sulfonates (LAS) are the most widely used synthetic anionic surfactants. They are anthropogenic, toxic compounds and are found in the primary sludge generated in municipal wastewater treatment plants. Primary sludge is usually stabilized anaerobically and therefore it is impor......Linear Alkylbenzene Sulfonates (LAS) are the most widely used synthetic anionic surfactants. They are anthropogenic, toxic compounds and are found in the primary sludge generated in municipal wastewater treatment plants. Primary sludge is usually stabilized anaerobically and therefore...... it is important to investigate the effect of these xenobiotic compounds on an anaerobic environment. The inhibitory effect of Linear Alkylbenzene Sulfonates (LAS) on the acetogenic and methanogenic step of the anaerobic digestion process was studied. LAS inhibit both acetogenesis from propionate...

  3. The shape of cells adhering to sulfonated copolymer surfaces. (United States)

    Kowalczyńska, Hanna M; Nowak-Wyrzykowska, Małgorzata; Inkielman, Marcin; Stołowska, Liliana; Marciniak, Ewa


    We studied the shape of L1210 leukaemia cells adhering in a protein-free medium to sulfonated (styrene/methyl methacrylate) copolymer surfaces of two sulfonic group densities, and thus of differing wettability. The use of our image analysis method and the mathematical procedure [Kowalczynska, H.M. et al, Colloids Surfaces B: Biointerfaces, 30 (2003) 193-206.] allowed us to calculate the values of the so-called shape parameter, which quantitatively determines the three-dimensional cell shape. Here, we show that the values of the shape parameter of the adhering cells and the F-actin concentration, in the region near the cell-substratum interface, depend on the density of sulfonic groups present on the substratum surface.

  4. Perfluoroalkyl sulfonates cause alkyl chain length-dependent hepatic steatosis and hypolipidemia mainly by impairing lipoprotein production in APOE*3-leiden CETP mice

    NARCIS (Netherlands)

    Bijland, S.; Rensen, P.C.N.; Pieterman, E.J.; Maas, A.C.E.; Hoorn, J.W. van der; Erk, M.J. van; Havekes, L.M.; Dijk, K.W. van; Chang, S.C.; Ehresman, D.J.; Butenhoff, J.L.; Princen, H.M.G.


    Perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) are stable perfluoroalkyl sulfonate (PFAS) surfactants, and PFHxS and PFOS are frequently detected in human biomonitoring studies. Some epidemiological studies have shown modest positive

  5. Surface properties of porous carbon obtained from polystyrene sulfonic acid-based organic salts. (United States)

    Hines, Deon; Bagreev, Andrey; Bandosz, Teresa J


    Pyrolysis ofpolysterene sulfonic acid-co-maleic acid salts at 800 degrees C resulted in formation of new materials consisting of porous carbon and metal species dispersed on the surface. After hydrochloric acid treatment, the metal oxides/salts were removed. Obtained materials were characterized using adsorption of nitrogen, thermogravimetric analysis, Raman spectroscopy, and scanning electron microscopy with energy dispersive analysis of X-rays. The results showed highly developed porous structures in the range of micro- and mesopores. The porous features of new materials resemble those characteristics for carbon foams. The differences in the porous structure are linked to the type of transition metal used for the modification of the initial polymer and the chelation process. Macro- and mesopores are spherical/cylindrical in shape, and they are likely formed when release of pyrolysis gases, such as CO2, NO2, SO2, H2S, and CxHy, occurs. Moreover, reduction of metal, its migration to the surface, and agglomeration contribute to development of porosity. Depending on the reactivity of the metal used for cation exchange (Fe, Co, or Ni) either sulfides (nickel and cobalt) or oxides (cobalt and iron) are formed on the carbon surface.

  6. Phase behavior of a pure alkyl aryl sulfonate surfactant. [Sodium 8-phenyl-n-hexadecyl-p-sulfonate

    Energy Technology Data Exchange (ETDEWEB)

    Franses, E.I.; Davis, H.T.; Miller, W.G.; Scriven, L.E.


    Specctroturbidimetry, visual and microscopic observations, ultracentrifugation and ultrafiltration, conductimetry, and /sup 13/C NMR were used to study the phase behavior of pure sodium 8-phenyl-n-hexadecyl-p-sulfonate in water--NaCl, decane, and water--decane. Solubility of the sulfonate in water is 0.06 wt % at 25/sup 0/C and 0.7 wt % at 90/sup 0/C, and it drops to 0.0002 wt % in 3 wt % NaCl (25/sup 0/C). A liquid crystalline phase in equilibrium with aqueous solution contains 25 wt % water. Nucleation of supersaturated solutions is slow. Dispersability of the sulfonate is high, but NaCl has an adverse effect. 39 references, 13 figs., 5 tables. (DLC)

  7. A novel "oxygen-induced" greening process in a cyanobacterial mutant lacking the transcriptional activator ChlR involved in low-oxygen adaptation of tetrapyrrole biosynthesis. (United States)

    Aoki, Rina; Hiraide, Yuto; Yamakawa, Hisanori; Fujita, Yuichi


    ChlR activates the transcription of the chlAII-ho2-hemN operon in response to low-oxygen conditions in the cyanobacterium Synechocystis sp. PCC 6803. Three genes in the operon encode low-oxygen-type enzymes to bypass three oxygen-dependent reactions in tetrapyrrole biosynthesis. A chlR-lacking mutant, ΔchlR, shows poor photoautotrophic growth due to low chlorophyll (Chl) content under low-oxygen conditions, which is caused by no induction of the operon. Here, we characterized the processes of etiolation of ΔchlR cells in low-oxygen conditions and the subsequent regreening of the etiolated cells upon exposure to oxygen, by HPLC, Western blotting, and low-temperature fluorescence spectra. The Chl content of the etiolated ΔchlR cells incubated under low-oxygen conditions for 7 days was only 10% of that of the wild-type with accumulation of almost all intermediates of the magnesium branch of Chl biosynthesis. Both photosystem I (PSI) and photosystem II (PSII) were significantly decreased, accompanied by a preferential decrease of antenna Chl in PSI. Upon exposure to oxygen, the etiolated ΔchlR cells resumed to produce Chl after a short lag (∼2 h), and the level at 72 h was 80% of that of the wild-type. During this novel "oxygen-induced" greening process, the PSI and PSII contents were largely increased in parallel with the increase in Chl contents. After 72 h, the PSI content reached ∼50% of the wild-type level in contrast to the full recovery of PSII. ΔchlR provides a promising alternative system to investigate the biogenesis of PSI and PSII.

  8. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl sulfates...

  9. Fast atom bombardment mass spectrometry of condensed tannin sulfonate derivatives (United States)

    J.J. Karchesy; L.Y. Foo; Richard W. Hemingway; E. Barofsky; D.F. Barofsky


    Condensed tannin sulfonate derivatives were studied by fast atom bombardment mass spectrometry (FAB-MS) to assess the feasibility of using this technique for determining molecular weight and structural information about these compounds. Both positive- and negative-ion spectra provided useful data with regard to molecular weight, cation species present, and presence of...

  10. Sorption of perfluorooctane sulfonate to carbon nanotubes in aquatic sediments

    NARCIS (Netherlands)

    Kwadijk, C.J.A.F.; Velzeboer, I.; Koelmans, A.A.


    To date, sorption of organic compounds to nanomaterials has mainly been studied for the nanomaterial in its pristine state. However, sorption may be different when nanomaterials are buried in sediments. Here, we studied sorption of Perfluorooctane sulfonate (PFOS) to sediment and to sediment with 4%

  11. Solid-supported sulfonic acid-containing catalysts efficiently ...

    Indian Academy of Sciences (India)

    Silica-functionalized sulfonic acid (SFSA) and sulfuric acid-modified polyethylene glycol-6000 (PEG-OSO3H) efficiently catalysed one-pot multi-component condensation of enolizable ketones or alkyl acetoacetates with arylaldehydes, acetonitrile and acetyl chloride to afford the corresponding -acetamido ketone or ester ...

  12. Electronic Conductivity of Polypyrrole−Dodecyl Benzene Sulfonate Complexes

    DEFF Research Database (Denmark)

    West, Keld; Bay, Lasse; Nielsen, Martin Meedom


    The electronic conductivity of the electroactive polymer polypyrrole-dodecyl benzene sulfonate (PPy-DBS) has been characterized as function of the redox level. The polymer was synthesized with different isomers of the dopant anions: the common mixed DBS tenside and three well-defined synthetic...

  13. Sulfonated polyimides containing triphenylphosphine oxide for proton exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Mandal, Arun Kumar; Bera, Debaditya; Banerjee, Susanta, E-mail:


    A series of sulfonated co-polyimides (co-SPI) were prepared by one pot polycondensation reaction of a combination of diamines namely; 4,4′-diaminostilbene-2,2′-disulfonic acid (DSDSA) and prepared non-sulfonated diamine (DATPPO) containing triphenylphosphine oxide with 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA). All these soluble co-SPI gave flexible membranes with high thermal stability and showed good mechanical property. Transmission electron microscopy (TEM) analysis revealed the microphase separated morphology with well-dispersed hydrophilic (cluster size in the range of 5–55 nm) domains. The co-SPI membranes showed high oxidative and hydrolytic stability with higher proton conductivity. All these co-SPI membranes exhibited low water uptake and swelling ratio. The co-SPI membrane TPPO-60 (60% degree of sulfonation) with IEC{sub W} = 1.84 mequiv g{sup −1} showed high proton conductivity (99 mS cm{sup −1} at 80 °C and 107 mS cm{sup −1} at 90 °C) in water with high oxidative (20 h) and hydrolytic stability (only 5% degradation in 24 h). - Highlights: • Triphenylphosphine oxide containing sulfonated polyimides (SPIs) was synthesized. • The SPIs showed good oxidative and hydrolytic stability and high proton conductivity. • TEM analysis revealed well separated morphology of the SPIs.

  14. Response of weeping willows to linear alkylbenzene sulfonate

    DEFF Research Database (Denmark)

    Yu, X.; Trapp, Stefan; Zhou, P.


    Linear alkylbenzene sulfonate (LAS) is the most commonly used anionic surfactant in laundry detergents and cleaning agents. LAS compounds are found in surface waters and soils. The short-term acute toxicity of LAS to weeping willows (Salix babylonica L.) was investigated. Willow cuttings were grown...

  15. Polyether sulfone membrane modeling and construction for the ...

    African Journals Online (AJOL)

    The aim of this study was constructed the polyether sulfone membrane and modelling it, and for checking impact pressure, the amount of iron nanoparticles and sulfate iron intervention in reducing nitrate irons from water. For the removal ion of nitrate at 50 ppm concentration of nitrate potassium, we made three membranes ...

  16. 40 CFR 721.1625 - Alkylbenzene sulfonate, amine salt. (United States)


    .... 721.1625 Section 721.1625 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... subject to reporting. (1) The chemical substance identified generically as alkylbenzene sulfonate, amine... this part apply to this section except as modified by this paragraph. (1) Recordkeeping. The following...

  17. Intrinsic and Ionic Conduction in Humidity-Sensitive Sulfonated Polyaniline

    NARCIS (Netherlands)

    Doan, D.C.T.; Ramaneti, R.; Baggerman, J.; Tong, H.D.; Marcelis, A.T.M.; Rijn, van C.J.M.


    The influence of humidity on the conductivity of sulfonated polyaniline (SPANI) and polyaniline (PANI) is investigated with electrochemical impedance spectroscopy (EIS). Separation of intrinsic (q) and ionic charge (i) mobility was observed using combination of ac and dc impedance measurements at

  18. Uptake of 4-Toluene Sulfonate by Comamonas testosteroni T-2

    NARCIS (Netherlands)


    The mechanism of transport of the xenobiotic 4-toluene sulfonate (TS) in Comamonas testosteroni T-2 was investigated. Rapid uptake of TS was observed only in cells grown with TS or 4-methylbenzoate as a carbon and energy source. Initial uptake rates under aerobic conditions showed substrate

  19. Fate of linear alkylbenzene sulfonate (LAS) in activated sludge plants

    NARCIS (Netherlands)

    Temmink, B.G.; Klapwijk, A.


    Monitoring data were collected in a pilot-scale municipal activated sludge plant to assess the fate of the C12-homologue of linear alkyl benzene sulfonate (LAS-C12). The pilot-plant was operated at influent LAS-C12 concentrations between 2 and 12 mg/l and at sludge retention times of 10 and 27

  20. Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes (United States)

    Hibbs, Michael; Fujimoto, Cy H.; Norman, Kirsten; Hickner, Michael A.


    An epoxy-crosslinked sulfonated poly(phenylene) copolymer composition used as proton exchange membranes, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cell, in electrode casting solutions and electrodes, and in sulfur dioxide electrolyzers. These improved membranes are tougher, have higher temperature capability, and lower SO.sub.2 crossover rates.

  1. Aligned electrospun nanofibers as proton conductive channels through thickness of sulfonated poly (phthalazinone ether sulfone ketone) proton exchange membranes (United States)

    Gong, Xue; He, Gaohong; Wu, Yao; Zhang, Shikai; Chen, Bo; Dai, Yan; Wu, Xuemei


    A novel approach is proposed to fabricate sulfonated poly (phthalazinone ether sulfone ketone) (SPPESK) proton exchange membranes with ordered through-plane electrospinning nanofibers, which provide nano-scale through-plane proton conductive channels along the thickness direction of the membranes, aiming to satisfy the challenging requirement of high through-plane proton conductivity in fuel cell operations. Induced by electrostatic attraction of strong electric field, the negatively charged sulfonic acid groups tend to aggregate towards surface of the electrospun fibers, which is evidenced by TEM and SAXS and further induces aggregation of the sulfonic acid groups in the SPPESK inferfiber voids filler along the surface of the nanofibers. The aligned electrospun nanofibers carries long-range ionic clusters along the thickness direction of the membrane and results in much higher total through-plane conductivity in the thickness aligned electrospun membranes, nearly twice as much as that of the cast SPPESK membrane. With smooth treatment, the thickness aligned electrospun SPPESK membranes exhibit higher single cell power density and tensile strength as compared with Nafion 115 (around 1.2 and 1.5 folds, respectively). Such a design of thickness aligned nano-size proton conductive channels provide feasibility for high performance non-fluorinated PEMs in fuel cell applications.

  2. Hypernatremia in a patient treated with sodium polystyrene sulfonate

    Directory of Open Access Journals (Sweden)

    Manish Nepal


    Full Text Available Manish Nepal, Ion Dan Bucaloiu, Evan R NorfolkGeisinger Medical Center, Department of Nephrology, Danville, PA, USAAbstract: Severe hyperkalemia requires urgent medical attention and correction in order to prevent arrhythmic complications. Sodium polystyrene sulfonate (SPS is a cation exchange resin commonly used in the management of hyperkalemia. A recent review raised concerns regarding its effectiveness and potential adverse effects. Hypernatremia in adults in the setting of sodium polystyrene sulfonate therapy has not been described in the literature. We report the case of a woman who developed hypernatremia in the setting of excessive SPS administration and hope to increase awareness among clinicians regarding this potential side effect of SPS therapy.Keywords: SPS, hyperkalemia 

  3. Mortar modified with sulfonated polystyrene produced from waste plastic cups

    Directory of Open Access Journals (Sweden)

    L. A. C. MOTTA

    Full Text Available Abstract In this work, we studied the addition of sulfonated polystyrene produced from waste plastic cups as an admixture for mortars. Mortars were analyzed with polystyrene content of 0.0; 0.2; 0.6; 1.0 and 1.4% in relation to the cement mass. The influence of polystyrene on the mortars' properties was evaluated by the consistency index, water retention, water absorption, porosity, elasticity modulus, compressive strength, flexural strength, bond tensile strength and microscopy. The increase in the sulfonated polystyrene content decreased the elasticity modulus of the mortar and, despite higher porosity, there was a reduction of water absorption by capillarity. In relation to mortar without admixture, the modified mortar showed an increase in water retention and consistency index, and a large increase in flexural strength and bond tensile strength. The significant increase of bond tensile strength (214% with admixture 1% highlights the potential of the produced material as an adhesive mortar.

  4. Proton conductive membranes based on doped sulfonated polytriazole

    Energy Technology Data Exchange (ETDEWEB)

    Boaventura, M.; Brandao, L.; Mendes, A. [Laboratorio de Engenharia de Processos, Ambiente e Energia (LEPAE), Faculdade de Engenharia da Universidade do Porto, Rua Roberto Frias, 4200-465 Porto (Portugal); Ponce, M.L.; Nunes, S.P. [GKSS Research Centre Geesthacht GmbH, Max Planck Str. 1, D-21502, Geesthacht (Germany)


    This work reports the preparation and characterization of proton conducting sulfonated polytriazole membranes doped with three different agents: 1H-benzimidazole-2-sulfonic acid, benzimidazole and phosphoric acid. The modified membranes were characterized by scanning electron microscopy (SEM), infrared spectra, thermogravimetric analysis (TGA), dynamical mechanical thermal analysis (DMTA) and electrochemical impedance spectroscopy (EIS). The addition of doping agents resulted in a decrease of the glass transition temperature. For membranes doped with 85 wt.% phosphoric acid solution proton conductivity increased up to 2.10{sup -3} S cm{sup -1} at 120 C and at 5% relative humidity. The performance of the phosphoric acid doped membranes was evaluated in a fuel cell set-up at 120 C and 2.5% relative humidity. (author)

  5. Nucleophilic tetrafluoroethylation of carbonyl compounds with fluorinated sulfones

    Czech Academy of Sciences Publication Activity Database

    Václavík, Jiří; Chernykh, Yana; Jurásek, Bronislav; Beier, Petr


    Roč. 169, Jan (2015), s. 24-31 ISSN 0022-1139 R&D Projects: GA ČR GAP207/11/0421 Grant - others:GA MŠk(CZ) ED3.2.00/08.0144; GA MŠk(CZ) LM2010005 Institutional support: RVO:61388963 Keywords : fluorine * tetrafluoroethylation * sulfones * nucleophilic addition * carbonyl compounds Subject RIV: CC - Organic Chemistry Impact factor: 2.213, year: 2015

  6. Monovinyl sulfone β-cyclodextrin. A flexible drug carrier system. (United States)

    del Castillo, Teresa; Marales-Sanfrutos, Julia; Santoyo-González, Francisco; Magez, Stefan; Lopez-Jaramillo, F Javier; Garcia-Salcedo, Jose A


    Cyclodextrins have been conjugated to target various receptors and have also been functionalized with carbohydrates for targeting specific organs. However, this approach is based on a rigid design that implies the ad hoc synthesis of each cyclodextrin-targeting agent conjugate. We hypothesized that: 1)a modular design that decouples the carrier function from the targeting function leads to a flexible system, 2) combining the reactivity of the vinyl sulfone group toward biomolecules that act as targeting agents with the ability of cyclodextrin to form complexes with a wide range of drugs may yield a versatile system that allows the targeting of different organs with different drugs, and 3) the higher reactivity of histidine residues toward the vinyl sulfone group can be exploited to couple the cyclodextrin to the targeting system with a degree of regioselectivity. As a proof of concept, we synthesized a monovinyl sulfone β-cyclodextrin (module responsible for the payload), which, after coupling to recombinant antibody fragments raised against Trypanosoma brucei (module responsible for targeting) and loading with nitrofurazone (module responsible for therapeutic action) resulted in an effective delivery system that targets the surface of the parasites and shows trypanocidal activity. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis of proton conducting sulfonated and phosphonated polybenzimidazoles

    Energy Technology Data Exchange (ETDEWEB)

    Ng, F.; Peron, J.; Salunke, A.; Jones, D.J.; Roziere, J. [Montpellier Univ., Montpellier (France). Lab. des Agregats Moleculaires et Materiaux Inorganiques


    A study was conducted in which a new flexible polybenzimidazoles (PBI) was synthesized with a proton conductivity higher than 10-3 S/cm at room temperature, in the absence of any unbound acid. Polybenzimidazoles are particularly robust polymers that are stable under various chemical and thermal environments. It is difficult to achieve direct sulfonation in solution of commercially available PBI, although alternative types of PBI with different solubility properties may be modified in this way. Reaction at high temperature of sulfuric acid-doped PBI membranes results in cross-linked and poorly conducting systems. Although acid-doped PBI membranes have high conductivity, acid loss occurs at temperature and load cycling in an operating fuel cell. Alternative approaches have been suggested, such as direct sulfonation and polycondensation reaction involving building blocks functionalized with protogenic groups that lead to new functionalized polybenzimidazoles with suitable properties for fuel cell application. The membrane microstructure can be modified by controlling the position, number and distribution of the sulfonic (phosphonic) acid groups along the backbone. This also affects membrane swelling and conductivity. This study also investigated the influence of the degree of protogenic group functionalization of polymer and membrane properties such as Tg, film forming properties, membrane water uptake and conductivity, and surface hydrophobic/philic properties. It was concluded that the polymer's conductivity depends on the ion exchange capacity and on the nature of the component diacids that give flexibility to the functionalized polybenzimidazole chains.

  8. Electric current-producing device having sulfone-based electrolyte (United States)

    Angell, Charles Austen; Sun, Xiao-Guang


    Electrolytic solvents and applications of such solvents including electric current-producing devices. For example, a solvent can include a sulfone compound of R1--SO2--R2, with R1 being an alkyl group and R2 a partially oxygenated alkyl group, to exhibit high chemical and thermal stability and high oxidation resistance. For another example, a battery can include, between an anode and a cathode, an electrolyte which includes ionic electrolyte salts and a non-aqueous electrolyte solvent which includes a non-symmetrical, non-cyclic sulfone. The sulfone has a formula of R1--SO2--R2, wherein R1 is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms, and R2 is a linear or branched or partially or fully fluorinated linear or branched oxygen containing alkyl group having 1 to 7 carbon atoms. The electrolyte can include an electrolyte co-solvent and an electrolyte additive for protective layer formation.

  9. NMR studies of sedimentary tetrapyrroles

    Energy Technology Data Exchange (ETDEWEB)

    Keely, B.J.; Maxwell, J.R. (Univ. of Bristol (England))

    Structural assignments of sedimentary biological markers rely mostly on the use of GC and GC-MS techniques, involving both chromatographic and mass spectral comparisons with synthetic standards in addition to de facto mass spectral interpretation. Difficulties experienced in the analysis of sedimentary porphyrins by GC-MS (which until very recently required derivatization), and the desire to understand the origins and geochemical transformations of these components and their precursors, have led to more extensive structural investigations than usually accorded to other classes of biological marker. This paper briefly reviews recent developments in {sup 1}H NMR studies of chlorins and porphyrins of sedimentary origin, with particular reference to correlated spectroscopy (COSY), which allows elucidation of spin-coupled systems.

  10. Sulfonation and characterization of styrene-indene copolymers for the development of proton conducting polymer membranes

    Directory of Open Access Journals (Sweden)

    Cristiane M. Becker


    Full Text Available The aim of this work is to obtain polymer precursors based on styrene copolymers with distinct degrees of sulfonation, as an alternative material for fuel cell membranes. Acetyl sulfate was used to carry out the sulfonation and the performance of the polyelectrolyte was evaluated based on the content of acid polar groups incorporated into the macromolecular chain. Polymeric films were produced by blending the sulfonated styrene-indene copolymer with poly(vinylidene fluoride. The degree of sulfonation of the polymer was strongly affected by the sulfonation reaction parameters, with a direct impact on the ionic exchange capacity and the ionic conductivity of the sulfonated polymers and the membranes obtained from them. The films produced with the blends showed more suitable mechanical properties, although the conductivity of the membranes was still lower than that of commercially available membranes used in fuel cells.

  11. Two-step sulfonation process for the conversion of polymer fibers to carbon fibers

    Energy Technology Data Exchange (ETDEWEB)

    Barton, Bryan E.; Patton, Jasson T.; Hukkanen, Eric J.; Bernius, Mark T.


    Disclosed herein are processes for preparing carbon fibers, comprising: sulfonating a polymer fiber with a sulfonating agent that is fuming sulfuric acid, sulfuric acid, chlorosulfonic acid, or a combination thereof; treating the sulfonated polymer with a heated solvent, wherein the temperature of the heated solvent is at least C.; and carbonizing the resulting product by heating it to a temperature of C. Carbon fibers prepared according to these methods are also disclosed herein.

  12. 3?-Daidzein sulfonate sodium improves mitochondrial functions after cerebral ischemia/reperfusion injury


    Wa Yuan; Qin Chen; Jing Zeng; Hai Xiao; Zhi-hua Huang; Xiao Li; Qiong Lei


    3′-Daidzein sulfonate sodium is a new synthetic water-soluble compound derived from daidzein (an active ingredient of the kudzu vine root). It has been shown to have a protective effect on cerebral ischemia/reperfusion injury in rats. We plan to study the mechanism of its protective effect. 3′-Daidzein sulfonate sodium was injected in rats after cerebral ischemia/reperfusion injury. Results showed that 3′-daidzein sulfonate sodium significantly reduced mitochondrial swelling, significantly el...

  13. Sulfonated phenolic material and its use in post primary oil recovery

    Energy Technology Data Exchange (ETDEWEB)

    Pardue, J. E.; Stapp, P. R.


    Sulfonated phenolic compounds as well as sulfomethylated phenolic compounds, surfactant systems containing such compound and the use of such surfactant systems in post primary oil recovery are disclosed.

  14. New Fluorinated and Sulfonated Block Copolymers Final Report (United States)


    fossil fuels, are a pressing need in the world we live in today. One such promising alternative is a fuel cell. Fuel Cells are typically classified...1H NMR . Some samples were neutralized to the cesium salt form , and the balance left in the acid form. The cesium form facilitates contrast in the x...characteristics: Mw =31,200 ,PDI=1.05, 27mol% PS. The fluorinated samples cast into membranes were sulfonated to 23,28 and 50 mol%, as determined by 1H NMR

  15. Toltrazuril sulfone sodium salt: synthesis, analytical detection, and pharmacokinetics in the horse. (United States)

    Dirikolu, L; Karpiesiuk, W; Lehner, A F; Tobin, T


    Toltrazuril sulfone (ponazuril) is a triazine-based antiprotozoal agent with clinical application in the treatment of equine protozoal myeloencephalomyelitis (EPM). In this study, we synthesized and determined the bioavailability of a sodium salt formulation of toltrazuril sulfone that can be used for the treatment and prophylaxis of EPM in horses. Toltrazuril sulfone sodium salt was rapidly absorbed, with a mean peak plasma concentration of 2400 ± 169 (SEM) ng/mL occurring at 8 h after oral-mucosal dosing and was about 56% bioavailable compared with the i.v. administration of toltrazuril sulfone in dimethylsulfoxide (DMSO). The relative bioavailability of toltrazuril sulfone suspended in water compared with toltrazuril sulfone sodium salt was 46%, indicating approximately 54% less oral bioavailability of this compound suspended in water. In this study, we also investigated whether this salt formulation of toltrazuril sulfone can be used as a feed additive formulation without significant reduction in oral bioavailability. Our results indicated that toltrazuril sulfone sodium salt is relatively well absorbed when administered with feed with a mean oral bioavailability of 52%. Based on these data, repeated oral administration of toltrazuril sulfone sodium salt with or without feed will yield effective plasma and cerebrospinal fluid (CSF) concentrations of toltrazuril sulfone for the treatment and prophylaxis of EPM and other protozoal diseases of horses and other species. As such, toltrazuril sulfone sodium salt has the potential to be used as feed additive formulations for both the treatment and prophylaxis of EPM and various other apicomplexan diseases. © 2011 Blackwell Publishing Ltd.

  16. Polyaniline synthesized with functionalized sulfonic acids for blends manufacture

    Directory of Open Access Journals (Sweden)

    Mara Joelma Raupp Cardoso


    Full Text Available Polyaniline (PAni, an electronic conductive polymer, has poor mechanical properties, such as low tensile, compressive and flexural strength that render PAni a non-ideal material to be processed for practical applications. Desired properties of polyaniline can be enhanced by mixing it with a polymer that has good mechanical properties. In this work, PAni was synthesised using functionalized sulfonic acids like camphorsulfonic acid (CSA and dodecilbenzene sulfonic acid (DBSA in order to promote PAni doping and improve its solubility, making possible conductive blends manufacture. The different forms of PAni were characterized by infra-red spectroscopy, thermal analysis, scanning electron microscopy and conductivity measurements. A conductive blend composed of PAni/DBSA and lower density polyethylene (LDPE was obtained via solubilization method and its thermal, morphological and electrical properties were investigated. Concentrations as low as 5 wt. (% of PAni was able to lead to electrical conductivities of PAni/LDPE blends in the range of 10-3, showing great potential to be used in antistatic packing, electromagnetic shielding, anti-corrosion shielding or as a semiconductor.

  17. Nanostructured membranes and electrodes with sulfonic acid functionalized carbon nanotubes

    KAUST Repository

    Tripathi, Bijay Prakash


    Herein we report the covalent functionalization of multiwall carbon nanotubes by grafting sulfanilic acid and their dispersion into sulfonated poly(ether ether ketone). The nanocomposites were explored as an option for tuning the proton and electron conductivity, swelling, water and alcohol permeability aiming at nanostructured membranes and electrodes for application in alcohol or hydrogen fuel cells and other electrochemical devices. The nanocomposites were extensively characterized, by studying their physicochemical and electrochemical properties. They were processed as self-supporting films with high mechanical stability, proton conductivity of 4.47 × 10 -2 S cm-1 at 30 °C and 16.8 × 10-2 S cm-1 at 80 °C and 100% humidity level, electron conductivity much higher than for the plain polymer. The methanol permeability could be reduced to 1/20, keeping water permeability at reasonable values. The ratio of bound water also increases with increasing content of sulfonated filler, helping in keeping water in the polymer in conditions of low external humidity level. © 2010 Elsevier B.V.

  18. Synthesis and Structure-Property Relationships of Poly(sulfone)s for Anion Exchange Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Yan, JL; Moore, HD; Hibbs, MR; Hickner, MA


    Membranes based on cationic polymers that conduct anions are important for enabling alkaline membrane fuel cells and other solid-state electrochemical devices that operate at high pH. Anion exchange membranes with poly(arylene ether sulfone) backbones are demonstrated by two routes: chloromethylation of commercially available poly(sulfone)s or radical bromination of benzylmethyl moieties in poly(sulfone)s containing tetramethylbisphenol A monomer residues. Polymers with tethered trimethylbenzyl ammonium moieties resulted from conversion of the halomethyl groups by quaternization with trimethyl amine. The water uptake of the chloromethylated polymers was dependent on the type of poly(sulfone) backbone for a given IEC. Bisphenol A-based Udel (R) poly(sulfone) membranes swelled in water to a large extent while membranes from biphenol-based Radel (R) poly(sulfone), a stiffer backbone than Udel, only showed moderate water uptake. The water uptake of cationic poly(sulfone)s was further reduced by synthesizing tetramethylbisphenol A and 4,4-biphenol-containing poly(sulfone) copolymers where the ionic groups were clustered on the tetramethylbisphenol A residues. The conductivity of all samples scaled with the bulk water uptake. The hydration number of the membranes could be increased by casting membranes from the ionic form polymers versus converting the halomethyl form cast polymers to ionic form in the solid state. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1790-1798, 2013

  19. Colonic necrosis due to calcium polystyrene sulfonate (Kalimate not suspended in sorbitol

    Directory of Open Access Journals (Sweden)

    María Dolores Castillo-Cejas


    Full Text Available Cation-exchange resins are used in the management of hyperkalemia, particularly in patients with end-stage renal disease. These resins were associated with gastrointestinal tract lesions, especially sodium polystyrene sulfonate (Kayexalate mixed with sorbitol. We present a case of colonic necrosis after the administration of calcium polystyrene sulfonate (Kalimate not suspended in sorbitol.

  20. Ionomeric membranes based on partially sulfonated poly(styrene) : synthesis, proton conduction and methanol permeation

    NARCIS (Netherlands)

    Picchioni, F.; Tricoli, V.; Carretta, N.


    Homogeneuosly sulfonated poly(styrene) (SPS) was prepared with various concentration of sulfonic acid groups in the base polymer. Membranes cast from these materials were investigated in relation to proton conductivity and methanol permeability in the temperature range from 20°C to 60°C. It was

  1. 40 CFR 721.10045 - Diazotized substituted heteromonocycle coupled with naphthalene sulfonic acid derivative, nickel... (United States)


    ... coupled with naphthalene sulfonic acid derivative, nickel complex, alkaline salt (generic). 721.10045... derivative, nickel complex, alkaline salt (generic). (a) Chemical substance and significant new uses subject... heteromonocycle coupled with naphthalene sulfonic acid derivative, nickel complex, alkaline salt (PMN P-02-737) is...

  2. Influence of some technological parameters on the formation of dimethyl sulfide, 2-mercaptoethanol, methionol, and dimethyl sulfone in port wines. (United States)

    Silva Ferreira, António César; Rodrigues, Paula; Hogg, Timothy; Guedes De Pinho, Paula


    Volatile sulfur compounds of 15 young port wines and 12 old port wines were determined. As there is a great difference in the pool of sulfur compounds between the two groups of wines, an experimental protocol was performed to determine which technological parameter (dissolved O(2), free SO(2) levels, pH, and time/temperature) was related with the formation/consumption of these compounds. Four sulfur compounds were selected for this purpose: dimethyl sulfide, 2-mercaptoethanol, dimethyl sulfone, and methionol. The synergistic effects of increasing temperature and O(2) at lower pH had the largest impact. Dimethyl sulfide was formed during the experimental period in the presence of O(2). Dimethyl sulfone had the same behavior. Methionol decreased significantly in the presence of O(2), but no methional was formed. 2-Mercaptoethanol, considered to be an important "off-flavor" in dry wines, also decreased during the experimental period (54 days) in the presence of O(2), and the respective disulfide was formed. These results corroborate the fact that old port wine (barrel aged) never develops "off-flavors" associated with the presence of methionol (cauliflower), 2-mercaptoethanol (rubber/burnt), or methional (cooked potato). In fact, temperature and oxygen are the major factors in the consumption of these molecules. However, some notes of "quince" and "metallic" can appear during port wine aging, and these can be associated with the presence of dimethyl sulfide.

  3. Radiation-chemical synthesis of polypropylene fabrics with sulfonic acid functional groups

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Hyun Kug; Park, Jung Soo; Han, Do Hung, E-mail:; Bondar, Iuliia, E-mail:


    A sorption-active material carrying sulfonic acid groups was synthesized by the radiation-induced graft polymerization of styrene monomer onto the surface of non-woven polypropylene fabric, followed by sulfonation of the grafted polystyrene chains. The effect of the main experimental parameters (absorbed dose, monomer concentration, reaction time) on the styrene degree of grafting was investigated. The sulfonation process with 5% chlorosulfonic acid at room temperature was investigated in detail and the optimal sulfonation conditions for the samples with a medium degree of grafting (70-140%) were determined. Densities of 3.5-5 meq/g were obtained by applying those sorption-active PP fabrics with a sulfonic acid group.

  4. New determination method for sulfonation degree of phthalic anhydride by RP-HPLC. (United States)

    Zhu, Lijun; Song, Lechun; Liu, Bin; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong


    A novel method was developed to monitor the reaction process and evaluate the sulfonation level in the sulfonation of phthalic anhydride by reversed-phase high-performance liquid chromatography (RP-HPLC). The product peak was identified in chromatograms through product analysis and by comparing its retention time with that of standard compounds. By comparing the hydrolysis and alcoholysis methods, optimized pretreatment of the sample was found for RP-HPLC. Based on the determined percentages of phthalic anhydride and sulfonated phthalic anhydride in the mixture, the degree of sulfonation was calculated. When the sulfonation degree of phthalic anhydride was in the range of 2.8-71%, the recovery of 97-104% was achieved, and the procedure was rapid and accurate.

  5. Enhancing the phase segregation and connectivity of hydrophilic channels by blending highly sulfonated graft copolymers with fluorous homopolymers

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller; Ching-Ching Yang, Ami; Jankova Atanasova, Katja


    The influence of tuning the ionic content of membranes by blending, as opposed to varying the degree of sulfonation, is evaluated. Membranes of fully sulfonated poly(vinylidene fluoride-co-chlorotrifluoroethylene)-g-poly(styrene sulfonic acid) blended with PVDF were prepared and investigated...

  6. Complexing activity and excretion of 2,3-dimercapto-1-propane sulfonate in rat kidney

    Energy Technology Data Exchange (ETDEWEB)

    Klotzbach, J.M.; Diamond, G.L.


    The renal handling of the heavy metal complexing agent, 2,3-dimercapto-1-propane sulfonate (DMPS), was examined in the isolated perfused rat kidney (IPRK). Net tubular secretion of DMPS was saturable and blocked by p-aminohippuric acid (PAH) and probenecid (PRB), indicating involvement of carrier-mediated transport in the excretion of DMPS. DMPS was oxidized to a disulfide form (DMPSS) in perfusate and reduced to a sulfhydryl form (DMPSH) in kidney. In kidneys isolated from rats pretreated with HgCl/sub 2/, DMPS produced a dose-dependent decrease in retention of inorganic mercury, an increase in urinary excretion of mercury, and an increase in the amount of mercury transferred from kidney into venous perfusate. At a maximally effective dose, 40% of the renal mercury content was excreted in urine during 30 min of perfusion. Urinary excretion of mercury induced by DMPS was completely blocked by concentrations of PRB that blocked tubular secretion of DMPS and decreased uptake of DMPS in kidney. Thus tubular secretion of DMPS and reduction of DMPSS to DMPSH are important in the renal handling of DMPS and may contribute to the activity of DMPS as a complexing agent for renal mercury.

  7. Poly (ether imide sulfone) membranes from solutions in ionic liquids

    KAUST Repository

    Kim, Dooli


    A membrane manufacture method based on non-volatile solvents and a high performance polymer, poly (ether imide sulfone) (EXTEM™), is proposed, as greener alternative to currently industrial process. We dissolved EXTEM™ in pure ionic liquids: 1-ethyl-3-methylimidalzolium thiocyanate ([EMIM]SCN), 1-butyl-3-methylimidalzolium thiocyanate ([BMIM]SCN), and 1-ethyl-3-methylimidalzolium acetate ([EMIM]OAc). The following polymer solution parameters were evaluated to optimize the manufacture: Gibbs free energy of mixing (G), intrinsic viscosity ([]) and hydrodynamic diameter. Membranes with sponge-like structure and narrow pore size distribution were obtained from solutions in [EMIM]SCN. They were tested for separation of proteins and deoxyribonucleic acids (DNA). Due to the polymer stability, we foresee that applications in more demanding chemical separations would be possible. [EMIM]SCN was 96 % purified and recovered after the membrane fabrication, contributing to the sustainability of the whole manufacturing process.

  8. Transesterification of soybean oil over sulfonic acid functionalised polymeric membranes

    Energy Technology Data Exchange (ETDEWEB)

    Guerreiro, L.; Castanheiro, J.E.; Fonseca, I.M.; Ramos, A.M.; Vital, J. [REQUIMTE, CQFB, Departamento de Quimica, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Martin-Aranda, R.M. [Departamento de Quimica Inorganica y Quimica Tecnica, UNED, Paseo Senda del Rey, 9, 28040 Madrid (Spain)


    The transesterification of soybean oil with methanol was studied using solid acid catalysts, at 60{sup o}C and atmospheric pressure. Nafion membranes, ion-exchange resins and poly(vinyl alcohol) membranes containing sulfonic groups were used as catalysts for the transesterification reaction studied. The reactions were carried out in a three-necked reactor using all the catalysts in the form of pellets. Nafion and PVA membranes in the form of film were also used in a membrane reactor. The PVA membrane modified with sulfossucinic acid was, in both cases, the most active catalyst. The concentration profiles obtained with the catalysts in the form of pellets exhibited an initial induction period, which disappears when the reaction is performed in the membrane reactor. (author)

  9. Layer-by-layer films of chitosan, poly(vinyl sulfonic acid), and platinum for methanol electrooxidation and oxygen electroreduction (United States)

    Cogo, Luciano C.; Batisti, Marcos V.; Pereira-da-Silva, Marcelo A.; Oliveira, Osvaldo N.; Nart, Francisco C.; Huguenin, Fritz

    We describe an approach for manipulation of biodegradable chitosan and poly(vinyl sulfonic acid) (PVS) in layer-by-layer (LBL) film adsorbed onto gold via ionic attraction. H 2PtCl 6 was deposited onto the LBL film, with chitosan/PVS layers serving as templates to yield metallic platinum. In electrochemical experiments this LBL film exhibited electrochemical stability, low permeability to methanol and conduction/diffusion of proton to maintain the electrolytic connection. The Pt/chitosan/PVS electrode also displayed electroreduction of molecular oxygen. With these features, this Pt/chitosan/PVS film may be used between the catalyst layer and the proton exchange membrane (PEM) in direct methanol fuel cells (DMFC) and biofuel cells.

  10. Radiation-induced crosslinking of poly(styrene–butadiene–styrene) block copolymers and their sulfonation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sun-Young [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Song, Ju-Myung; Sohn, Joon-Yong [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Shul, Yong-Gun [Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Shin, Junhwa, E-mail: [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)


    Highlights: • The c-SBS films were prepared using a gamma ray or electron beam. • The crosslinking degree of the c-SBS films were increased with the irradiation dose. • The prepared c-SBS films were sulfonated with various concentration of CSA. • The sulfonation of the c-SBS film is largely dependent on the concentration of CSA. • The sulfonation process is progressed from the surface to the inner part of c-SBS film. -- Abstract: Several crosslinked poly(styrene–butadiene–styrene) (c-SBS) block copolymer films were prepared using a gamma ray or electron beam with various irradiation doses and the prepared c-SBS film was then subjected to sulfonation using a chlorosulfonic acid (CSA) solution to introduce a sulfonic acid group. To estimate the degree of crosslinking, the gel fractions and FT-IR spectra of the c-SBS films were used and the results indicate that the degree of crosslinking is increased with an increase in the radiation dose. The surface morphology and mechanical property of the c-SBS films were observed using SEM and UTM instruments, respectively. The sulfonated c-SBS films were investigated by measuring the ion exchange capacity (IEC) and by observing the cross-sectional distribution patterns of sulfonic acid group using an SEM-EDX instrument. The IEC and SEM-EDX studies indicate that the sulfonated c-SBS membranes can be successfully prepared through the radiation crosslinking of the SBS film and the subsequent sulfonation with a diluted CSA solution.

  11. Raman and Luminescent Spectra of Sulfonated Zn Phthalocyanine Enhanced by Gold Nanoparticles (United States)

    Kavelin, V.; Fesenko, O.; Dubyna, H.; Vidal, C.; Klar, T. A.; Hrelescu, C.; Dolgov, L.


    Sulfonated Zn phthalocyanine, as a prospective photosensitizer in the photodynamic therapy of tumors, is investigated by means of Raman, infrared, and fluorescence spectroscopies. Conventional and surface-enhanced spectra from this photosensitizer are obtained and compared. Gold nano-islands attached to silica cores (Au-SiO2) are proposed as nanostructures providing plasmonically enhanced signals. Pronounced enhancement of Raman and infrared spectral bands from sulfonated Zn phthalocyanine allows their more convenient assignment with vibrational modes of sulfonated Zn phthalocyanine. In comparison to Raman and IR, the fluorescence is less enhanced by Au-SiO2 particles.

  12. Derivatives of phenyl tribromomethyl sulfone as novel compounds with potential pesticidal activity

    Directory of Open Access Journals (Sweden)

    Krzysztof M. Borys


    Full Text Available A halogenmethylsulfonyl moiety is incorporated in numerous active herbicides and fungicides. The synthesis of tribromomethyl phenyl sulfone derivatives as novel potential pesticides is reported. The title sulfone was obtained by following three different synthetic routes, starting from 4-chlorothiophenol or 4-halogenphenyl methyl sulfone. Products of its subsequent nitration were subjected to the SNAr reactions with ammonia, amines, hydrazines and phenolates to give 2-nitroaniline, 2-nitrophenylhydrazine and diphenyl ether derivatives. Reduction of the nitro group of 4-tribromomethylsulfonyl-2-nitroaniline yielded the corresponding o-phenylenediamine substrate for preparation of structurally varied benzimidazoles.

  13. Sulfonated copolyimide membranes derived from a novel diamine monomer with pendant benzimidazole groups for fuel cells

    DEFF Research Database (Denmark)

    Li, Wei; Guo, Xiaoxia; Aili, David


    Sulfonated polyimides are among the most interesting proton exchange membrane materials with high proton conductivity and good mechanical characteristics. As a major challenge the hydrolytic instability of the polymer backbone is addressed by introducing basic moieties in the polymer main chain....... A series of sulfonated copolyimides (SPI) are prepared via random copolymerizatio of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) with a new diamine monomer with pendant benzimidazole groups, 2,2'-bis(4-(1H-benzo[d]imidazol-2-yl)phenoxy)benzidine (BIPOB), and a sulfonated diamine monomer 4,4'-bis...

  14. Degradation and contamination of perfluorinated sulfonic acid membrane due to swelling-dehydration cycles

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma; Morgen, Per; Skou, Eivind Morten

    Formation of sulfonic anhydride S-O-S (from the condensation of sulfonic acids) was known one of the important degradation mechanisms [i] for Nafion membrane under hydrothermal aging condition, which is especially critical for hydrogen fuel cells. Similar mechanism would also have be desirable...... to the membrane degradation in direct methanol fuel cells (DMFCs), where liquid water has direct contact with the electrolyte. An ex-situ experiment was established with swelling-dehydration cycles on the membrane. However, formation of sulfonic anhydride was not detected during the entire treatment; instead...

  15. Use of an automatic control system for the production of sulfonate additives

    Energy Technology Data Exchange (ETDEWEB)

    Barnaev, V.A.; Cherednichenko, G.I.; Gordash, Iu.T.; Manoilo, A.M.


    On the bases of industrial means for local information control systems, a system for the automatic control of industrial operations of periodic processes of volumetric decomposition of ammonium sulfonates with lime and the preparation of reagent for methanol carbonation, taking place at an improved stage of the production of sulfonate additives for motor oils in devices having periodic functioning has been worked out. The technical process, the structure and the industrial data on the control system are briefly described. A ''Carboncycle'' system, which makes it possible to intensify the production of sulfonate additives, has been developed.

  16. Effect of sulfonated steroids on steroidogenic cytochrome P450-dependent steroid hydroxylases. (United States)

    Neunzig, J; Bernhardt, R


    In the last decades, sulfonated steroids evolved from inactive metabolites intended for excretion to highly relevant compounds involved in many physiological processes. Investigations of the impact of sulfonated steroids on the steroid hormone biosynthesis revealed that, on the one hand, these can serve as substrate for steroidogenic cytochromes P450 and, on the other hand, these are able to influence the catalytic properties of these enzymes. In this review the relevance of sulfonated steroids for the steroid hormone biosynthesis will be discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Mixed Membrane Matrices Based on Nafion/UiO-66/SO3H-UiO-66 Nano-MOFs: Revealing the Effect of Crystal Size, Sulfonation, and Filler Loading on the Mechanical and Conductivity Properties. (United States)

    Donnadio, Anna; Narducci, Riccardo; Casciola, Mario; Marmottini, Fabio; D'Amato, Roberto; Jazestani, Mehdi; Chiniforoshan, Hossein; Costantino, Ferdinando


    Mixed membrane matrices (MMMs) made up with Nafion and nanocrystals of zirconium metal-organic framework (MOF) UiO-66 or the analogous sulfonated SO3H-UiO-66 were prepared by varying the filler loading and the size of the crystals. The combined effects of size and loading, together with the presence of sulfonic groups covalently linked to the MOFs, were studied with regard to the conductivity and mechanical properties of the obtained composite matrices. A large screening of membranes was preliminarily made and, on the most promising samples, an accurate conductivity study at different relative humidities and temperatures was also carried out. The results showed that membranes containing large crystals (200 nm average size) in low amounts (around 2%) displayed the best results in terms of proton conductivity values, reaching values by 30% higher than those of pure Nafion, while leaving the mechanical properties substantially unchanged. On the contrary, MMMs containing MOFs of small size (20 nm average size) did not show any conductivity improvements if compared to pure Nafion membranes. The effect of MOF sulfonation was negligible at low filler loading whereas it became important at loading values around 10%. Finally, membranes with a high filler loading (up to 60 wt %) of sulfonated UiO-66 showed a slight reduction of conductivity in comparison with membranes loaded at 20% of nonsulfonated ones.

  18. Sulfonated Polyimide-Clay Thin Films for Energy Application. (United States)

    Ali, Farman; Saeed, Shaukat; Shah, Syed Sakhawat; Rahim, Fazal; Duclaux, Laurent; Levêque, Jean-Marc; Reinert, Laurence


    Sulfonated polyimides (SPIs) are considered as the promising alternatives to Nafion as membrane materials for the polymer electrolyte membrane (PEM). They generally exhibit high ionic conductivity, good mechanical properties, excellent thermal and chemical stabilities. The six-membered ring, naphthalenic anhydride-based SPIs, not only exhibit superior chemical and thermo-oxidative stabilities but are also more resistant to hydrolysis than their five-membered phthalic anhydride-based SPIs. The composites based on napthalenic polyimides are also significantly stable in high temperature environment and show better stability to hydrolysis. Incorporation of inorganic fillers into organic polymers has gained tremendous attention and these new materials are called organic-inorganic hybrids. Few patents related to the synthesis and performance PEM materials have been reviewed and cited. Keeping in view the importance of sulfonated polyimide based nanocomposites as potential membrane materials for PEM in fuel cell, we have synthesized SPIs clay based nanocomposite as potential membrane material. The objective of this work was to synthesize clay based SPIs thin films which could be used as membrane materials in PEM fuel cell for energy applications. Methods/Experimental: At the first step the nanometric sheets of vermiculite clay prepared via sonication was surface modified by grafting 3-APTES. Then the SPI was synthesized via one-step high temperature direct imidization method, which serve as a matrix material. The organo modified VMT was dispersed via sonication in the SPI matrix. Four different sets of organic-inorganic nanocomposite membranes thin films, having VMT contents in the range of 1 to 7 wt.% were prepared by casting, curing and acidification route. The synthesis of SPIs clay based thin films were carried out at three different steps and fully characterized. The synthesis of SPIs and SPIs clay based thin films were analyzed via different analytical techniques

  19. Proton-Conducting Sulfonated Ionomers by Chemical Modification and Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller

    (PSU), Udel, is chosen as backbone due to its mechanical and thermal properties. Sulfonic acid functionalized, dendronised side chains are attached by click chemistry in the study of hydrocarbon structures with highly flexible spacers. Various degrees of sulfonation (DS) are used in the perspectivation...... to a partially fluorinated system that is based on a poly(vinylidene fluoride) (PVDF)-containing backbone with fully sulfonated PS grafts. To counteract the dimensional change upon water contact that is a result of the increased IEC, the ionomer is blended with a high molecular weight PVDF, which contributes....... The blends are highly humidity sensitive, yet, despite lower absolute conductivities than Nafion, they display a reduced dependence on both humidity and temperature. Under fully humidified conditions the blends perform superior to fully sulfonated graft copolymer analogues. The combination of a high degree...

  20. Preparation of a Sulfonated Carbonaceous Material from Lignosulfonate and Its Usefulness as an Esterification Catalyst

    Directory of Open Access Journals (Sweden)

    Duckhee Lee


    Full Text Available Sulfonated carbonaceous material useful as a solid acid catalyst was prepared from lignosulfonate, a waste of the paper-making industry sulfite pulping process, and characterized by 13C-NMR, FT-IR, TGA, SEM and elemental analysis, etc. The sulfonic acid group density and total density of all acid groups in the sulfonated carbonaceous material was determined by titration to be 1.24 mmol/g and 5.90 mmol/g, respectively. Its catalytic activity in the esterification of cyclohexanecarboxylic acid with anhydrous ethanol was shown to be comparable to that of the ionic exchange resin Amberlyst-15, when they were used in the same amount. In the meantime, the sulfonic acid group was found to be leached out by 26%–29% after it was exposed to hot water (95 °C for 5 h. The catalytic usefulness of the prepared carbonaceous material was investigated by performing esterifications.

  1. Magnetite-supported sulfonic acid: a retrievable nanocatalyst for the Ritter reaction and multicomponent reactions (United States)

    Magnetite-sulfonic acid (NanocatFe-OSO3H), prepared by wet-impregnation method, serves as a magnetically retrievable sustainable catalyst for the Ritter reaction which can be used in several reaction cycles without any loss of activity.

  2. Preparation of a sulfonated carbonaceous material from lignosulfonate and its usefulness as an esterification catalyst. (United States)

    Lee, Duckhee


    Sulfonated carbonaceous material useful as a solid acid catalyst was prepared from lignosulfonate, a waste of the paper-making industry sulfite pulping process, and characterized by 13C-NMR, FT-IR, TGA, SEM and elemental analysis, etc. The sulfonic acid group density and total density of all acid groups in the sulfonated carbonaceous material was determined by titration to be 1.24 mmol/g and 5.90 mmol/g, respectively. Its catalytic activity in the esterification of cyclohexanecarboxylic acid with anhydrous ethanol was shown to be comparable to that of the ionic exchange resin Amberlyst-15, when they were used in the same amount. In the meantime, the sulfonic acid group was found to be leached out by 26%-29% after it was exposed to hot water (95 °C) for 5 h. The catalytic usefulness of the prepared carbonaceous material was investigated by performing esterifications.

  3. Destructive effect of polystyrene sulfonate on the structure of hemoproteins (United States)

    Saburova, E. A.; Basova, L. V.; Dybovskaya, Yu. N.; Sukhorukov, B. I.


    The mechanism of the destruction of horse heart hemoglobin (Hb) and spermwhale muscle myoglobin (Mb), two hem-containing proteins, by polystyrene sulfonate, an anionic polyelectrolyte, was studied. Measurements of the optical absorption of the prostetic group of the hem in the visible spectrum and of the circular dichroism in the absorption bands of the peptide groups and aromatic amino acid residues demonstrated that the compact structure of both proteins experiences destruction in the presence of polystyrene sulfonate (PSS) at PSS concentrations ten times as low as that of the protein (in wt %) and that the content of α-helix structure in Hb and Mb decreases from 81% in the native state to 43% in their complexes with PSS. The distinctions in the mechanisms of the destruction of Hb and Mb by PSS were found to be as follows: (1) in contrast to Mb, Hb forms insoluble complexes with PSS at low PSS concentrations and (2) Mb-PSS solutions at Mb-to-PSS ratios >1 were found to contain free hems (that absorb at 397 nm), a feature not observed for Hb; the kinetics of the destruction of both the proteins by the polyelectrolyte was demonstrated to be a two-stage process. The first stage of the destruction of Hb (τ ≈ 24.5 s) was found to be four times as slow as that of Mb (τ ≈ 6 s); the second (slow) stage had a halftime of ˜6 h for both the proteins under study. To determine the localization of regions at the protein molecule surface that are capable of binding polyelectrolyte molecules, the distribution of the electrostatic potential over the surface of the Hb and Mb molecules was numerically calculated with the help of the Poisson-Boltzmann equation at pH 6.2 and an ionic strength of 100 mmol/l. Based on experimental and theoretical studies of the mechanism of the interaction of the polyelectrolyte with the proteins, the structural-functional properties of proteins responsible for their destruction by the polyelectrolyte are determined.

  4. Urea-hydrogen peroxide prompted the selective and controlled oxidation of thioglycosides into sulfoxides and sulfones. (United States)

    Singh, Adesh Kumar; Tiwari, Varsha; Mishra, Kunj Bihari; Gupta, Surabhi; Kandasamy, Jeyakumar


    A practical method for the selective and controlled oxidation of thioglycosides to corresponding glycosyl sulfoxides and sulfones is reported using urea-hydrogen peroxide (UHP). A wide range of glycosyl sulfoxides are selectively achieved using 1.5 equiv of UHP at 60 °C while corresponding sulfones are achieved using 2.5 equiv of UHP at 80 °C in acetic acid. Remarkably, oxidation susceptible olefin functional groups were found to be stable during the oxidation of sulfide.

  5. Urea–hydrogen peroxide prompted the selective and controlled oxidation of thioglycosides into sulfoxides and sulfones


    Adesh Kumar Singh; Varsha Tiwari; Kunj Bihari Mishra; Surabhi Gupta; Jeyakumar Kandasamy


    A practical method for the selective and controlled oxidation of thioglycosides to corresponding glycosyl sulfoxides and sulfones is reported using urea–hydrogen peroxide (UHP). A wide range of glycosyl sulfoxides are selectively achieved using 1.5 equiv of UHP at 60 °C while corresponding sulfones are achieved using 2.5 equiv of UHP at 80 °C in acetic acid. Remarkably, oxidation susceptible olefin functional groups were found to be stable during the oxidation of sulfide.

  6. Urea?hydrogen peroxide prompted the selective and controlled oxidation of thioglycosides into sulfoxides and sulfones


    Singh, Adesh Kumar; Tiwari, Varsha; Mishra, Kunj Bihari; Gupta, Surabhi; Kandasamy, Jeyakumar


    A practical method for the selective and controlled oxidation of thioglycosides to corresponding glycosyl sulfoxides and sulfones is reported using urea?hydrogen peroxide (UHP). A wide range of glycosyl sulfoxides are selectively achieved using 1.5 equiv of UHP at 60 ?C while corresponding sulfones are achieved using 2.5 equiv of UHP at 80 ?C in acetic acid. Remarkably, oxidation susceptible olefin functional groups were found to be stable during the oxidation of sulfide.

  7. Water and Salt Transport Properties of Triptycene-Containing Sulfonated Polysulfone Materials for Desalination Membrane Applications. (United States)

    Luo, Hongxi; Aboki, Joseph; Ji, Yuanyuan; Guo, Ruilan; Geise, Geoffrey M


    A series of triptycene-containing sulfonated polysulfone (TRP-BP) materials was prepared via condensation polymerization, and the desalination membrane-relevant fundamental water and salt transport properties (i.e., sorption, diffusion, and permeability coefficients) of the polymers were characterized. Incorporating triptycene into sulfonated polysulfone increased the water content of the material compared to sulfonated polysulfone materials that do not contain triptycene. No significant difference in salt sorption was observed between TRP-BP membranes and other sulfonated polysulfone membranes, suggesting that the presence of triptycene in the polymer did not dramatically affect thermodynamic interactions between salt and the polymer. Both water and salt diffusion coefficients in the TRP-BP membranes were suppressed relative to other sulfonated polysulfone materials with comparable water content, and these phenomena may result from the influence of triptycene on polymer chain packing and/or free-volume distribution, which could increase the tortuosity of the transport pathways in the polymers. Enhanced water/salt diffusivity selectivity was observed for some of the TRP-BP membranes relative to those materials that did not contain triptycene, and correspondingly, incorporation of triptycene into sulfonated polysulfone resulted in an increase, particularly for acid counterion form TRP-BP materials, in water/salt permeability selectivity, which is favorable for desalination membrane applications.

  8. Chronic perfluorooctane sulfonate (PFOS) exposure induces hepatic steatosis in zebrafish

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Jiangfei; Lv, Suping; Nie, Shangfei; Liu, Jing; Tong, Shoufang; Kang, Ning; Xiao, Yanyan; Dong, Qiaoxiang [Zhejiang Provincial Key Laboratory for Technology and Application of Model Organisms (China); Institute of Environmental Safety and Human Health, Wenzhou Medical University, Wenzhou, 325035 (China); Huang, Changjiang, E-mail: [Zhejiang Provincial Key Laboratory for Technology and Application of Model Organisms (China); Institute of Environmental Safety and Human Health, Wenzhou Medical University, Wenzhou, 325035 (China); Yang, Dongren, E-mail: [Zhejiang Provincial Key Laboratory for Technology and Application of Model Organisms (China); Institute of Environmental Safety and Human Health, Wenzhou Medical University, Wenzhou, 325035 (China)


    Highlights: • PFOS chronic exposure induces sex-dependent hepatic steotosis in zebrafish. • PFOS interferes with β-oxidation, lipid synthesis, and lipid hepatic export process. • Zebrafish could be used as an alternative model for PFOS chronic toxicity screening. - Abstract: Perfluorooctane sulfonate (PFOS), one persistent organic pollutant, has been widely detected in the environment, wildlife and human. Currently few studies have documented the effects of chronic PFOS exposure on lipid metabolism, especially in aquatic organisms. The underlying mechanisms of hepatotoxicity induced by chronic PFOS exposure are still largely unknown. The present study defined the effects of chronic exposure to low level of PFOS on lipid metabolism using zebrafish as a model system. Our findings revealed a severe hepatic steatosis in the liver of males treated with 0.5 μM PFOS as evidenced by hepatosomatic index, histological assessment and liver lipid profiles. Quantitative PCR assay further indicated that PFOS significantly increase the transcriptional expression of nuclear receptors (nr1h3, rara, rxrgb, nr1l2) and the genes associated with fatty acid oxidation (acox1, acadm, cpt1a). In addition, chronic PFOS exposure significantly decreased liver ATP content and serum level of VLDL/LDL lipoprotein in males. Taken together, these findings suggest that chronic PFOS exposure induces hepatic steatosis in zebrafish via disturbing lipid biosynthesis, fatty acid β-oxidation and excretion of VLDL/LDL lipoprotein, and also demonstrate the validity of using zebrafish as an alternative model for PFOS chronic toxicity screening.

  9. Pre-treatment of biomasses using magnetised sulfonic acid catalysts

    Directory of Open Access Journals (Sweden)

    Yane Ansanay


    Full Text Available There is a significant interest in employing solid acid catalysts for pre-treatment of biomasses for subsequent hydrolysis into sugars, because solid acid catalysts facilitate reusability, high activity, and easier separation. Hence the present research investigated pretreatment of four lignocellulosic biomasses, namely Switchgrass (Panicum virgatum L ‘Alamo’, Gamagrass (Tripsacum dactyloides, Miscanthus (Miscanthus × giganteus and Triticale hay (Triticale hexaploide Lart. at 90°C for 2 h using three carbon-supported sulfonic acid catalysts. The catalysts were synthesized via impregnating p-Toluenesulfonic acid on carbon (regular and further impregnated with iron nitrate via two methods to obtain magnetic A and magnetic B catalysts. When tested as pre-treatment agents, a maximum total lignin reduction of 17.73±0.63% was observed for Triticale hay treated with magnetic A catalyst. Furthermore, maximum glucose yield after enzymatic hydrolysis was observed to be 203.47±5.09 mg g–1 (conversion of 65.07±1.63% from Switchgrass treated with magnetic A catalyst. When reusability of magnetised catalysts were tested, it was observed that magnetic A catalyst was consistent for Gamagrass, Miscanthus × Giganteus and Triticale hay, while magnetic B catalyst was found to maintain consistent yield for switchgrass feedstock. Our results suggested that magnetised solid acid catalyst could pre-treat various biomass stocks and also can potentially reduce the use of harsh chemicals and make bioenergy processes environment friendly.

  10. Thyroid disruption by perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). (United States)

    Coperchini, F; Awwad, O; Rotondi, M; Santini, F; Imbriani, M; Chiovato, L


    Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are two fluorinated compounds widely used in industry because of their useful chemical characteristics. They were identified as endocrine disruptors due to their ability to interfere with thyroid function. The resistance of PFOA and PFOS to environmental degradation, their bio-accumulation in food chains, and their long half-life raised concern in the scientific community, and several studies were performed with the aim to establish the real dangerousness of these compounds for the human health. The present review will focus on the effects of PFOA and PFOS on the thyroid gland taking into account in vitro experiments, animal studies, and human data. PFOS and PFOA reduce the circulating levels of thyroid hormones in diet-exposed animals, mainly by increasing their metabolic clearance rate. An accumulation of PFOS and PFOA was documented in thyroid cells, and a cytotoxic effect was observed after exposure to extremely high concentrations of these compounds. In environmentally exposed communities and in the general population, the most consistent effect of exposure to PFOA, and to a less extent to PFOS, is the occurrence of hypothyroidism. Women and children appear to be more at risk of developing mild thyroid failure. Pregnant women with circulating thyroid antibodies might be at risk of developing subclinical hypothyroidism, mainly when exposed at high doses of PFOS. The relative risks for thyroid cancer in people exposed to PFOA and PFOS were low and based on a few cases. Moreover, there was no consistent finding across all or even most studies.

  11. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination from textiles. (United States)

    Supreeyasunthorn, Phenpimuk; Boontanon, Suwanna K; Boontanon, Narin


    The goals of this study were to determine the concentrations of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in textiles and to determine PFOS and PFOA contamination in textile washing water. Quantification analysis was performed by high performance liquid chromatography coupled with tandem mass spectrometry. Analysis of 32 textile samples by methanol extraction revealed that the average concentrations of PFOS and PFOA were 0.18 µg m(-2) (0.02 to 0.61 µg m(-2)) and 2.74 µg m(-2) (0.31 to 14.14 µg m(-2)), respectively. Although the average concentration of PFOS found in textile samples was below European Union (EU) Commission regulations (textile samples had PFOA concentrations exceeding 1 µg m(-2). Thus, based on these results, the concentration of PFOA in products should also be regulated. Experiments on PFOS and PFOA leaching into washing water were conducted. The maximum concentrations of PFOS and PFOA were measured after the first washing; the concentrations gradually decreased with each subsequent washing. PFOS and PFOA migrated from textiles and were released into the environment, with disappearance percentages of 29.8% for PFOS and 99% for PFOA. The data presented in this study showed that textiles could be a significant direct and indirect source of PFOS and PFOA exposure for both humans and the environment.

  12. Modulating the solubility of zwitterionic poly((3- methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties


    Hildebrand, Viet; Laschewsky, André; Wischerhoff, Erik


    Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl)dimethylammonio) propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl) dimethylammonio)propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl)dimethylammonio)-butane-1-sulfonate (SBP) were synthesised and polymerised by reversible addition–fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematicall...

  13. Anion exchange membranes based on terminally crosslinked methyl morpholinium-functionalized poly(arylene ether sulfone)s (United States)

    Kwon, Sohyun; Rao, Anil H. N.; Kim, Tae-Hyun


    Azide-assisted terminal crosslinking of methyl morpholinium-functionalized poly(arylene ether sulfone) block copolymers yields products (xMM-PESs) suitable for use as anion exchange membranes. By combining the advantages of bulky morpholinium conductors and our unique polymer network crosslinked only at the termini of the polymer chains, we can produce AEMs that after the crosslinking show minimal loss in conductivity, yet with dramatically reduced water uptake. Terminal crosslinking also significantly increases the thermal, mechanical and chemical stability levels of the membranes. A high ion conductivity of 73.4 mS cm-1 and low water uptake of 26.1% at 80 °C are obtained for the crosslinked membrane with higher amount of hydrophilic composition, denoted as xMM-PES-1.5-1. In addition, the conductivity of the crosslinked xMM-PES-1.5-1 membrane exceeds that of its non-crosslinked counterpart (denoted as MM-PES-1.5-1) above 60 °C at 95% relative humidity because of its enhanced water retention capacity caused by the terminally-crosslinked structure.

  14. Metal dependence of the nonplanar distortion of octaalkyltetraphenylporphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Sparks, L.D.; Shelnutt, J.A. (Sandia National Laboratories, Albuquerque, NM (United States) Univ. of New Mexico, Albuquerque (United States)); Medforth, C.J.; Senge, M.O.; Smith, K.M. (Univ. of California, Davis (United States)); Park, M.S.; Ondrias, M.R. (Univ. of New Mexico, Albuquerque (United States)); Chamberlain, J.R. (Sandia National Laboratories, Albuquerque, NM (United States))


    The biological activity of porphyrins and related tetrapyrroles in proteins may be modulated by nonplanar conformational distortions; consequently, two aspects of nonplanarity have been investigated in the highly nonplanar octaalkyltetraphenylporphyrins (OATPPs). In the first part, the effect of the central metal ion (M = Ni(II), Co(II), Cu(II), Zn(II), Co(III), Fe(III)) on the conformation of the OATPP macrocycle has been determined. Crystallographic studies reveal that the sterically encumbered, nonplanar porphyrin 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin (OETPP) remains sufficiently flexible to show a small decrease in nonplanarity for large metal ions. This decrease in nonplanarity for the OETPP metal complexes is predicted by using a molecular mechanics force field derived from structural and vibrational data for planar metalloporphyrins. A detailed analysis of the crystal structures of the Co(II) and Cu(II) complexes of OETPP reveals that the metal-dependent changes in bond lengths and bond angles are qualitatively similar to the changes observed for the OEP complexes. As the metal size increases, both OEPs and OETPPs exhibit expansion of the meso bridges (increases in the C[sub [alpha

  15. Nitric Acid Dehydration Using Perfluoro Carboxylate and Mixed Sulfonate/Carboxylate Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Ames, Richard L. [Colorado School of Mines, Golden, CO (United States)


    Perfluoro ionomer membranes are tetrafluoro ethylene-based materials with microheterogeneous structures consisting of a hydrophobic polymer backbone and a hydrophilic side-chain cluster region. Due to the ionomer cluster morphology, these films exhibit unique transport properties. Recent investigations with perfluoro sulfonate and perfluoro sulfonate/carboxylate composite polymers have demonstrated their value in the dehydration of nitric acid and they show potential as an alternative to conventional, energy intensive unit operations in the concentration of acid feeds. As a result, investigations were conducted to determine the feasibility of using pure perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films for the dehydration of nitric acid because of the speculation of improved water selectivity of the carboxylate pendant chain. During the first phase of these investigations the effort was focused on generating a thin, solution cast perfluoro carboxylate ionomer film, to evaluate the general, chemical and physical characteristics of the polymer, and to assess the material's aqueous transport performance (flux and nitrate separation efficiencies) in pervaporation and high-pressure environments. Results demonstrated that generating robust solution-cast films was difficult yet a number of membranes survived high trans-membrane pressures up to 700 psig. General characterization of the solution cast product showed reduced ion exchange capacities when compared with thicker, ''as received'' perfluoro carboxylate and similar sulfonate films. Small angle x-ray scattering analysis results suggested that the solution cast carboxylate films contained a small fraction of sulfonate terminated side-chains. Aqueous transport experimentation showed that permeate fluxes for both pure water and nitric acid were approximately two orders of magnitude smaller for the carboxylate solution cast membranes when compared to their sulfonate

  16. New acid dyes and their metal complexes based on substituted phenols for leather: Synthesis, characterization and optical studies

    Directory of Open Access Journals (Sweden)

    Ghulam Hussain


    Full Text Available The present investigation deals with synthesis of new acid dyes from 4-amino-1-(4-sulfophenyl-3-methyl-5-pyrazolone and phenol derivatives and their metal complexes (Cu (II and Fe (II. The phenol derivatives include 4-chlorophenol, 4-nitrophenol, 4-hydroxybenzene sulfonic acid, 2-nitrophenol-4-sulfonic acid, resorcinol and bisphenol A and bisphenol S. The newly synthesized dyes were applied to crust leather to assess their dyeing properties. The fastness properties of unmetallized dyes were less as compared to metal complexes due to the strong interaction of metals with leather protein. The structures of these dyes were also confirmed by UV, FTIR and NMR studies.

  17. Sulfonation Process and Desalination Effect of Polystyrene/PVDF Semi-Interpenetrating Polymer Network Cation Exchange Membrane


    Yin-lin Lei; Yun-jie Luo; Fei Chen; Le-he Mei


    With the classical sulfonation method of polystyrene-based strongly acidic cation exchange resins, polystyrene/polyvinylidene fluoride (PVDF) alloy particles were sulfonated to obtain a cation exchange resin, which was then directly thermoformed to prepare a semi-interpenetrating polymer network (semi-IPN) cation exchange membrane. The effects of the swelling agent, sulfonation time and temperature and the relative contents of polystyrene and divinylbenzene (DVB) in the alloy particles on the...

  18. Sulfonated carbon black-based composite membranes for fuel cell ...

    Indian Academy of Sciences (India)

    sulfophenyl-phosphonate, heteropolyacid, layered silicates. (such as laponite, modified montmorillonite), zeolites, boron phosphate silicates and functionalized silicates, metal oxides and sulfated zirconia have been embedded into SPEEK membranes (Herring 2006). Recently, carbon nanotubes (CNTs) have attracted parti ...

  19. Grafting titanium nitride surfaces with sodium styrene sulfonate thin films (United States)

    Zorn, Gilad; Migonney, Véronique; Castner, David G.


    The importance of titanium nitride lies in its high hardness and its remarkable resistance to wear and corrosion, which has led to its use as a coating for the heads of hip prostheses, dental implants and dental surgery tools. However, the usefulness of titanium nitride coatings for biomedical applications could be significantly enhanced by modifying their surface with a bioactive polymer film. The main focus of the present work was to graft a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film from titanium nitride surfaces via a two-step procedure: first modifying the surface with 3-methacryloxypropyltrimethoxysilane (MPS) and then grafting the pNaSS film from the MPS modified titanium through free radical polymerization. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used after each step to characterize success and completeness of each reaction. The surface region of the titanium nitride prior to MPS functionalization and NaSS grafting contained a mixture of titanium nitride, oxy-nitride, oxide species as well as adventitious surface contaminants. After MPS functionalization, Si was detected by XPS, and characteristic MPS fragments were detected by ToF-SIMS. After NaSS grafting, Na and S were detected by XPS and characteristic NaSS fragments were detected by ToF-SIMS. The XPS determined thicknesses of the MPS and NaSS overlayers were ∼1.5 and ∼1.7 nm, respectively. The pNaSS film density was estimated by the toluidine blue colorimetric assay to be 260 ± 70 ng/cm2. PMID:25280842

  20. Synthesis and characterization of sulfonated polyesters derived from glycerol; Sintese e caracterizacao de poliesteres sulfonados obtidos a partir do glicerol

    Energy Technology Data Exchange (ETDEWEB)

    Fiuza, R.A.; Jose, N.M.; Boaventura, J.S. [Universidade Federal da Bahia (IQ/UFBA), Salvador, BA (Brazil). Inst. de Quimica; Fiuza, R.P. [Universidade Federal da Bahia (EP/UFBA), Salvador, BA (Brazil). Escola Politecnica. Curso de Mestrado em Engenharia Quimica


    In this work were synthesized polyesters from glycerol and acid sulfonated phthalic previously. The materials were characterized by DSC, TGA, FTIR, SEM, XRD and XRF. The results showed effective sulfonation of phthalic acid. The presence of sulfonic groups promoted strong changes in the crystallinity of the new material makes the lens. The polyesters made from phthalic acid sulfonated combine characteristics such as heat resistance and groups that drivers potentiate the electrolyte for application in fuel cells proton exchange membrane and also for gas separation. (author)

  1. Phosphoric Acid-Mediated Synthesis of Vinyl Sulfones through Decarboxylative Coupling Reactions of Sodium Sulfinates with Phenylpropiolic Acids. (United States)

    Rong, Guangwei; Mao, Jincheng; Yan, Hong; Zheng, Yang; Zhang, Guoqi


    A novel phosphoric acid -mediated synthesis of vinyl sulfones through decarboxylative coupling reactions of sodium sulfinates with phenylpropiolic acids is described. This transformation is efficient and environmentally friendly.

  2. Highly Sulfonated Diamine Synthesized Polyimides and Protic Ionic Liquid Composite Membranes Improve PEM Conductivity

    Directory of Open Access Journals (Sweden)

    Bor-Kuan Chen


    Full Text Available A novel sulfonated diamine was synthesized from 1,4-bis(4-aminophenoxy benzene [pBAB]. Sulfonated polyimides (SPIs were synthesized from sulfonated pBAB, 1,4-bis(4-aminophenoxy-2-sulfonic acid benzenesulfonic acid [pBABTS], various diamines and aromatic dianhydrides. Composite proton exchange membranes (PEMs made of novel SPIs and a protic ionic liquid (PIL 1-vinyl-3-H-imidazolium trifluoromethanesulfonate [VIm][OTf] showed substantially increased conductivity. We prepared an SPI/PIL composite PEM using pBABTS, 4,4′-(9-fluorenylidene dianiline (9FDA as diamine, 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA as dianhydride and 40 wt % [VIm][OTf] with a high conductivity of 16 mS/cm at 120 °C and anhydrous condition. pBABTS offered better conductivity, since the chemical structure had more sulfonated groups that provide increased conductivity. The new composite membrane could be a promising anhydrous or low-humidity PEM for intermediate or high-temperature fuel cells.

  3. Hydrocarbon and partially fluorinated sulfonated copolymer blends as functional membranes for proton exchange membrane fuel cells (United States)

    Arnett, Natalie Y.; Harrison, William L.; Badami, Anand S.; Roy, Abhishek; Lane, Ozma; Cromer, Frank; Dong, Limin; McGrath, James E.

    Polymer blending is recognized as a valuable technique used to modify and improve the mechanical, thermal, and surface properties of two different polymers or copolymers. This paper investigated the solution properties and membrane properties of a biphenol-based disulfonated poly (arylene ether sulfone) random copolymer (BPS-35) with hexafluoroisopropylidene bisphenol based sulfonated poly (arylene ether sulfone) copolymers (6FSH) and an unsulfonated biphenol-based poly (arylene ether sulfone)s. The development of blended membranes with desirable surface characteristics, reduced water swelling and similar proton conductivity is presented. Polymer blends were prepared both in the sodium salt and acid forms from dimethylacetamide (DMAc). Water uptake, specific conductivity, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and contact angles were used to characterize the blended films. Surface enrichment of the fluorinated component is illustrated by an significant increase in the water-surface contact angle was observed when 10 wt.% 6FBPA-00 (106°) was added to BPS 35 (80°). Water weight gain was reduced by a factor of 2.

  4. Copoly(arlene ether)s containing pendant sulfonic acid groups as proton exchange membrane

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu Seung [Los Alamos National Laboratory; Kim, Dae Sik [CANADA NRC; Robertson, Gilles [CANADA NRC; Guiver, Michael [CANADA NRC


    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The P AE and PAEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2-phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. The sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sP AE and sP AEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (DS) of 1.0 had high ion exchange capacities (IEC{sub v}(wet) (volume-based, wet state)) of 1.77 and 2.55 meq./cm{sup 3}, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5-51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the area of outstanding properties in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based). Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  5. The host cell sulfonation pathway contributes to retroviral infection at a step coincident with provirus establishment.

    Directory of Open Access Journals (Sweden)

    James W Bruce


    Full Text Available The early steps of retrovirus replication leading up to provirus establishment are highly dependent on cellular processes and represent a time when the virus is particularly vulnerable to antivirals and host defense mechanisms. However, the roles played by cellular factors are only partially understood. To identify cellular processes that participate in these critical steps, we employed a high volume screening of insertionally mutagenized somatic cells using a murine leukemia virus (MLV vector. This approach identified a role for 3'-phosphoadenosine 5'-phosphosulfate synthase 1 (PAPSS1, one of two enzymes that synthesize PAPS, the high energy sulfate donor used in all sulfonation reactions catalyzed by cellular sulfotransferases. The role of the cellular sulfonation pathway was confirmed using chemical inhibitors of PAPS synthases and cellular sulfotransferases. The requirement for sulfonation was mapped to a stage during or shortly after MLV provirus establishment and influenced subsequent gene expression from the viral long terminal repeat (LTR promoter. Infection of cells by an HIV vector was also shown to be highly dependent on the cellular sulfonation pathway. These studies have uncovered a heretofore unknown regulatory step of retroviral replication, have defined a new biological function for sulfonation in nuclear gene expression, and provide a potentially valuable new target for HIV/AIDS therapy.

  6. Potential contact and intraocular lenses based on hydrophilic/hydrophobic sulfonated syndiotactic polystyrene membranes

    Directory of Open Access Journals (Sweden)

    Simona Zuppolini


    Full Text Available Crystalline films of syndiotactic polystyrene (s-PS, a commercially available thermoplastic polymer, having a highly hydrophilic amorphous phase, were achieved by using a mild solid-state sulfonation procedure. Despite the used mild process conditions, an easy and uniform sulfonation of the phenyl rings of the amorphous phase is obtained. The crystallinity of the polymer was not affect by the sulfonation degree (S, at least at S less than 20%, and the obtained polymer films show the nanoporous crystalline form of s-PS. As widely reported in literature, the nanoporous nature of the polymer crystalline phase gives to these materials the ability to absorb and release organic molecules of appropriate size and polarity. This property, coupled to transparency, makes these materials potentially useful intraocular lens (IOLs and contact lens applications. Sulfonation procedure and sulfonated film samples characterization by using wide-angle X-ray diffraction (WAXD, Fourier-transform infrared (FTIR and ultraviolet-visible (UV-vis spectroscopy techniques and water sorption tests were reported. Furthermore, the biocompatibility study demonstrated no cytotoxicity and appropriate cell interaction properties for the specific applications.

  7. Conformational-induced doping effect of sodium dodecyl benzene sulfonate on single walled carbon nanotubes. (United States)

    Lee, Jin-Hyon; Yoon, Seon-Mi; Park, Sam-Jin; Cha, In-Sung; Shin, Hyeon-Jin; Choi, Jae-Young; Kim, Jong Min; Paik, Ungyu


    The doping behavior of single-walled carbon nanotubes (SWCNTs) was investigated with an emphasis on the control of the conformation of sodium dodecylbenzene sulfonate (NaDDBS) with sulfonate groups acting as an electro-withdrawing group. The conformation of adsorbed NaDDBS on SWCNTs was controlled as a function of the amount of NaDDBS. The doping behavior of SWCNTs was significantly affected by the dosing amount of NaDDBS due to the conformational change of NaDDBS adsorbed on the SWCNT surface, which affected the spatial distance between the SWCNT surface and the sulfonate groups in NaDDBS. At a higher concentration, the spatial distance between the sulfonate group in NaDDBS and SWCNT was not sufficiently close enough to dope SWCNT due to the repulsive forces between the sulfonate groups in NaDDBS. Alternatively, at a lower concentration, NaDDBS acted as a p-type dopant for SWCNTs. To this end, this paper demonstrates a new tendency of doping that is related to the adsorbed behavior of a dispersant.

  8. Analysis of sulfonated compounds by ion-exchange high-performance liquid chromatography-mass spectrometry. (United States)

    Socher, G; Nussbaum, R; Rissler, K; Lankmayr, E


    Ion-exchange high-performance liquid chromatography (HPIEC)-mass spectrometry (MS) was used for the analysis of different sulfonated compounds. HPIEC was performed on an aminopropyl column applying a gradient with increasing concentration of a buffer consisting of ammonium acetate-acetic acid and acetonitrile as the organic modifier. HPIEC is well suited to highly efficient separation of sulfonated compounds and furthermore, due to the volatility of ammonium acetate, the method is also appropriate for LC-MS coupling by the means of either atmospheric pressure chemical ionization or electrospray ionization. The applicability range of HPIEC-MS is demonstrated on the basis of a complex mixture of model substances consisting of sulfonated aromatics and textile dyes largely differing from each other in their structural properties.

  9. Nuclear Magnetic Resonance Identification of New Sulfonic Acid Metabolites of Chloroacetanilide Herbicides (United States)

    Morton, M.D.; Walters, F.H.; Aga, D.S.; Thurman, E.M.; Larive, C.K.


    The detection of the sulfonic acid metabolites of the chloroacetanilide herbicides acetochlor, alachlor, butachlor, propachlor, and, more recently, metolachlor in surface and ground water suggests that a common mechanism for dechlorination exists via the glutathione conjugation pathway. The identification of these herbicides and their metabolites is important due to growing public awareness and concern about pesticide levels in drinking water. Although these herbicides are regulated, little is known about the fate of their metabolites in soil. The sulfonic acid metabolites were synthesized by reaction of the parent compounds with an excess of sodium sulfite. Acetochlor, alachlor, butachlor, metolachlor, and propachlor and their sulfonic acid metabolites were studied by nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. This paper provides a direct method for the preparation and characterization of these compounds that will be useful in the analysis and study of chloracetanilide herbicides and their metabolites.

  10. Synthesis and Process Optimization of Electrospun PEEK-Sulfonated Nanofibers by Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Carlo Boaretti


    Full Text Available In this study electrospun nanofibers of partially sulfonated polyether ether ketone have been produced as a preliminary step for a possible development of composite proton exchange membranes for fuel cells. Response surface methodology has been employed for the modelling and optimization of the electrospinning process, using a Box-Behnken design. The investigation, based on a second order polynomial model, has been focused on the analysis of the effect of both process (voltage, tip-to-collector distance, flow rate and material (sulfonation degree variables on the mean fiber diameter. The final model has been verified by a series of statistical tests on the residuals and validated by a comparison procedure of samples at different sulfonation degrees, realized according to optimized conditions, for the production of homogeneous thin nanofibers.

  11. Periodic Mesoporous Organosilica Functionalized with Sulfonic Acid Groups as Acid Catalyst for Glycerol Acetylation

    Directory of Open Access Journals (Sweden)

    Pascal Van Der Voort


    Full Text Available A Periodic Mesoporous Organosilica (PMO functionalized with sulfonic acid groups has been successfully synthesized via a sequence of post-synthetic modification steps of a trans-ethenylene bridged PMO material. The double bond is functionalized via a bromination and subsequent substitution obtaining a thiol functionality. This is followed by an oxidation towards a sulfonic acid group. After full characterization, the solid acid catalyst is used in the acetylation of glycerol. The catalytic reactivity and reusability of the sulfonic acid modified PMO material is investigated. The catalyst showed a catalytic activity and kinetics that are comparable with the commercially available resin, Amberlyst-15, and furthermore our catalyst can be recycled for several subsequent catalytic runs and retains its catalytic activity.

  12. [Sensitivity to sodium dodecyl benzene sulfonate: a supplementary test for bacterial identification]. (United States)

    Serov, G D


    The susceptibility to sodium dodecylbenzene sulfonate, an anion-active detergent, was studied with 10 Gram-positive and 18 Gram-negative bacterial cultures. According to this susceptibility, the cultures were subdivided into two groups identical in their tinctorial properties. The bacteria growing at a 0.05% concentration of sodium dodecylbenzene sulfonate or at its higher concentrations were Gram-negative. The threshold concentration of this compound in the medium at which Gram-positive cultures could grow was 0.008%; some of the bacteria ceased growing even at a 0.002% concentration. The bacteria varied in their susceptibility to the detergent also within one and the same group, and even within one and the same species. The subdivision of bacteria on the basis of their susceptibility to sodium dodecylbenzene sulfonate may be considered as a taxonomic feature.

  13. Synthesis and detection of toltrazuril sulfone and its pharmacokinetics in horses following administration in dimethylsulfoxide. (United States)

    Dirikolu, L; Karpiesiuk, W; Lehner, A F; Hughes, C; Granstrom, D E; Tobin, T


    Triazine-based antiprotozoal agents are known for their lipophylic characteristics and may therefore be expected to be well absorbed following oral administration. However, although an increase in lipid solubility generally increases the absorption of chemicals, extremely lipid-soluble chemicals may dissolve poorly in gastrointestinal (GI) fluids, and their corresponding absorption and bioavailability would be low. Also, if the compound is administered in solid form and is relatively insoluble in GI fluids, it is likely to have limited contact with the GI mucosa, and therefore, its rate of absorption will be low. Based on the above considerations, we sought a solvent with low or no toxicity that would maintain triazine agents in solution. As the oral route is most preferred for daily drug therapy, such a solvent would allow an increased rate of absorption following oral administration. In present study, it was demonstrated that dimethylsulfoxide (DMSO) increased the oral bioavailability of toltrazuril sulfone (Ponazuril) threefold, relative to oral administrations of toltrazuril sulfone suspended in water. The cross-over study of toltrazuril sulfone formulated in DMSO indicated that the absolute oral bioavailability of toltrazuril sulfone in DMSO is 71%. The high bioavailability of the DMSO-preparation suggests that its daily oral administration will routinely yield effective plasma and cerebral spinal fluid (CSF) concentrations in all horses treated. Also, this improved formulation would allow clinicians to administer loading doses of toltrazuril sulfone in acute cases of Equine Protozoal Myeloencephalitis. Another option would involve administration of toltrazuril sulfone in DMSO mixed with feed (1.23 kg daily dose) meeting the US Food and Drug Administration (FDA) recommendations for the levels of DMSO permissible in pharmaceutical preparations.

  14. Study of high-anionic conducting sulfonated microporous membranes for zinc-air electrochemical cells

    Energy Technology Data Exchange (ETDEWEB)

    Wu, G.M. [Institute of Electro-Optical Engineering, Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan 333, Taiwan (China)], E-mail:; Lin, S.J.; You, J.H. [Institute of Electro-Optical Engineering, Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan 333, Taiwan (China); Yang, C.C. [Ming Chi University of Technology, Taipei 243, Taiwan (China)


    High-performance electrochemical membranes have been in great demand due to the rapid market growth in the portable power source devices. The electrochemical characteristics of high-anionic conducting membrane separators were studied in this report using microporous membranes with different sulfonation degrees obtained by changing the sulfonation reaction time. The degree of sulfonation treatment and the effects on the membrane separators were carefully investigated. The room temperature anionic conductivity of the membranes was improved by 132% to 3.52 x 10{sup -2} S cm{sup -1} when the sulfonation treatment time was 128 h. It was about 1.52 x 10{sup -2} S cm{sup -1} for the unsulfonated membranes. The anionic transport number in 1 M KOH aqueous solution was also improved to 0.89 from 0.79. The characteristic properties of these membrane separators were studied by infrared spectroscopy (IR), elemental analysis (EA), X-ray diffraction (XRD), scanning electron microscopy (SEM), AC impedance, contact angle measuring system and stress-strain tests. In addition, the solid-state zinc-air cells assembled from the sulfonated membrane separators showed enhanced battery power density of 38 mW cm{sup -2} while the discharge current density was higher at 45 mA cm{sup -2}. The battery power density was around 20 mW cm{sup -2} and the discharge current density was 25 mA cm{sup -2} for the unsulfonated samples. Therefore, the sulfonated microporous membranes could be tailored for the different electrochemical cell applications.

  15. Synthesis and ATRP of novel fluorinated aromatic monomer with pendant sulfonate group

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren


    Novel, fluorinated monomer with pendant sulfonate group was synthesized utilizing a two-step derivatization of 2,3,4,5,6-pentafluorostyrene (FS). The first step was a nucleophilic substitution of the fluorine atom in para position by hydroxyl group followed by sulfopropylation. The monomer...... was polymerized under aqueous ATRP conditions to yield phenyl-fluorinated aromatic homopolymer bearing pendant sulfonates on each repeating unit. Furthermore, this polymer was used as macroinitiator for the ATRP of poly(ethylene glycol) methacrylate. The polymers were characterized by 1H NMR, SEC and FTIR...

  16. Microwave Assisted Hydrolysis of Holocellulose Catalyzed with Sulfonated Char Derived from Lignin-Rich Residue

    Directory of Open Access Journals (Sweden)

    Kui Wang


    Full Text Available A microwave assisted green process has been developed for production of sugars through liquefying holocellulose catalyzed with sulfonated char derived from the lignin-rich residue produced during pretreatment of lignocellulose. Various reaction parameters including the hydrolysis temperature, hydrolysis time, catalyst content, and the ratio of water to feedstock were evaluated. The maximum sugars yield of 82.6% (based on the dry mass of holocellulose was obtained under the optimum reaction conditions. The sulfonated char showed superior catalytic performance to that of dilute sulfuric acid in converting holocellulose into sugars under microwave irradiation.

  17. Urea–hydrogen peroxide prompted the selective and controlled oxidation of thioglycosides into sulfoxides and sulfones

    Directory of Open Access Journals (Sweden)

    Adesh Kumar Singh


    Full Text Available A practical method for the selective and controlled oxidation of thioglycosides to corresponding glycosyl sulfoxides and sulfones is reported using urea–hydrogen peroxide (UHP. A wide range of glycosyl sulfoxides are selectively achieved using 1.5 equiv of UHP at 60 °C while corresponding sulfones are achieved using 2.5 equiv of UHP at 80 °C in acetic acid. Remarkably, oxidation susceptible olefin functional groups were found to be stable during the oxidation of sulfide.

  18. Sulfonic-based precursors (SAPs for silica mesostructures: Advances in synthesis and applications

    Directory of Open Access Journals (Sweden)

    Sadegh Rostamnia*


    Full Text Available Sulfonic acid-based precursors (SAP play an important role in tailoring mesoporous silica’s and convert them to a solid acid catalyst with a Bronsted-type nature. These kinds of solid acids contribute to sustainable and green chemistry by their heterogeneous, recyclable, and high efficiency features. Therefore, knowing the properties and reactivity of SAPs can guide us to manufacture a sulfonated mesostructures compatible with reaction type and conditions. In the present review, some of the important SAPs, their reactivity and mechanism of functionalization are discussed.

  19. [Bonding of MMA-BPO. DMPT resin to bovine tooth coated by poly (methyl methacrylate-co-p-styrene sulfonic acid)]. (United States)

    Kinoshita, T; Yamamoto, T; Nagata, K; Nakabayashi, N


    The objective of this study was to prepare a new type water-soluble bonding agent, methyl methacrylate (MMA)-p-styrene sulfonic acid copolymer (MS), and to investigate the effect of MS on bonding between resins and tooth substrates. MS is cross-linked with Ca2+ released from ground enamel and dentin and could be immobilized on their surface. A sample was prepared by bonding an acrylic rod with a BPO-amine catalyzed self-curing resin to ground enamel and dentin coated with an aqueous mixture of FeCl3 and 10 wt% MS. After immersion in water for 24 hrs, the tensile bond strength was measured. The bond strength to both enamel and dentin was only 2 MPa and adhesive failure occurred at the interface between cured MS and self-curing resin. This suggested that cured MS could adversely effect the polymerization of self-curing resins. A second treatment of cured MS on the tooth surface with metallic cations was carried out to minimize the amount of free sulfonic acids in the MS disturbing radical formation in self-curing resin. The second treatment improved the bond strength to 6 MPa.

  20. Metal effects on the structure of non-planar porphyrins

    Energy Technology Data Exchange (ETDEWEB)

    Sparks, L.D.; Sparks, M.S.; Chamberlain, J.R.; Ondrias, M.R.; Shelnutt, J.A. (Sandia National Lab., Albuquerque, NM (United States) Univ. of New Mexico, Albuquerque (United States)); Medforth, C.J.; Senge, M.; Smith, K.M. (Univ. of California, Davis (United States))


    Porphyrin planarity, is though to influence chemical and electron-transfer properties of tetrapyrroles in methylreductase and the photosynthetic reaction center. The authors are investigating the effect of differing metals on the conformation of the porphyrin ring for a series of highly non-planar porphyrins. The non-planarity of these octaalkyl-tetraphenylporphyrins results from steric crowding of substituents at the periphery of the planarity of the macrocycle. However, the metals incorporated into the central core effect the planarity of the macrocycle and the metal core geometry. The series of octaethyl-tetraphenylporphyrin (OETPP) metal derivaties (M=N(II), Co(II), Co(III)OAc, Cu(II), Zn(II), Fe(III)Cl) is investigated using UV-visible adsorption spectroscopy, dual-channel resonance Raman spectroscopy, and X-ray crystallography. A comparison is made between the non-planar OETPPs and the planar octaethylporphyrins (OEPs) and tetraphenylporphyrins (TPPs). Molecular mechanics calculations are also used to calculate the molecular conformations for the metal OETPPs and corresponding metal OEPs and TPPs. The calculated conformations and compared with the experimetal stuctures. Generally, the macrocycle planarity of the OETPPs decreases as the metal size increases, although all of the metal derivatives maintain considerable non-plarity. Core sizes for the MOETPP series vary over the entire range of the observed core sizes for all planar metalloporphyrins. Nevertheless, a plot of the Raman frequencies versus porphyrin core size indicates that there is little or no core-size dependence of the Raman modes v[sub 2], v[sub 3] and v[sub 4].

  1. Influence of degree of sulfonation of BDPP upon enantioselectivity in rhodium-BDPP catalyzed hydrogenation reactions in a two phase system

    NARCIS (Netherlands)

    Lensink, Cornelis; Rijnberg, Evelien; Vries, Johannes G. de


    Asymmetric hydrogenation experiments were carried out with catalysts prepared in situ from [Rh(COD)Cl]2 and 2 eq. of a sulfonated (2S,4S)-bis-2,4-(diphenylphosphino)pentane carrying 0-4 sulfonate groups, in a two phase aqueous organic system. The effect of degree of sulfonation on enantioselectivity

  2. Characterisation of perfluorooctane sulfonate (PFOS) in a terrestrial ecosystem near a fluorochemical plant in Flanders, Belgium

    NARCIS (Netherlands)

    D'Hollander, W.; De Bruyn, L.; Hagenaars, A; de Voogt, P.; Bervoets, L.


    Bioaccumulation of perfluorooctane sulfonate (PFOS) in a restricted terrestrial food chain was investigated with the omnivorous wood mouse (Apodemus sylvaticus) on top of the studied food chain. The levels detected are very high compared with literature as a result of the presence of fluorochemical

  3. Synthesis of Highly Sulfonated Poly(arylene ether Containing Multiphenyl for Proton Exchange Membrane Materials

    Directory of Open Access Journals (Sweden)

    Yi-Chiang Huang


    Full Text Available A series of sterically hindered, sulfonated, poly(arylene ether polymers were synthesized by nucleophilic polycondensation reaction using 4,4′′′′-difluoro-3,3′′′′-bistrifluoromethyl-2′′,3′′,5′′,6′′-tetraphenyl-[1,1′;4′,1′′;4′′,1′′′;4′′′,1′′′′]-pentaphenyl and 4,4′-biphenol and were prepared through postpolymerization sulfonation. The chemical structures were confirmed by 1H NMR. Subsequent to sulfonation, solvent-casting membranes were provided ion exchange capacity (IEC values ranging from 0.39 to 2.90 mmol/g. Proton conductivities of membranes ranged from 143 to 228 mS/cm at 80°C under fully humidified conditions which were higher than that of Nafion 117. The membrane also exhibited considerably dimension stability, oxidative stability, and hydrolytic stability. The microphase structure was investigated by transmission electron microscopy (TEM and the ionic aggregation of sulfonic acid groups exhibited spherical ionic clusters with well-developed phase separated morphology. The results indicated that the membranes are promising candidates for application as proton exchange membranes. This investigation demonstrates introducing multiphenylated moieties to create a high free volume polymer that provides dimensionally stable and high proton conductivity membranes.

  4. Gene expression profiling identifies mechanisms of protection to recurrent trinitrobenzene sulfonic acid colitis mediated by probiotics

    NARCIS (Netherlands)

    Mariman, R.; Kremer, S.H.A.; Erk, M. van; Lagerweij, T.; Koning, F.; Nagelkerken, L.


    Background: Host-microbiota interactions in the intestinal mucosa play a major role in intestinal immune homeostasis and control the threshold of local inflammation. The aim of this study was to evaluate the efficacy of probiotics in the recurrent trinitrobenzene sulfonic acid (TNBS)-induced colitis

  5. Sulfonated mesoporous silica-carbon composites and their use as solid acid catalysts (United States)

    Valle-Vigón, Patricia; Sevilla, Marta; Fuertes, Antonio B.


    The synthesis of highly functionalized porous silica-carbon composites made up of sulfonic groups attached to a carbon layer coating the pores of three types of mesostructured silica (i.e. SBA-15, KIT-6 and mesocellular silica) is presented. The synthesis procedure involves the following steps: (a) removal of the surfactant, (b) impregnation of the silica pores with a carbon precursor, (c) carbonization and (d) sulfonation. The resulting silica-carbon composites contain ˜30 wt % of carbonaceous matter with a high density of acidic groups attached to the deposited carbon (i.e.sbnd SO3H, sbnd COOH and sbnd OH). The structural characteristics of the parent silica are retained in the composite materials, which exhibit a high surface area, a large pore volume and a well-ordered porosity made up uniform mesopores. The high density of the sulfonic groups in combination with the mesoporous structure of the composites ensures that a large number of active sites are easily accessible to reactants. These sulfonated silica-carbon composites behave as eco-friendly, active, selective, water tolerant and recyclable solid acids. In this study we demonstrate the usefulness of these composites as solid acid catalysts for the esterification of maleic anhydride, succinic acid and oleic acid with ethanol. These composites exhibit a superior intrinsic catalytic activity to other commercial solid acids such as Amberlyst-15.

  6. Pharmacokinetic profiles of perfluorobutane sulfonate and activation of hepatic genes in mice (United States)

    Polyfluoroalkyl substances (PFAS) are organic chemicals with wide industrial and consumer uses. They are found ubiquitously at low levels in the environment and detectable in humans and wildlife. Perfluorobutane Sulfonate (PFBS) is a short-chained PFAS used to replace perfluorooc...

  7. Antibacterial surface modified of novel nanocomposite sulfonated polyethersulfone/polyrhodanine membrane (United States)

    Rostam, Abbas Babaei; Peyravi, Majid; Ghorbani, Mohsen; Jahanshahi, Mohsen


    In this study, sulfonated-polyethersulfone/polyrhodanine (SPES/PRh) membranes with antibacterial behavior were fabricated. Polyethersulfone (PES) sulfonation was performed to enhance its hydrophilicity and next polyrhodanine nanoparticles (PRhNPs) were synthesized along with the sulfonated PES (SPES) by polyrhodanine (PRh) in situ polymerization. The sulfonation step also helps making composite membrane due to development of probable bondings and polymers engagements. The constructed membranes characterization was performed by FTIR, FESEM, contact angle, 1H NMR, TGA and EDS analyses. SPES/PRh membrane had enhanced hydrophilicity and consequently better fluxes for aqueous solutions. The composite SPES/PRh membrane flux was improved to 139/78 L/m2 h comparing 58.21 L/m2 h for SPES one. Membrane operational performances, antibacterial and antibiofouling tests showed improved flux, better rejection and appropriate antibacterial and antibiofouling properties for SPES/PRh membrane. The 100% bacteria mortality for specified concentrations and appropriate inhibition zones up to 9 mm have been achieved. It is generally a suitable membrane to provide proper performance beside antibacterial and antibiofouling behavior.

  8. Sodium polyanethole sulfonate as an inhibitor of activation of complement function in blood culture systems

    DEFF Research Database (Denmark)

    Palarasah, Yaseelan; Skjoedt, Mikkel-Ole; Vitved, Lars


    Sodium polyanethole sulfonate (SPS; trade name, Liquoid) is a constituent in culture media used to grow bacteria from blood samples from patients suspected of bacteremia. SPS prevents the killing of bacteria by innate cellular and humoral factors. We analyzed the effect of SPS on the three...

  9. Polybenzimidazole and sulfonated polyhedral oligosilsesquioxane composite membranes for high temperature polymer electrolyte membrane fuel cells

    DEFF Research Database (Denmark)

    Aili, David; Allward, Todd; Alfaro, Silvia Martinez


    Composite membranes based on poly(2,2′(m-phenylene)-5,5́bibenzimidazole) (PBI) and sulfonated polyhedral oligosilsesquioxane (S-POSS) with S-POSS contents of 5 and 10wt.% were prepared by solution casting as base materials for high temperature polymer electrolyte membrane fuel cells. With membranes...

  10. Sulfonation of cPTFE Film grafted Styrene for Proton Exchange Membrane Fuel Cell

    Directory of Open Access Journals (Sweden)

    Yohan Yohan


    Full Text Available Sulfonation of γ-ray iradiated and styrene-grafted crosslinked polytetrafluoroethylene film (cPTFE-g-S film have been done. The aim of the research is to make hydropyl membrane as proton exchange membrane fuel cell. Sulfonation was prepared with chlorosulfonic acid in chloroethane under various conditions. The impact of the percent of grafting, the concentration of chlorosulfonic acid, the reaction time,and the reaction temperature on the properties of sulfonated film is examinated. The results show that sulfonation of surface-grafted films is incomplete at room  temperature. The increasing of concentration of chlorosulfonic acid and reaction temperature accelerates the reaction but they also add favor side reactions. These will lead to decreasing of the ion-exchange capacity, water uptake, and proton conductivity but increasing the resistance to oxidation in a perhidrol solution. The cPTFE-g-SS membrane which is resulted has stability in a H2O2 30% solution for 20 hours.

  11. Condensed tannin-sulfonate derivatives in cold-setting wood-laminating adhesives (United States)

    Roland E. Kreibich; Richard W. Hemingway


    Extraction of southern pine bark with 4.0 percent sodium sulfite and 0.4-percent sodium carbonate(based on ovendry bark weight) gives epicatechin-(4β)-sulfonate and oligomeric procyanidin-4-sulfonatee that show great promise to replace about 50 percent of the phenol-resorcinol-formaldehyde resin in coldsetting wood-laminating adhesives. Bonds in Douglas-fir...

  12. 40 CFR 721.950 - Sodium salt of an alkylated, sulfonated aromatic (generic name). (United States)


    ... PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES... chemical substance identified generically as a sodium salt of an alkylated, sulfonated aromatic (PMN P-84... requirements. The provisions of subpart A of this part apply to this section except as modified by this...

  13. Covalently Cross-Linked Sulfone Polybenzimidazole Membranes with Poly(Vinylbenzyl Chloride) for Fuel Cell Applications

    DEFF Research Database (Denmark)

    Yang, Jingshuai; Aili, David; Li, Qingfeng


    Covalently cross-linked polymer membranes were fabricated from poly(aryl sulfone benzimidazole) (SO(2) PBI) and poly(vinylbenzyl chloride) (PVBCl) as electrolytes for high-temperature proton-exchange-membrane fuel cells. The cross-linking imparted organo insolubility and chemical stability agains...

  14. Asymmetric, Organocatalytic, 3-Step Synthesis of γ-Hydroxy-(E)-α-β-Unsaturated Sulfones and Esters (United States)

    Petersen, Kimberly S.


    Efficient and enantiocontrolled synthesis of γ-hydroxy-α,β-unsaturated sulfones and esters are reported through the reaction of enantioenriched α-selenyl aldehydes with EWG-stabilized carbanions and then a one pot selenide oxidation, in situ epoxide formation, and final in situ epoxide opening. PMID:18811178

  15. 40 CFR 721.9674 - Sulfonated-copper phthalocyanine salt of a triarylmethane dye (generic). (United States)


    ... of a triarylmethane dye (generic). 721.9674 Section 721.9674 Protection of Environment ENVIRONMENTAL... triarylmethane dye (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as sulfonated-copper phthalocyanine salt of a triarylmethane dye...

  16. Sulfonate-immobilized artificial cathode electrolyte interphases layer on Ni-rich cathode (United States)

    Chae, Bum-Jin; Yim, Taeeun


    Although lithium nickel cobalt manganese layered oxides with a high nickel composition have gained great attention due to increased overall energy density for energy conversion/storage systems, poor interfacial stability is considered a critical bottleneck impeding its widespread adoption. We propose a new approach based on immobilizing the artificial cathode-electrolyte interphase layer, which effectively reduces undesired surface reactions, leading to high interfacial stability of cathode material. For installation of artificial cathode-electrolyte interphases, a sulfonate-based amphiphilic organic precursor, which effectively suppresses electrolyte decomposition, is synthesized and subjected to immobilization on cathode material via simple wet-coating, followed by heat treatment at low temperature. The sulfonate-based artificial cathode-electrolyte interphase layer is well-developed on the cathode surface, and the cell controlled by the sulfonate-immobilized cathode exhibits remarkable electrochemical performance, including a high average Coulombic efficiency (99.8%) and cycling retention (97.4%) compared with pristine cathode material. The spectroscopic analyses of the cycled cathode show that the sulfonate-based artificial cathode-electrolyte interphase layer effectively mitigates electrolyte decomposition on the cathode surface, resulting in decreased interfacial resistance between electrode and electrolyte.

  17. Multi-block sulfonated poly(phenylene) copolymer proton exchange membranes (United States)

    Fujimoto, Cy H [Albuquerque, NM; Hibbs, Michael [Albuquerque, NM; Ambrosini, Andrea [Albuquerque, NM


    Improved multi-block sulfonated poly(phenylene) copolymer compositions, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cells, in electrode casting solutions and electrodes. The multi-block architecture has defined, controllable hydrophobic and hydrophilic segments. These improved membranes have better ion transport (proton conductivity) and water swelling properties.

  18. succinimide-n-sulfonic acid as an efficient recyclable catalyst for the ...

    African Journals Online (AJOL)

    -amino-4,5-dihydro-4- phenylpyrano[3,2-b]indole-3-carbonitrile derivatives with coumarin-3-carboxylic acid employing succinimide-N- sulfonic acid (SuSA) as catalyst for the synthesis of a series of 5 ...

  19. Printing properties of the red reactive dyes with different number sulfonate groups on cotton fabric. (United States)

    Xie, Kongliang; Gao, Aiqin; Li, Min; Wang, Xiao


    Cellulose fabric is an important printing substrate. Four red azo reactive dyes based on 1-naphthol-8-amino-3,6-disulfonic acid for cotton fabric printing were designed. Their UV-Vis spectra and printing properties for cotton were investigated. The relationship between the chemical structures of the dyes and their printing properties on cotton fabric was discussed. The results show that the color yield (K/S) values of the printed fabrics decreased with the increase of sulfonate groups, but the fixation and penetration of the reactive dyes on cotton fabric increased. The reactive dyes with fewer number sulfonate groups were sensitive to alkaline and urea. Whereas, the reactive dyes with numerous sulfonate groups were not sensitive to urea and had good leveling properties, penetration uniformity, and good wet fastness for cotton fabric. Surface wettability of all cotton fabrics printed with four dyes was excellent. It is possible to print cotton fabric urea-free using the reactive dyes with numerous sulfonate groups. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. A novel guanidinium grafted poly(aryl ether sulfone) for high-performance hydroxide exchange membranes. (United States)

    Zhang, Qiang; Li, Shenghai; Zhang, Suobo


    A novel poly(aryl ether sulfone) ionomer containing hexaalkylguanidinium groups was synthesized, and membranes formed from this polymer displayed large ionic clusters, high hydroxide conductivity, and excellent solubility in low boiling point water-soluble solvents such as ethanol and methanol.

  1. Electrochemically reduced graphene oxide / sulfonated polyether ether ketone composite membrane for electrochemical applications (United States)

    Seetharaman, S.; Ramya, K.; Dhathathreyan, K. S.


    A simple and effective method for the preparation of sulfonated polyether ether ketone (SPEEK) based composites with electrochemical reduced graphene oxide (EGO) as inorganic fillers has been described. The resulting dispersions are homogeneous and the cast membranes show significant improvement on tensile strength and thermal properties. It has high ionic conductivity and is cost effective making it a promising alternative membrane for electrochemical applications.

  2. Interaction of multi-walled carbon nanotubes with perfluorinated sulfonic acid ionomers and surface treatment studies

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma; Dhiman, Rajnish; Borghei, Maryam


    The interaction between high surface area nano-carbon catalyst supports for proton exchange membrane fuel cells (PEMFCs) and perfluorinated sulfonic acid (Nafion®) ionomer was studied 19 fluorine nuclear magnetic resonance spectroscopy (19F-NMR). The method was developed and improved for more...

  3. Sulfonated poly(ether ether ketone) based composite membranes for nanofiltration of acidic and alkaline media

    NARCIS (Netherlands)

    Dalwani, M.R.; Bargeman, Gerrald; Hosseiny, Seyed Schwan; Schwan Hosseiny, Seyed; Boerrigter, M.E.; Wessling, Matthias; Benes, Nieck Edwin


    Several thin film composite nanofiltration membranes have been prepared by spin coating a sulfonated poly(ether ether ketone) solution on a polyethersulfone support, followed by thermal treatment. The most optimal developed nanofiltration membrane shows a clean water permeance of ∼4.5 L m−2 h−1

  4. Azadirachta indica Attenuates Colonic Mucosal Damage in Experimental Colitis Induced by Trinitrobenzene Sulfonic Acid. (United States)

    Gautam, M K; Goel, Shalini; Ghatule, R R; Singh, A; Joshi, V K; Goel, R K


    Azadirachta indica leaves indicated the presence of active principles with proven antioxidants, antiinflammatory, immunomodulatory, free radical scavenging and healing properties. In the present study we evaluated the healing effects of 50% ethanol extract of dried leaves of Azadirachta indica on trinitrobenzene sulfonic acid-induced colitis in rats. Azadirachta indica extract (500 mg/kg) was administered orally, once daily for 14 days and studied for its effects on diarrhoea, food and water intake, body weight changes, colonic damage and inflammation, histology, antibacterial activity and free radicals (nitric oxide and lipid peroxidation), antioxidants (superoxide dismutase, catalase and reduced glutathione) and myeloperoxidase activities in colonic tissue. Intracolonic trinitrobenzene sulfonic acid increased colonic mucosal damage and inflammation, diarrhea, but decreased body weight which were reversed by Azadirachta indica extract and sulfasalazine (positive control) treatments. Azadirachta indica extract showed antibacterial activity. Azadirachta indica extract and sulfasalazine enhanced the antioxidants but decreased free radicals and myeloperoxidase activities affected in trinitrobenzene sulfonic acid-induced colitis. Azadirachta indica extract, thus seemed to be effective in healing trinitrobenzene sulfonic acid-induced colitis in rats.

  5. Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells. (United States)

    Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam


    Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

  6. 40 CFR 417.110 - Applicability; description of the SO3 solvent and vacuum sulfonation subcategory. (United States)


    ... 40 Protection of Environment 28 2010-07-01 2010-07-01 true Applicability; description of the SO3 solvent and vacuum sulfonation subcategory. 417.110 Section 417.110 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS SOAP AND DETERGENT MANUFACTURING...

  7. 40 CFR 417.90 - Applicability; description of the oleum sulfonation and sulfation subcategory. (United States)


    ... 40 Protection of Environment 28 2010-07-01 2010-07-01 true Applicability; description of the oleum sulfonation and sulfation subcategory. 417.90 Section 417.90 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS SOAP AND DETERGENT MANUFACTURING POINT SOURCE...

  8. Distribution and excretion of perfluorooctane sulfonate (PFOS) in beef cattle (Bos taurus) (United States)

    Perfluorooctane sulfonate (PFOS), a perfluoroalkyl surfactant used in many industrial products, is present in industrial wastes and in wastewater treatment plant biosolids. Biosolids are commonly applied to pastures and crops used for animal feed; consequently, PFOS may accumulate in the edible tis...

  9. Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene (United States)

    Lohrasbi, Elaheh; Javanbakht, Mehran; Mozaffari, Sayed Ahmad


    The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO3sbnd groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm-2 Pt) reaches to a maximum of 530 mW cm-2 at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

  10. Highly selective colorimetric detection of Ni2+ using silver nanoparticles cofunctionalized with adenosine monophosphate and sodium dodecyl sulfonate (United States)

    Feng, Jiayu; Jin, Weiwei; Huang, Pengcheng; Wu, Fangying


    We report a dual-ligand strategy based on silver nanoparticles (AgNPs) for highly selective detection of Ni2+ using colorimetric techniques. Adenosine monophosphate (AMP) and sodium dodecyl sulfonate (SDS) were both used as ligands to modify AgNPs. The presence of Ni2+ induces the aggregation of AgNPs through cooperative electrostatic interaction and metal-ligand interaction, resulting in a color change from bright yellow to orange. The cofunctionalized AgNPs showed obvious advantages over the ones functionalized only by AMP or SDS in terms of selectivity. Under the optimized conditions, this sensing platform for Ni2+ works in the concentration range of 4.0 to 60 μM and has a low detection limit of 0.60 μM. In addition, the colorimetric assay is very fast, and the whole analysis can be completed within a few minutes. Thus, it can be directly used in tap water and lake water samples. [Figure not available: see fulltext.

  11. Polyaniline-silver composites prepared by the oxidation of aniline with silver nitrate in solutions of sulfonic acids

    Energy Technology Data Exchange (ETDEWEB)

    Bober, Patrycja, E-mail: bober@imc.cas.c [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Trchova, Miroslava [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Prokes, Jan; Varga, Martin [Faculty of Mathematics and Physics, Charles University Prague, 182 00 Prague 8 (Czech Republic); Stejskal, Jaroslav [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic)


    Aniline was oxidized with silver nitrate in aqueous solutions of sulfonic acids: camphorsulfonic, methanesulfonic, sulfamic, or toluenesulfonic acids. Polyaniline-silver composites were produced slowly in 4 weeks in good yield, except for the reaction, which took place in sulfamic acid solution, where the yield was low. Polyaniline in the emeraldine form was identified with UV-visible, FTIR, and Raman spectra. Thermogravimetric analysis was used to determine the silver content, which was close to the theoretical prediction of 68.9 wt.%. Transmission electron microscopy demonstrated the presence of silver nanoparticles of ca 50 nm average sizes as the dominating species, and hairy polyaniline nanorods having diameter 150-250 nm accompanied them. The highest conductivity of 880 S cm{sup -1} was found with the composite prepared in methanesulfonic acid solution. Its conductivity decreased with temperature increasing in the 70-315 K range, which is typical of metals such as silver. The conductivity of composites prepared in solutions of other acids was lower and increased with increasing temperature. Such dependence is typical of semiconductors, reflecting the dominating role of polyaniline in the conductivity behaviour. It is proposed that interfaces between the polyaniline matrix and dispersed silver nanoparticles play a dominating role in macroscopic level of conductivity.

  12. Copoly(arylene ether)s containing pendant sulfonic acid groups as proton exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Dae Sik, Kim [Los Alamos National Laboratory; Yu Seung, Kim [Los Alamos National Laboratory; Gilles, Robertson [CANADA-NRC; Guiver, Michael D [CANADA-NRC


    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The PAE and P AEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sPAE and sPAEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (OS) of 1.0 had high ion exchange capacities (IEC{sub v})(wet) (volume-based, wet state) of 1.77 and 2.55 meq./cm3, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5 -51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the upper left-hand corner in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based), i.e., high proton conductivity and low water uptake. Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  13. Synthesis of sulfonated porous carbon nanospheres solid acid by a facile chemical activation route

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Binbin, E-mail:; Guo, Yanzhen; Yin, Hang; Zhang, Shouren; Yang, Baocheng, E-mail:


    Generally, porous carbon nanospheres materials are usually prepared via a template method, which is a multi-steps and high-cost strategy. Here, we reported a porous carbon nanosphere solid acid with high surface area and superior porosity, as well as uniform nanospheical morphology, which prepared by a facile chemical activation with ZnCl{sub 2} using resorcinol-formaldehyde (RF) resins spheres as precursor. The activation of RF resins spheres by ZnCl{sub 2} at 400 °C brought high surface area and large volume, and simultaneously retained numerous oxygen-containing and hydrogen-containing groups due to the relatively low processing temperature. The presence of these functional groups is favorable for the modification of –SO{sub 3}H groups by a followed sulfonation treating with sulphuric acid and organic sulfonic acid. The results of N{sub 2} adsorption–desorption and electron microscopy clearly showed the preservation of porous structure and nanospherical morphology. Infrared spectra certified the variation of surface functional groups after activation and the successful modification of –SO{sub 3}H groups after sulfonation. The acidities of catalysts were estimated by an indirect titration method and the modified amount of –SO{sub 3}H groups were examined by energy dispersive spectra. The results suggested sulfonated porous carbon nanospheres catalysts possessed high acidities and –SO{sub 3}H densities, which endowed their significantly catalytic activities for biodiesel production. Furthermore, their excellent stability and recycling property were also demonstrated by five consecutive cycles. - Graphical abstract: Sulfonated porous carbon nanospheres with high surface area and superior catalytic performance were prepared by a facile chemical activation route. - Highlights: • Porous carbon spheres solid acid prepared by a facile chemical activation. • It owns high surface area, superior porosity and uniform spherical morphology. • It possesses

  14. Superoxide converts indigo carmine to isatin sulfonic acid: implications for the hypothesis that neutrophils produce ozone. (United States)

    Kettle, Anthony J; Clark, Bruce M; Winterbourn, Christine C


    Recently, it was proposed that neutrophils generate ozone (Wentworth, P. J., McDunn, J. E., Wentworth, A. D., Takeuchi, C., Nieva, J., Jones, T., Bautista, C., Ruedi, J. M., Gutierrez, A., Janda, K. D., Babior, B. M., Eschenmoser, A., and Lerner, R. A. (2002) Science 298, 2195-2199; Babior, B. M., Takeuchi, C., Ruedi, J., Gutierrez, A., and Wentworth, P. J. (2003) Proc. Natl. Acad. Sci. U. S. A. 100, 3031-3034). Evidence for the proposal was based largely on the chemistry of ozone reacting with indigo carmine to produce isatin sulfonic acid. In this investigation, we have examined the specificity of this reaction and whether it can be used as unequivocal evidence of ozone production by neutrophils. Stimulated neutrophils promoted the loss of indigo carmine and formation of isatin sulfonic acid in a reaction that was completely inhibited by superoxide dismutase. Methionine, which scavenges ozone, singlet oxygen, and hypochlorous acid, had no effect on the reaction. Neither did catalase or azide, which scavenge hydrogen peroxide and inhibit myeloperoxidase, respectively. From these results, it is apparent that superoxide was responsible for bleaching indigo carmine. Superoxide generated using xanthine oxidase and acetaldehyde also converted indigo carmine to isatin sulfonic acid in a reaction that was completely inhibited by superoxide dismutase and unaffected by catalase. When the xanthine oxidase reaction was carried out in H(2)(18)O, the proportion of (18)O incorporated into the isatin sulfonic acid was the same as that found for ozone. Thus, reactions of ozone and superoxide with indigo carmine are indistinguishable with respect to isatin sulfonic acid formation. We conclude that bleaching of indigo carmine cannot be used to invoke ozone production by neutrophils. Studies using indigo carmine to implicate ozone in other biological processes should also be interpreted with caution.

  15. Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Silva, V.S.; Boaventura, M.; Mendes, A.M.; Madeira, L.M. [LEPAE, Chemical Engineering Department, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Ruffmann, B.; Vetter, S.; Nunes, S.P. [GKSS Research Centre, Max-Planck Str., 21502 Geesthacht (Germany)


    Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion{sup (R)} 112 was used as reference material. DMFC tests were also performed at 50{sup o}C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion{sup (R)} 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD=71% showed to have similar performance, or even better, as that of Nafion{sup (R)} 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD=52%. (author)

  16. Sulfonic Groups Originated Dual-Functional Interlayer for High Performance Lithium-Sulfur Battery. (United States)

    Lu, Yang; Gu, Sui; Guo, Jing; Rui, Kun; Chen, Chunhua; Zhang, Sanpei; Jin, Jun; Yang, Jianhua; Wen, Zhaoyin


    The lithium-sulfur battery is one of the most prospective chemistries in secondary energy storage field due to its high energy density and high theoretical capacity. However, the dissolution of polysulfides in liquid electrolytes causes the shuttle effect, and the rapid decay of lithium sulfur battery has greatly hindered its practical application. Herein, combination of sulfonated reduced graphene oxide (SRGO) interlayer on the separator is adopted to suppress the shuttle effect. We speculate that this SRGO layer plays two roles: physically blocking the migration of polysulfide as ion selective layer and anchoring lithium polysulfide by the electronegative sulfonic group. Lewis acid-base theory and density functional theory (DFT) calculations indicate that sulfonic groups have a strong tendency to interact with lithium ions in the lithium polysulfide. Hence, the synergic effect involved by the sulfonic group contributes to the enhancement of the battery performance. Furthermore, the uniformly distributed sulfonic groups working as active sites which could induce the uniform distribution of sulfur, alleviating the excessive growth of sulfur and enhancing the utilization of active sulfur. With this interlayer, the prototype battery exhibits a high reversible discharge capacity of more than 1300 mAh g-1 and good capacity retention of 802 mAh g-1 after 250 cycles at 0.5 C rate. After 60 cycles at different rates from 0.2 to 4 C, the cell with this functional separator still recovered a high specific capacity of 1100 mAh g-1 at 0.2 C. The results demonstrate a promising interlayer design toward high performance lithium-sulfur battery with longer cycling life, high specific capacity, and rate capability.

  17. Investigation of Ag-poly(3,4-ethylenedioxythiophene):polystyrene sulfonate nanocomposite films prepared by a one-step aqueous method (United States)

    Wang, Seok-Joo; Choi, Yong-June; Park, Hyung-Ho


    Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) hybrid films containing Ag nanoparticles were synthesized by a one-step aqueous method. The embedded Ag nanoparticles were produced using PEDOT as a reducing agent and PSS as a stabilizer. We have also demonstrated nanoparticle growth with increasing reaction time and silver nitrate content. Finally, as a nanocomposite-containing nanoparticle without surface-capping molecules and embedded in a conducting polymer matrix, the Ag NPs-PEDOT:PSS nanocomposite is interesting because it represents a type of material in which a metallic nano-island is embedded in the semiconducting matrix with a pure interface. One-step synthesized silver nanoparticles were found to induce a lowering of the work function and an increase of the highest occupied molecular orbital level in pristine PEDOT:PSS films by electron exchange with PEDOT, and also induced an inhibition of the electrostatic bond between PEDOT and PSS.

  18. Encapsulation of Crabtree's catalyst in sulfonated MIL-101(Cr): enhancement of stability and selectivity between competing reaction pathways by the MOF chemical microenvironment. (United States)

    Rosseinsky, Matthew J; Grigoropoulos, Alexios; McKay, Alasdair I; Katsoulidis, Alexandros P; Davies, Robert P; Haynes, Anthony; Brammer, Lee; Xiao, Jianliang; Weller, Andrew S


    Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL-101(Cr) metal-organic framework by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non-functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well-defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Self-assembled systems of water soluble metal 8-hydroxyquinolates with surfactants and conjugated polyelectrolytes

    DEFF Research Database (Denmark)

    Burrows, Hugh D.; Costa, Telma; Luisa Ramos, M.


    We have studied the interaction of 8-hydroxyquinoline-5-sulfonate (8-HQS) with the metal ions Al(III) and Zn(II) in aqueous solution in the presence of tetraalkylammonium surfactants using UV/vis absorption, fluorescence, NMR spectroscopy and electrical conductivity measurements, complemented...

  20. Effects of lignin-metal complexation on enzymatic hydrolysis of cellulose (United States)

    H. Liu; Junyong Zhu; S.Y. Fu


    This study investigated the inhibition of enzymatic hydrolysis by unbound lignin (soluble and insoluble) with or without the addition of metal compounds. Sulfonated, Organosolv, and Kraft lignin were added in aqueous enzyme-cellulose systems at different concentrations before hydrolysis. The measured substrate enzymatic digestibility (SED) of cellulose was decreased by...

  1. Demographic, reproductive, and dietary determinants of perfluorooctane sulfonic (PFOS) and perfluorooctanoic acid (PFOA) concentrations in human colostrum

    NARCIS (Netherlands)

    Jusko, T.A.; Oktapodas, M.; Palkovičová Murinová, L.; Babjaková, J.; Verner, M.A.; DeWitt, J.C.; Babinská, K.; Thevenet-Morrison, K.; Čonka, K.; Drobná, B.; Thurston, S.W.; Lawrence, B.P.; Dozier, A.M.; Jarvinen-Seppo, K.M.; Patayová, H.; Trnovec, T.; Legler, J.; Hertz-Picciotto, I.; Lamoree, M.H.


    To determine demographic, reproductive, and maternal dietary factors that predict perfluoroalkyl substance (PFAS) concentrations in breast milk, we measured perfluorooctane sulfonic (PFOS) and perfluorooctanoic acid (PFOA) concentrations, using liquid chromatography-mass spectrometry, in 184

  2. Surface Structural Studies of Methane Sulfonic Acid at Air/Aqueous Solution Interfaces using Vibrational Sum Frequency Spectroscopy

    National Research Council Canada - National Science Library

    Allen, H


    Atmospheric gas phase species such as methane sulfonic acid (MSA) are adsorbed and accommodated into atmospheric aqueous-phase aerosols and in some cases MSA is thought to be produced via aerosol surface chemistry...


    A facile, general and high yielding protocol for the synthesis of novel α-tosyloxy β-keto sulfones is described utilizing relatively non-toxic, [hydroxy(tosyloxy)iodo]benzene, under solvent-free conditions at room temperature.

  4. Electrolytic membrane formation of fluoroalkyl polymer using a UV-radiation-based grafting technique and sulfonation

    Energy Technology Data Exchange (ETDEWEB)

    Shironita, Sayoko; Mizoguchi, Satoko; Umeda, Minoru, E-mail: [Department of Materials Science and Technology, Nagaoka University of Technology, 1603-1 Kamitomioka, Nagaoka 940-2188, Niigata (Japan)


    A sulfonated fluoroalkyl graft polymer (FGP) membrane was prepared as a polymer electrolyte. First, the FGP membrane was grafted with styrene under UV irradiation. The grafted FGP was then sulfonated to functionalize it for proton conductivity. The grafting degree of the membrane increased with increasing grafting time during UV irradiation. The proton conductivity of the membrane increased with increasing grafting degree. The swelling ratio was independent of the grafting time, however, the water uptake increased with increasing grafting degree. Based on these results, it was found that the UV-initiated styrene grafting occurred along the membrane thickness direction. Moreover, the membrane was embedded within the glass fibers of the composite. This composite electrolytic membrane had 1.15 times the proton conductivity of a Nafion 117 membrane.

  5. Proton conducting, composite sulfonated polymer membrane for medium temperature and low relative humidity fuel cells (United States)

    Shin, Dong Won; Kang, Na Rae; Lee, Kang Hyuck; Cho, Doo Hee; Kim, Ji Hoon; Lee, Won Hyo; Lee, Young Moo


    Inorganic-organic composite membranes are fabricated using zirconium acetylacetonate nanoparticles and biphenol-based sulfonated poly(arylene ether sulfone) as an inorganic, proton conducting nanomaterial and a polymer matrix, respectively. An amphiphilic surfactant (Pluronic®) induces distribution of the inorganic nanoparticles over the entire polymer membrane. The composite membranes are thermally stable up to 200 °C. Zirconium acetylacetonate improves inter-chain interactions and the robustness of polymer membranes resulting in excellent membrane mechanical properties. In addition, composite membranes show outstanding proton conductivity compared to that of the pristine membrane at medium temperatures (80-120 °C) and low relative humidity (<50%) conditions. This improvement is due to the presence of acetylacetonate anions, which bind water molecules and act as an additional proton conducting site and/or medium. Therefore, the composite membranes significantly outperform the pristine membrane in fuel cell performance tests at medium temperatures and low relative humidity.

  6. Controlled disulfonated poly(arylene ether sulfone) multiblock copolymers for direct methanol fuel cells. (United States)

    Li, Qing; Chen, Yu; Rowlett, Jarrett R; McGrath, James E; Mack, Nathan H; Kim, Yu Seung


    Structure-property-performance relationships of disulfonated poly(arylene ether sulfone) multiblock copolymer membranes were investigated for their use in direct methanol fuel cell (DMFC) applications. Multiple series of reactive polysulfone, polyketone, and polynitrile hydrophobic block segments having different block lengths and molecular composition were synthesized and reacted with a disulfonated poly(arylene ether sulfone) hydrophilic block segment by a coupling reaction. Large-scale morphological order of the multiblock copolymers evolved with the increase of block size that gave notable influence on mechanical toughness, water uptake, and proton/methanol transport. Chemical structural changes of the hydrophobic blocks through polar group, fluorination, and bisphenol type allowed further control of the specific properties. DMFC performance was analyzed to elicit the impact of structural variations of the multiblock copolymers. Finally, DMFC performances of selected multiblock copolymers were compared against that of the industrial standard Nafion in the DMFC system.

  7. Moving beyond mass-based parameters for conductivity analysis of sulfonated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yu Seung [Los Alamos National Laboratory; Pivovar, Bryan [NREL


    Proton conductivity of polymer electrolytes is critical for fuel cells and has therefore been studied in significant detail. The conductivity of sulfonated polymers has been linked to material characteristics in order to elucidate trends. Mass based measurements based on water uptake and ion exchange capacity are two of the most common material characteristics used to make comparisons between polymer electrolytes, but have significant limitations when correlated to proton conductivity. These limitations arise in part because different polymers can have significantly different densities and conduction happens over length scales more appropriately represented by volume measurements rather than mass. Herein, we establish and review volume related parameters that can be used to compare proton conductivity of different polymer electrolytes. Morphological effects on proton conductivity are also considered. Finally, the impact of these phenomena on designing next generation sulfonated polymers for polymer electrolyte membrane fuel cells is discussed.

  8. Protein adsorption characteristics of a sulfonic-acid-group-containing nonwoven fabric (United States)

    Kim; Sasaki; Saito; Sugita; Sugo


    A sulfonic acid (SO3H)-group-containing nonwoven fabric was prepared by radiation-induced graft polymerizaton of an epoxy-group-containing monomer, glycidyl methacrylate, onto a nonwoven fabric and subsequent sulfonation. The nonwoven fabric containing SO3H groups at different densities was equilibrated with lysozyme in a buffer (pH 6.0). The equilibrium binding capacity (EBC) of lysozyme increased linearly with increasing SO3H group density. The SO3H-group-containing polymer chains extended from the pore surface due to mutual electrostatic repulsion and held lysozyme in multilayers. The maximum EBC was 0.7 kg/kg at a SO3H group density of 1.7 mol/kg.

  9. Meaning of leprosy for people who have experienced treatment during the sulfonic and multidrug therapy periods

    Directory of Open Access Journals (Sweden)

    Karen da Silva Santos


    Full Text Available AbstractObjective: to analyze the meanings of leprosy for people treated during the sulfonic and multidrug therapy periods.Method: qualitative nature study based on the Vigotski's historical-cultural approach, which guided the production and analysis of data. It included eight respondents who have had leprosy and were submitted to sulfonic and multidrug therapy treatments. The participants are also members of the Movement for Reintegration of People Affected by Leprosy.Results: the meanings were organized into three meaning cores: spots on the body: something is out of order; leprosy or hanseniasis? and leprosy from the inclusion in the Movement for Reintegration of People Affected by Leprosy.Conclusion: the meanings of leprosy for people submitted to both regimens point to a complex construction thereof, indicating differences and similarities in both treatments. Health professionals may contribute to the change of the meanings, since these are socially constructed and the changes are continuous.

  10. Direct esterification of olive-pomace oil using mesoporous silica supported sulfonic acids

    Directory of Open Access Journals (Sweden)

    F. Alrouh


    Full Text Available Mesoporous silica MCM-41 and SBA-15 containing propyl sulfonic acid groups were synthesized according to the literature and were characterized by X-ray diffraction, N2 adsorption and the H+ exchange capacities of the sulfonic acid groups were titrated. The esterification reaction of glycerol with olive-pomace oil has been carried out by using prepared functionalized mesoporous silica (MCM-41 and SBA-15 as catalysts. It has been monitored by GC two fatty acids (palmitic and oleic acids as reactants in olive-pomace oil and their related monoacylglycerols (Glycerol monopalmitate GMP and monooleate GMO as reaction product. The catalytic activities of the functionalized mesoporous silica were compared with commercial catalysts, these included homogeneous catalysts (p-toluenesulfonic acid and heterogeneous catalysts (Amberlyst-15. The total yield of monoacylglycerols (GMO + GMP was nearly 40%. Remarkably, we found that MCM-41-SO3H was recycled at least 3 times without any loss of activity.

  11. Stabilized sulfonated aromatic polymers by in situ solvothermal cross-linking

    Directory of Open Access Journals (Sweden)

    Maria Luisa eDi Vona


    Full Text Available The cross-link reaction via sulfone bridges of sulfonated polyetheretherketone (SPEEK by thermal treatment at 180 °C in presence of dimethylsulfoxide (DMSO is discussed. The modifications of properties subsequent to the cross-linking are presented. The mechanical strength as well as the hydrolytic stability increased with the thermal treatment time, i.e., with the degree of cross-linking. The proton conductivity was determined as function of temperature, IEC, degree of cross-linking and hydration number. The memory effect, which is the membrane ability to remember the water uptake reached at high temperature also at lower temperature, is exploited in order to achieve high values of conductivity. Membranes swelled at 110 °C can reach a conductivity of 0.14 S/cm at 80°C with a hydration number ( of 73.

  12. Adsorption behavior of perfluorinated sulfonic acid ionomer on highly graphitized carbon nanofibers and their thermal stabilities

    DEFF Research Database (Denmark)

    Andersen, Shuang Ma; Borghei, Maryam; Dhiman, Rajnish


    isotherm), the ionomer has varying affinities for CNFs (Keq. = between 5 and 22) as compared to Vulcan (Keq. = 18), depending on surface treatments. However, the interactions are most likely governed by different adsorption mechanisms depending on hydrophilicity / hydrophobicity of the adsorbent carbon......A systematic adsorption study of perfluorinated sulfonic acid Nafion® ionomer on ribbon type highly graphitized carbon nanofibers (CNFs) was carried out using 19 fluorine nuclear magnetic resonance spectroscopy. Based on the values obtained for the equilibrium constant (Keq., derived from Langmuir....... The ionomer is probably adsorbed via the polar sulfonic group on hydrophilic Vulcan, whereas, it is adsorbed primarily via hydrophobic -CF2- backbone on the highly hydrophobic pristine CNFs. Ionomer adsorption behavior is gradually altered from apolar to polar group adsorption for the acid modified CNFs...

  13. In silico approach to investigating the adsorption mechanisms of short chain perfluorinated sulfonic acids and perfluorooctane sulfonic acid on hydrated hematite surface. (United States)

    Feng, Hongru; Lin, Yuan; Sun, Yuzhen; Cao, Huiming; Fu, Jianjie; Gao, Ke; Zhang, Aiqian


    Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants. Copyright © 2017. Published by Elsevier Ltd.

  14. Sulfonation of maternal steroids is a conserved metabolic pathway in vertebrates. (United States)

    Paitz, Ryan T; Bowden, Rachel M


    All vertebrate embryos develop in the presence of maternally derived steroids, and maternal steroids have been hypothesized to link phenotype of the offspring to maternal physiology. In placental vertebrates, it is known that maternally derived steroids are metabolized during development via the sulfonation pathway. We used eggs from the red-eared slider turtle (Trachemys scripta) to determine whether the same metabolic pathway is used to metabolize maternally derived steroids in an oviparous vertebrate. To examine the relationship between estradiol and estrogen sulfates during development, levels of maternally derived estradiol were compared with levels of estradiol sulfate, estrone sulfate, and estriol sulfate at oviposition and after 20 days of embryonic development. Estrone sulfate was the only detectable estrogen sulfate. At oviposition, levels of both estradiol and estrone sulfate varied seasonally with clutches from later in the nesting season having significantly higher concentrations of both steroids. Levels of estrone sulfate increased during development, demonstrating that the sulfonation of maternally derived steroids occurs in oviparous vertebrates as well as in placental vertebrates. We also found that exogenous estrone sulfate increases the production of female hatchlings, thereby demonstrating the ability of this metabolite to influence embryonic development. To examine the role of sulfonation in the metabolism of maternal progesterone and testosterone, we characterized the metabolic fate of both steroids by applying tritiated forms of each steroid at oviposition and characterizing metabolites after 20 days of incubation. Similar to what was demonstrated for estradiol, both progesterone and testosterone are converted to sulfonated metabolites during embryonic development. These data suggest that steroid sulfates, both those that are maternally derived and those resulting from the metabolism of maternal steroids, are a key component of the mechanism

  15. Solvent and irradiation doses effects on the ion exchange capacity of sulfonated styrene grafted PVDF

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Henrique P.; Parra, Duclerc F.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)


    Polymers exhibiting ion exchange capacity are studied for many years due to their application in several fields, such as membranes for proton exchange fuel cells, filtration membranes, heavy ions recovery and artificial muscles and sensors. Radiation induced grafting followed by sulfonation is a well-known way to obtain ion exchange polymers. Fluorinated polymers are frequently used as polymeric matrix for grafting due to their excellent physicochemical properties. Radiation induced grafting of styrene into poly (vinylidene fluoride) (PVDF) by simultaneous method in 1:1 styrene/toluene or styrene/N,N-dimethylformamide solutions was studied. Irradiations were performed under nitrogen atmosphere, room temperature and at doses of 5, 10 and 20 kGy with dose rate of 5 kGy.h{sup -1} from a {sup 60}Co gamma source. After washing, grafted materials were sulfonated in 10% chlorosulfonic acid/1,2-dichloroethane solutions for 4 h at room temperature. Characterization shows that increasing irradiation dose corresponds to increases in the grafting yield (GY %) gravimetrically calculated and these different solvents shows different grafting behaviors. Toluene allows no more than 3 % of grafting while DMF allows up to 55 % of grafting in the same condition. Grafting in toluene solution occurs on the surface and in DMF solution it occurs in the bulk, as confirmed by SEM. Both irradiation doses and solvent used have direct effects in the ion exchange capacities (calculated after titrations). FT-IR spectra exhibit new peaks after grafting and after sulfonation, attributed to grafted monomer and sulfonic groups attached to the styrene. DSC shows differences in thermal behavior of the polymer before and after each step. (author)

  16. Evaluation of Sulfonate-Based Collectors with Different Hydrophobic Tails for Flotation of Fluorite

    Directory of Open Access Journals (Sweden)

    Renji Zheng


    Full Text Available This investigation aims to demonstrate the effects of hydrophobic tails on the affinity and relevant flotation response of sulfonate-based collectors for fluorite. For this purpose, a series of alkyl sulfonates with different hydrophobic tails, namely sodium decanesulfonate (C10, sodium dodecylsulfate (C12, sodium hexadecanesulfonate (C16, and sodium dodecylbenzenesulfonate (C12B were applied. The flotation tests showed that C12 and C12B had a better collecting performance than C10 and C16 at pH < 10, and the flotation recovery of fluorite was higher when adopting C12B as a collector compared with C12 with a strong base. The adsorption behaviors of collectors on the fluorite surface were studied through zeta potential, Fourier transform infrared (FTIR, and X-ray photoelectron spectroscopy (XPS analyses. It was found that the affinity of alkyl sulfonates for fluorite was enhanced with the increase of the alkyl chain length from C10 to C16. The existence of phenyl in the hydrophobic tail of sulfonates could improve its activity for fluorite by reducing its surface tension. The abnormal phenomenon C16 with a high affinity for fluorite had a low collecting performance for fluorite mainly due to its overlong alkyl chain, resulting in low solubility in pulp, which restrained its interaction with fluorite. We concluded that C12B was the most applicable collector for fluorite among these reagents due to its high activity, high solubility, and low cost, which was further substantiated by calculating their molecular frontier orbital energy.

  17. The design and synthesis of novel spirocyclic heterocyclic sulfone ROMK inhibitors as diuretics. (United States)

    Chobanian, Harry R; Guo, Yan; Pio, Barbara; Tang, Haifeng; Teumelsan, Nardos; Clements, Matthew; Frie, Jessica; Ferguson, Ronald; Guo, Zach; Thomas-Fowlkes, Brande S; Felix, John P; Liu, Jessica; Kohler, Martin; Priest, Birgit; Hampton, Caryn; Pai, Lee-Yuh; Corona, Aaron; Metzger, Joseph; Tong, Vincent; Joshi, Elizabeth M; Xu, Ling; Owens, Karen; Maloney, Kevin; Sullivan, Kathleen; Pasternak, Alexander


    A spirocyclic class of ROMK inhibitors was developed containing a structurally diverse heterocyclic sulfone moiety and spirocyclic core starting from lead 1. These compounds not only displayed exquisite ROMK potency but significantly improved selectivity over hERG. The lead compounds were found to have favorable pharmacokinetic properties and displayed robust diuretic, natriuretic and blood pressure lowering effects in spontaneously hypertensive rats. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Subcritical mineralization of sodium salt of dodecyl benzene sulfonate using sonication-wet oxidation (SONIWO) technique. (United States)

    Dhale, A D; Mahajani, V V


    Subcritical mineralization of sodium salt of dodecyl benzene sulfonate via hybrid process-sonication followed by wet oxidation (SONIWO) has been investigated. Sonication of the compound enhanced the rates and % COD reduction during wet oxidation. In this process, homogenous CuSO4 catalyst was found to be effective. In wet oxidation studies, phenol, hydroquinone, maleic acid, oxalic acid, propionic acid, and acetic acid were identified as intermediates. The global rate equations for wet oxidation in terms of COD reduction were developed.

  19. Synthesis and Characterization of Sulfonated Polyimides as Proton Exchange Membranes for Fuel Cells


    Gunduz, Nazan


    Series of homo- and copolyimides containing controlled degrees of sulfonic acid ion conducting pendant groups have been synthesized from both phthalic (five-) and naphthalic (six-membered) dianhydrides and appropriate wholly aromatic diamines and heterocyclic analogues. The goal is to identify thermally and hydrolytically stable ion conducting polymers (ICP) suitable as proton exchange membranes, PEM, for fuel cells. The candidate ICP's have been synthesized and characterized for molecular we...

  20. Sulfonation Process and Desalination Effect of Polystyrene/PVDF Semi-Interpenetrating Polymer Network Cation Exchange Membrane

    Directory of Open Access Journals (Sweden)

    Yin-lin Lei


    Full Text Available With the classical sulfonation method of polystyrene-based strongly acidic cation exchange resins, polystyrene/polyvinylidene fluoride (PVDF alloy particles were sulfonated to obtain a cation exchange resin, which was then directly thermoformed to prepare a semi-interpenetrating polymer network (semi-IPN cation exchange membrane. The effects of the swelling agent, sulfonation time and temperature and the relative contents of polystyrene and divinylbenzene (DVB in the alloy particles on the feasibility of the membrane formation are discussed. The results indicate that a favorable sulfonation degree above 80% and a suitable ion exchange capacity of 1.5–2.4 mmol/g can be gained, with concentrated sulfuric acid as the sulfonation agent and 1,2-dichloroethane as the swelling agent. The running electrical resistance and desalination effect of the prepared cation exchange membrane were measured in a pilot-scale electrodialyser and not only obviously exceeded a commercial heterogeneous cation exchange membrane, but was also very close to a commercial homogenous membrane. In this way, the authors have combined the classical sulfonation method of polystyrene-based cation exchange resins with the traditional thermoforming manufacturing process of heterogeneous cation exchange membranes, to successfully develop a novel, low-price, but relatively high-performance polystyrene/PVDF cation exchange membrane with the semi-IPN structure.

  1. Evaluation of urinary mercury excretion after administration of 2,3-dimercapto-1-propane sulfonic acid to occupationally exposed men. (United States)

    Torres-Alanís, O; Garza-Ocañas, L; Pineyro-Lopez, A


    The purpose of this study was to determine the clinical efficacy of 2,3-dimercapto-1-propane sulfonic acid, Na salt, on the urinary excretion of mercury as well as its possible adverse effects. Ten men with occupational mercury exposure (urinary level of 50 micrograms/g creatinine or more) were assigned to receive 2,3-dimercapto-1-propane sulfonic acid p.o. (DIMAVAL capsules, 100 mg) 300 mg/d for five days. Informed written consent was obtained from each subject. Hematology analyses, blood, chemistry, and urinalysis were obtained at the start of the study, at the end of the 2,3-dimercapto-1-propane sulfonic acid treatment and 72 hours after the administration of the final dose of 2,3-dimercapto-1-propane sulfonic acid. Twenty-four-hour urine mercury levels were closely monitored throughout therapy. All data and measurements before and during drug doses were evaluated by analyses of variance. In all subjects mean urine mercury was significantly increased (p propane sulfonic acid treatment. One subject had a moderate hypersensitivity reaction (rash) to 2,3-dimercapto-1-propane sulfonic acid but no other toxic effects were observed.

  2. QENS investigation of proton confined motions in hydrated perfluorinated sulfonic membranes and self-assembled surfactants

    Directory of Open Access Journals (Sweden)

    Berrod Quentin


    Full Text Available We report on QuasiElastic Neutron Scattering (QENS investigations of the dynamics of protons and water molecules confined in nanostructured perfluorinated sulfonic acid (PFSA materials, namely a commercial Aquivion membrane and the perfluorooctane sulfonic acid (PFOS surfactant. The former is used as electrolyte in low-temperature fuel cells, while the latter forms mesomorphous self-assembled phases in water. The dynamics was investigated as a function of the hydration level, in a wide time range by combining time-of-flight and backscattering incoherent QENS experiments. Analysis of the quasielastic broadening revealed for both systems the existence of localized translational diffusive motions, fast rotational motions and slow hopping of protons in the vicinity of the sulfonic charges. The characteristic times and diffusion coefficients have been found to exhibit a very similar behaviour in both membrane and surfactant structures. Our study provides a comprehensive picture of the proton motion mechanisms and the dynamics of confined water in model and real PFSA nanostructures.

  3. Synergistic Effects of Mixing Sulfone and Ionic Liquid as Safe Electrolytes for Lithium Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liao, Chen; Guo, Bingkun; Sun, Xiao-Guang; Dai, Sheng


    Here we report a strategy of mixing both the ionic liquid and sulfone with synergistic effects of reducing viscosity, increasing ionic conductivity, reducing the polysulfide dissolution, and improving the safety. The mixtures of the ionic liquids and sulfones also show distinctly different physicochemical properties, including the thermal properties and crystallization behavior. Using these electrolytes, lithium sulfur batteries assembled with lithium and mesoporous carbon composites show a reversible specific capacity of 1265 mAh g-1 (second cycle) by using 40% 1.0 M LiTFSI in MPPY∙TFSI with 60% 1.0 M LiTFSI in MIPS in the first cycle. This capacity is slightly lower than what was obtained in the pure 1.0 M LiTFSI in the sulfone electrolytes; however, it exhibits an excellent cycling stability and remains as high as 655 mAh g-1 even after 50 cycles. Our strategy provides a method to alleviate the polysulfide dissolution and redox shuttle phenomenon, with an improved ionic conductivity at the same time.

  4. Comparative effects of fipronil and its metabolites sulfone and desulfinyl on the isolated rat liver mitochondria. (United States)

    Tavares, Marco A; Palma, Ivo D F; Medeiros, Hyllana C D; Guelfi, Marieli; Santana, Andréia T; Mingatto, Fábio E


    Fipronil is an insecticide extensively used to control pests in crops and animals. There are relates of poisoning due to exposure of fipronil in mammals and the liver has been suggested as potential target. In this study, we evaluated the effects of fipronil and its metabolites sulfone and desulfinyl on the bioenergetics, reactive oxygen species (ROS) production and calcium efflux from mitochondria isolated from rat liver. Fipronil (5-25 μM) inhibited state-3 respiration in mitochondria energized with glutamate plus malate, substrates of complex I of the respiratory chain and decreased the mitochondrial membrane potential resulting in inhibition of ATP synthesis. Fipronil also caused uncoupling in succinate-energized mitochondria and calcium efflux. The metabolites sulfone and desulfinyl also acted as mitochondrial inhibitors and uncouplers and caused calcium efflux, but with different potencies, being the sulfone the more potent one. These effects of fipronil and its metabolites on mitochondrial bioenergetics and calcium homeostasis may be related to toxic effects of the insecticide in the liver. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Conversion of lipids from wet microalgae into biodiesel using sulfonated graphene oxide catalysts. (United States)

    Cheng, Jun; Qiu, Yi; Zhang, Jie; Huang, Rui; Yang, Weijuan; Fan, Zhentao


    Four solid acid catalysts including graphene oxide (GO), sulfonated graphene oxide (SGO), sulfonated graphene (SG), and sulfonated active carbon (SAC) were used to convert lipids in wet microalgae into biodiesel. The physiochemical properties of the catalysts were characterized with scanning electron microscope, X-ray diffraction, and thermogravimetric analysis. SGO provided the highest conversion efficiency (84.6% of sulfuric acid) of lipids to fatty acid methyl esters (FAME). Whereas SAC converted few lipids into FAME. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and elemental analysis revealed that much higher hydrophilic hydroxyl content in SGO catalyst resulted in a considerable higher conversion efficiency of lipids to FAME than that (48.6%) catalyzed by SG, although SO3H groups (0.44mmol/g) in SGO were less than those (1.69mmol/g) in SG. Given its higher SO3H group content than GO (0.38mmol/g), SGO had higher conversion efficiency than GO (73.1%), when they had similar hydrophilic hydroxyl contents. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. The Effects of Sulfonated Poly(ether ether ketone Ion Exchange Preparation Conditions on Membrane Properties

    Directory of Open Access Journals (Sweden)

    Rebecca S. L. Yee


    Full Text Available A low cost cation exchange membrane to be used in a specific bioelectrochemical system has been developed using poly(ether ether ketone (PEEK. This material is presented as an alternative to current commercial ion exchange membranes that have been primarily designed for fuel cell applications. To increase the hydrophilicity and ion transport of the PEEK material, charged groups are introduced through sulfonation. The effect of sulfonation and casting conditions on membrane performance has been systematically determined by producing a series of membranes synthesized over an array of reaction and casting conditions. Optimal reaction and casting conditions for producing SPEEK ion exchange membranes with appropriate performance characteristics have been established by this uniquely systematic experimental series. Membrane materials were characterized by ion exchange capacity, water uptake, swelling, potential difference and NMR analysis. Testing this extensive membranes series established that the most appropriate sulfonation conditions were 60 °C for 6 h. For mechanical stability and ease of handling, SPEEK membranes cast from solvent casting concentrations of 15%–25% with a resulting thickness of 30–50 µm were also found to be most suitable from the series of tested casting conditions. Drying conditions did not have any apparent impact on the measured parameters in this study. The conductivity of SPEEK membranes was found to be in the range of 10−3 S cm−1, which is suitable for use as a low cost membrane in the intended bioelectrochemical systems.

  7. Study of Synthesis Polyethylene glycol oleate Sulfonated as an Anionic Surfactant for Enhanced Oil Recovery (EOR) (United States)

    Sampora, Yulianti; Juwono, Ariadne L.; Haryono, Agus; Irawan, Yan


    Mechanical Enhanced Oil Recovery (EOR) through chemical injection is using an anionic surfactant to improve the recovery of oil residues, particularly in a reservoir area that has certain characteristics. This case led the authors to conduct research on the synthesis of an anionic surfactant based on oleic acid and polyethylene glycol 400 that could be applied as a chemical injection. In this work, we investigate the sulfonation of Polyethylene glycol oleate (PDO) in a sulfuric acid agent. PDO in this experiment was derived from Indonesian palm oil. Variation of mole reactant and reaction time have been studied. The surfactant has been characterized by measuring the interfacial tension, acid value, ester value, saponification value, iodine value, Fourier Transform Infrared (FTIR), and particle size analyzer. There is a new peak at 1170-1178 cm-1 indicating that S=O bond has formed. PDO sulfonate exhibits good surface activity due to interfacial tension of 0,003 mN/m. Thus, polyethylene glycol oleate sulfonate was successfully synthesized and it could be useful as a novel an anionic surfactant.

  8. Synthesis, structural, solubility and anticancer activity studies of salts using nucleobases and sulfonic acids coformer (United States)

    Singh, Neetu; Singh, Udai P.; Nikhil, Kumar; Roy, Partha; Singh, Hariji


    The reactions of natural and unnatural nucleobases (cytosine (Cyt), adenine (Ade), 5-aminouracil (AU) and caffeine (Caff)) with sulfonic acids coformer (1,5-naphthalenedisulfonic acid, NDSA; 5-sulfosalicylic acid, SSA) resulted in the formation of salts viz. [NDSA.Cyt] (1), [NDSA.Ade] (2), [NDSA.AU] (3), [NDSA.Caff] (4), [SSA.Cyt] (5), [SSA.Ade] (6), [SSA.AU] (7), and [SSA.Caff] (8). The structural analysis revealed that salts 1, 4, 6 and 7 have intermolecular interactions between adjacent nucleobases which form two different homodimer shown in R22 (8) motif and assembled via complementary Nsbnd H⋯O and Nsbnd H⋯N interactions. However, in all other salts an intermediate supramolecular synthon pattern was observed between nucleobases and sulfonic acids. The lattice energy was also calculated by DFT to investigate whether salts were thermodynamically more stable than its coformer. The same was further confirmed by differential scanning calorimetry-thermogravimetric (DSC-TG) analysis. The anticancer activity study of individual nucleobases and their NDSA salts were also performed on human breast (MCF-7) and lung (A 549) cancer cell. The salts formation of nucleobases with sulfonic acids improved their solubility, thereby demonstrating up to 8-fold increase in solubility of nucleobases.

  9. A polyvinyl alcohol/ p-sulfonate phenolic resin composite proton conducting membrane (United States)

    Wu, Chien-Shun; Lin, Fan-Yen; Chen, Chih-Yuan; Chu, Peter P.

    Membranes composed of poly(vinyl alcohol) (PVA) and a proton source polymer, sulfonated phenolic resin (s-Ph) displayed good proton conductivity of the order of 10 -2 S cm -1 at ambient temperatures. Upon cross-linking above 110 °C, covalent links between the sulfonate groups of the phenolic resin and the hydroxyl groups of the PVA were established. Although this sacrificed certain sulfonate groups, the conductivity value was still preserved at the 10 -2 S cm -1 level. In sharp contrast to Nafion, the current membrane (both before and after cross-linking) was also effective in reducing the methanol uptake where the swelling ratio decreased with increase of methanol concentration. Although both the methanol permeation and the proton conductivity were lower compared to Nafion, the conductivity/permeability ratio of 0.97 for the PVA/s-Ph is higher than that determined for Nafion. The results suggested the effectiveness of proton transport in the polymer-complex structure and the possibility that a high proton conductivity can be realized with less water.

  10. Properties of Polymer Electrolyte Membranes Prepared by Blending of Sulfonated Polystyrene-Lignosulfonate

    Directory of Open Access Journals (Sweden)

    Siang Tandi Gonggo


    Full Text Available Electrolyte polymer membrane widely used in PEMFC and DMFC is a perfluorosulfonated membrane such as Nafion. This membrane material exhibits good chemical stability and proton conductivity, but it is very expensive and difficult to recycle. It has high cross-over methanol in DMFC that causes the decrease efficiency and performance of fuel cell, so that the electrolyte polymer membrane with low cross-over methanol has been needed to substitute Nafion membrane. One of the materials used as a polymer electrolyte membrane is polyblends of a sulfonated polystyrene-lignosulfonate (SPS-LS. These polyblends have been prepared by casting polymer solution and characterized as a polyelectrolyte membrane for DMFC. SPS was prepared by sulfonation of polystyrene with acetyl sulfate used as a sulfonating agent. The membranes of SPS-LS were characterized by analysis of functional groups, mechanical properties, and methanol permeability. The maximum mechanical properties of the SPS-LS membrane were observed in LS ratio of 7.5%. However, the methanol permeability of membrane increases as the increase of LS ratio in SPS-LS membranes. The properties of membranes, especially the mechanical property and methanol permeability close to that of Nafion® 117 membrane, so the SPS-LS membrane is highly potential used as the electrolyte membrane for direct methanol fuel cell.

  11. Blends of a Polymer of Intrinsic Microporosity and Partially Sulfonated Polyphenylenesulfone for Gas Separation. (United States)

    Yong, Wai Fen; Lee, Zhi Kang; Chung, Tai-Shung; Weber, Martin; Staudt, Claudia; Maletzko, Christian


    Polyphenylenesulfone (PPSU) and sulfonated polyphenylenesulfone (sPPSU) are widely used for liquid separations in the medical and food industries. However, their potential applications for gas separation have not been studied extensively owing to their low intrinsic gas permeability. We report here for the first time that blending with sPPSU can significantly improve the gas separation performance of highly permeable polymers of intrinsic microporosity (PIMs), specifically PIM-1, because of the strong molecular interactions of the sulfonic acid groups of sPPSU with CO2 and O2 . In addition, a novel co-solvent system has been discovered to overcome the immiscibility of these polymers. The presence of a higher degree of sulfonation in sPPSU results in better gas separation performance of the blend membranes close to or above the Robeson upper bound lines for O2 /N2 , CO2 /N2 and CO2 /CH4 separations. Interestingly, the blend membranes have comparable gas selectivity to sPPSU even though their sPPSU content is only 5-20 wt %. Moreover, they also display improved anti-plasticization properties up to 30 atm (3 MPa) using a binary CO2 /CH4 feed gas. The newly developed PIM-1/sPPSU membranes are potential candidates for air separation, natural gas separation, and CO2 capture. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Synthesis of Graphene Oxide-Based Sulfonated Oligoanilines Coatings for Synergistically Enhanced Corrosion Protection in 3.5% NaCl Solution. (United States)

    Lu, Hao; Zhang, Shengtao; Li, Weihua; Cui, Yanan; Yang, Tao


    As a vital derivative of graphene, graphene oxide (GO) is widely applied in various fields, such as transparent electrodes, solar cells, energy storage, and corrosion protection due to the large specific surface area and abundant active sites. However, compared with graphene, the application of GO has been less reported in metal corrosion protection field. Therefore, in our study, 3-aminobenzenesulfonic acid was selected to combine with oligoanilines to fabricate the GO-based sulfonated oligoanilines coatings for marine corrosion protection application. The obtained composite coatings were covered on the surface of Q235 steel, which is one of the most important structural marine materials. Fourier transform infrared spectra were utilized to prove the existence of different bonds and functional groups of aniline trimer and sulfonated aniline trimer (SAT). Scanning electron microscopy was applied to verify the combination of GO and SAT. What's more, transmission electron microscopy was applied to observe the surface appearance of the obtained GO-SAT composite material. Besides, the results of electrochemical measurements performed in 3.5 wt % NaCl solution showed excellent corrosion-protective properties of GO/SAT-coated epoxy resin with a dosage of 10 mg of GO compared with the pure epoxy resin. Moreover, the enhancement of surface hydrophobic property, to some extent, is in favor of preventing the absorption of corrosive medium and water molecules revealed by contact angle test. The addition of GO can make the diffusion pathway of the corrosive medium longer and more circuitous, while SAT has displayed excellent solvent solubility while maintaining corrosion-protective properties similar to those of polyanilines so that the corrosion-protective properties of the modified coatings improve significantly due to the synergistically enhanced corrosion protection of GO and SAT.

  13. Photochemical decomposition of 1H,1H,2H,2H-perfluorooctane sulfonate (6:2FTS) induced by ferric ions. (United States)

    Jin, Ling; Jiang, Chuanjia; Zhang, Pengyi


    Perfluorooctane sulfonate (PFOS) had wide applications, such as in the electroplating industry, but its use was restricted in 2009 by the Stockholm Convention, due to its environmental persistence and potential hazards. As the most common PFOS alternative, 1H,1H,2H,2H-perfluorooctane sulfonic acid (6:2FTS) and its salts have been increasingly used. However, little is known about its photochemical decomposition. This paper reports the ferric ion-induced efficient decomposition and defluorination of 6:2FTS under 254nm ultraviolet (UV) irradiation; the underlying mechanisms were also investigated. In the presence of 100μmol/L ferric ion and at pH3.0, the first-order decomposition rate constant of 6:2FTS (10mg/L) was 1.59/hr, which was 6 times higher than for direct UV photolysis. The effects of the ferric ion concentration and the solution pH on the 6:2FTS photodecomposition were investigated and the optimal reaction conditions were determined. In addition to fluoride and sulfate ions, shorter-chain PFCAs (C2-C7) were detected as major intermediates. The addition of hydrogen peroxide or oxalic acid accelerated the decomposition of 6:2FTS under UV irradiation, but not its defluorination, indicating that hydroxyl radicals can directly react with 6:2FTS but not with the shorter-chain PFCAs. Accordingly, a mechanism for 6:2FTS photochemical decomposition in the presence of ferric ion was proposed, which comprises two reaction pathways. First, hydroxyl radicals can directly attack 6:2FTS, leading to CC bond cleavage. Alternatively, 6:2FTS coordinates with ferric ion to form Fe(III)-6:2FTS complexes, which can undergo ligand-to-metal charge transfer under UV irradiation, causing CS bond cleavage. Copyright © 2016. Published by Elsevier B.V.

  14. Metal-metal-hofteproteser

    DEFF Research Database (Denmark)

    Ulrich, Michael; Overgaard, Søren; Penny, Jeannette


    In Denmark 4,456 metal-on-metal (MoM) hip prostheses have been implanted. Evidence demonstrates that some patients develope adverse biological reactions causing failures of MoM hip arthroplasty. Some reactions might be systemic. Failure rates are associated with the type and the design of the Mo...

  15. Synthesis and characterization of nanostructured sulfonated polyimides for proton exchange membrane fuel cells (United States)

    Zou, Lijun

    Sulfonated polyimides (SPI) are considered to be good candidates for proton exchange membranes (PEMs) since they exhibit high strength, good film-forming ability, chemical resistance, thermal stability, and, in their hydrated state, relatively high proton conductivity. Despite intense research in the area of SPIs, fundamental investigations of hydrophilic/hydrophobic phase segregation and studies of humidity dependent morphologies are scarce. In an effort to influence the order and distribution of ionic groups in rigid-rod SPIs and to understand the interrelationships between morphology, hydration and proton conductivity, two novel model systems of SPI polymers containing hydrophobic polysiloxane (SPI-PSX) and hydrophilic silica nanoparticles (SPI-Si) were developed. The first model system of sulfonated polyimide containing hydrophobic polysiloxane segmented copolymers was prepared by a one-pot synthesis. SPI-PSX materials were evaluated using 1H NMR, size-exclusion chromatography. The presence of ion-containing diamines in the reaction mixture was found to inhibit stoichiometric incorporation of hydrophobic siloxane segments. Siloxane segments were found to lower the thermal stability of the polyimide host. Equilibrium water sorption studies of free standing films of copolymers with and without siloxane segments show that the presence of siloxane segments does not interfere with water swelling, which suggests a microphase-segregated morphology may exist. TEM and SAXS analyses show evidence of phase-segregation in sulfonated polyimides and reveal that siloxane segments strongly affect ionic clustering. However, proton conductivity only changes slightly when polysiloxane segments are incorporated. Sulfonated polyimides containing hydrophilic silica nanoparticles is our second model system developed for stabilizing the dispersed morphologies to promote proton conductivity. SPI-Si nanocomposites were prepared by a pre-polymer of anhydride-terminated sulfonated

  16. Metallated metal-organic frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.


    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  17. Metallated metal-organic frameworks (United States)

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.


    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  18. CYP450-Dependent Biotransformation of the Insecticide Fipronil into Fipronil Sulfone Can Mediate Fipronil-Induced Thyroid Disruption in Rats (Full paper and erratum)


    ROQUES, Beatrice; Lacroix, Marlène; Puel, Sylvie; Gayrard-Troy, Véronique; Hagen-Picard, Nicole; Jouanin, Isabelle; Perdu, Elisabeth; Martin, Pascal; Viguie, Catherine


    In rats, the widely used insecticide fipronil increases the clearance of thyroxine (T-4). This effect is associated with a high plasma concentration of fipronil sulfone, the fipronil main metabolite in several species including rats and humans. In sheep, following fipronil treatment, fipronil sulfone plasma concentration and thyroid disruption are much lower than in rats. We postulated that fipronil biotransformation into fipronil sulfone by hepatic cytochromes P450 (CYP) could act as a pote...

  19. Fipronil sulfone induced higher cytotoxicity than fipronil in SH-SY5Y cells: Protection by antioxidants. (United States)

    Romero, A; Ramos, E; Ares, I; Castellano, V; Martínez, M; Martínez-Larrañaga, M R; Anadón, A; Martínez, M A


    Fipronil is a broad spectrum insecticide from the phenyl pyrazole family, which targets GABA receptor. Limited information is available about the metabolite fipronil sulfone cytotoxic actions. This study examined in vitro neurotoxicity of fipronil and fipronil sulfone and evaluated Trolox (vitamin E analog) (0.3, 1μM), N-acetyl-cysteine (0.5, 1mM), melatonin (0.1, 1μM) and Tempol (superoxide dismutase analog) (0.3, 0.5mM) protective role in SH-SY5Y cells. MTT and LDH assays were carried out to assess the cytotoxicity of fipronil and fipronil sulfone at 3-100μM concentrations. Fipronil sulfone was more toxic than fipronil. Tempol showed the best neuroprotectant profile against fipronil (50 and 150μM) and fipronil sulfone (3 and 10μM) reaching control levels. Fipronil (100μM) and fipronil sulfone (3μM) treatments induced a 4.7- and 5-fold increases in lipid peroxides measured as malondialdehyde (MDA) and a 2.2- and 2.0-fold increases in the levels of nitric oxide (NO). These results suggest that oxidative stress observed may be one of the major mechanisms of fipronil-induced neurotoxicity and it may be attributed in part to fipronil disposition and metabolism. Our results led us postulate that metabolite fipronil sulfone might be responsible for the fipronil-induced toxicity rather than fipronil itself. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  20. Synthesis and Antibacterial Evaluation of New Sulfone Derivatives Containing 2-Aroxymethyl-1,3,4-Oxadiazole/Thiadiazole Moiety

    Directory of Open Access Journals (Sweden)

    Shihu Su


    Full Text Available Sulfones are one of the most important classes of agricultural fungicides. To discover new lead compounds with high antibacterial activity, a series of new sulfone derivatives were designed and synthesized by introducing the aroxymethyl moiety into the scaffold of 1,3,4-oxadiazole/thiadiazole sulfones. Antibacterial activities against three phytopathogens (Xanthomonas oryzae pv. oryzae, Ralstonia solanacearum, Xanthomonas axonopodis pv. citri. were assayed in vitro. As compared to the control of commercial fungicides and some reported sulfone fungicides, seven compounds 5I-1–5I-7 exerted remarkably higher activities with EC50 values ranging from 0.45–1.86 μg/mL against X. oryzae and 1.97–20.15 μg/mL against R. solanacearum. Exhilaratingly, 5I-1, 5I-2 and 5I-4 displayed significant in vivo activity against X. oryzae with protective effect of 90.4%, 77.7%, and 81.1% at 200 μg/mL, respectively, much higher than that exhibited by Bismerthiazol (25.6% and Thiadiazole-copper (32.0%. And the differential phytotoxicity of active derivatives was preliminarily checked. The results demonstrated that derivative of 2-aroxymethyl-1,3,4-oxadiazole/thiadiazole sulfone can serve as potential alternative bactericides for the management of plant bacterial diseases.

  1. Improving the Conductivity of Sulfonated Polyimides as Proton Exchange Membranes by Doping of a Protic Ionic Liquid

    Directory of Open Access Journals (Sweden)

    Bor-Kuan Chen


    Full Text Available Proton exchange membranes (PEMs are a key component of a proton exchange membrane fuel cell. Sulfonated polyimides (SPIs were doped by protic ionic liquid (PIL to prepare composite PEMs with substantially improved conductivity. SPIs were synthesized from diamine, 2,2-bis[4-(4-amino-phenoxyphenyl]propane (BAPP, sulfonated diamine, 4,4'-diamino diphenyl ether-2,2'-disulfonic acid (ODADS and aromatic anhydride. BAPP improved the mechanical and thermal properties of SPIs, while ODADS enhanced conductivity. A PIL, 1-vinylimidazolium trifluoromethane-sulfonate ([VIm][OTf], was utilized. [VIm][OTf] offered better conductivity, which can be attributed to its vinyl chemical structure attached to an imidazolium ring that contributed to ionomer-PIL interactions. We prepared sulfonated polyimide/ionic liquid (SPI/IL composite PEMs using 50 wt% [VIm][OTf] with a conductivity of 7.17 mS/cm at 100 °C, and in an anhydrous condition, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride (DSDA was used in the synthesis of SPIs, leading to several hundred-times improvement in conductivity compared to pristine SPIs.

  2. Thiophene-degrading Escherichia coli mutants possess sulfone oxidase activity and show altered resistance to sulfur-containing antibiotics

    Energy Technology Data Exchange (ETDEWEB)

    Juhl, M.J.; Clark, D.P. (Southern Illinois Univ., Carbondale (USA))


    The authors have previously isolated mutants of Escherichia coli which show increased oxidation of heterocyclic furan and thiophene substrates. They have now found that strains carrying the thdA mutation express a novel enzyme activity which oxidizes a variety of substrates containing a sulfone (e.g., ethyl sulfone) were oxidized. The thdA mutants were more resistant than wild-type strains to aromatic sulfone antibiotics such as dapsone. In contrast they showed increased susceptibility to thiolutin, a cyclic antibiotic containing sulfur at the sulfide level of oxidation. Several new thdA mutant alleles were isolated by selecting for increased oxidation of various aliphatic sulfur compounds. These new thdA mutants showed similar sulfone oxidase activity and the same map location (at 10.7 min) as the original thdA1 mutation. The constitutive fadR mutation was required for the phenotypic expression of thdA-mediated oxidation of sulfur compounds. However, the thdA-directed expression of sulfone oxidase activity was not fadR dependent. The thdC and thdD mutations probably protect against the toxicity of thiophene derivatives rather than conferring improved metabolic capability.

  3. Functional differences between antiviral activities of sulfonated and intact intravenous immunoglobulin preparations toward varicella-zoster virus and cytomegalovirus. (United States)

    Yajima, Misako; Shiraki, Atsuko; Daikoku, Tohru; Oyama, Yukari; Yoshida, Yoshihiro; Shiraki, Kimiyasu


    Intravenous immunoglobulin (IVIG) is used to treat severe viral infection, especially varicella-zoster virus (VZV) and cytomegalovirus (CMV) infections. The neutralization antibody titers of eleven IVIG preparations from four companies were examined using VZV and CMV with and without complement. The neutralizing antibody titers of intact IgG preparations were three to six times higher after addition of complement. The effectiveness of the sulfonated IgG preparation was not enhanced by complement, but desulfonated IgG regained enhanced neutralization activity with complement. Antibody-dependent cellular cytotoxicity (ADCC) toward VZV-infected cells was observed with both intact and sulfonated IVIG and guinea pig splenocytes, but ADCC toward CMV-infected cells was not, although NK cell activity toward cells infected with VZV or CMV was detected by splenocytes. Sulfonated IVIG had no complement-activated neutralization of VZV and CMV but retained ADCC toward VZV with less activity after dilution than with intact IVIG. Because sulfonated IVIG is converted to the intact form after intravenous administration, it would show complement-enhanced neutralization and ADCC activity similar to that of intact IVIG in vivo. In this study we showed the effects of intact and sulfonated IgG on the functional activity of IgG against VZV and CMV. Copyright © 2015 Japanese Society of Chemotherapy and The Japanese Association for Infectious Diseases. Published by Elsevier Ltd. All rights reserved.


    Directory of Open Access Journals (Sweden)

    Yohan Yohan


    Full Text Available Sulfonation of g-ray iradiated and styrene-grafted crosslinked polytetrafluoro ethylene film (cPTFE-g-S film have been done. The aim of the research was to make hydrophyl membrane as proton exchange membrane fuel cell. Sulfonation was prepared by using chlorosulfonic acid in chloroethane under various conditions. The impact of the percentage of grafting, the concentration of chlorosulfonic acid, the reaction time,and the reaction temperature on the properties of sulfonated film were examined. The results show that sulfonation of surface-grafted films was incomplete at room temperature. Increasing concentration of chlorosulfonic acid and reaction temperature accelerate the reaction but they also favor side reactions. These lead to the decrease of the ion-exchange capacity, water uptake, and proton conductivity but the increase of the resistance to oxidation in a perhydrol solution. The resulted cPTFE-g-SS membraneis stabile in a H2O2 30% solution for 20 h.   Keywords: Chorosulfonic acid, sulfonation, PTFE film, proton excange membrane.

  5. Synthesis of dodecyl lauroyl benzene sulfonate and its application in enhanced oil recovery

    Energy Technology Data Exchange (ETDEWEB)

    Cui, Zhenggang; Wu, Le; Sun, Mingming; Jiang, Jian-zhong; Wang, Feng [Jiangnan Univ., Wuxi (China). School of Chemical and Material Engineering


    A new hydrophobic surfactant, dodecyl lauroyl benzene sulfonate (DLBS), was synthesized and its application in enhanced oil recovery by alkali-surfactant-polymer (ASP) flooding was studied. The results show that DLBS can be synthesized by reaction of industrial dodecyl benzene with lauroyl chloride in the presence of AlCl{sub 3}, followed by sulfonation with ClSO{sub 3}H and neutralization with NaOH. The lauroyl-group is confirmed to be connected to the para-position of the alkylbenzene by1HNMR spectrum. The synthesized DLBS is well soluble in pure water and reservoir (connate) water at 45 C. It is highly surface active which is indicated by its low CMC of 1.1 . 10{sup -5} mol/L, and its low surface tension, {gamma}{sub cmc} of 28.6 mN m{sup -1}. By mixing with heavy alkylbenzene sulfonates of relatively low average molar mass (387g mol{sup -1}) at a total surfactant concentration of 5 mM, DLBS can reduce the interfacial tension of Daqing crude oil/connate water to an order of 10{sup -3} mN/m at 45 C in the presence of 0.5-1.0 wt.% NaOH and 1000 mg L{sup -1} of polymer. If the NaOH was replaced by a gentle alkaline salt, Na{sub 2}CO{sub 3}, certain amounts of dodecyl dimethyl carboxy betaine were added and the concentration of Na{sub 2}CO{sub 3} was increased to 1.2-2.0 wt.%, the interfacial tension of Daqing crude oil/connate water can also be reduced to an ultralow value. Therefore DLBS is a good hydrophobic surfactant applicable in ASP flooding with either NaOH or Na{sub 2}CO{sub 3} as alkaline agents. (orig.)

  6. The Role of Moderate Static Magnetic Fields on Biomineralization of Osteoblasts on Sulfonated Polystryene Films

    Energy Technology Data Exchange (ETDEWEB)

    X Ba; M Hadjiargyrou; E DiMasi; Y Meng; M Simon; Z Tan; M Rafailovich


    We have investigated the effects of moderate static magnetic fields (SMFs) on murine MC3T3-E1 osteoblasts, and found that they enhance proliferations and promote differentiation. The increase in proliferation rates in response to SMFs was greater in cultures grown on partially sulfonated polytstyrene (SPS, degree of sulfonation: 33%) than in cultures grown on tissue culture plastic. We have previously shown that when the degree of sulfonation exceeded a critical value (12%) [1], spontaneous fibrillogenesis occured which allowed for direct observation of the ECM fibrillar organization under the influence of external fields. We found that the ECM produced in cultures grown on the SPS in the presence of the SMFs assembled into a lattice with larger dimensions than the ECM of the cultures grown in the absence of SMFs. During the early stages of the biomineralization process (day 7), the SMF exposed cultures also templated mineral deposition more rapidly than the control cultures. The rapid response is attributed to orientation of diamagnetic ECM proteins already present in the serum, which could then initiate further cellular signaling. SMFs also influenced late stage osteoblast differentiation as measured by the increased rate of osteocalcin secretion and gene expression beginning 15 days after SFM exposure. This correlated with a large increase in mineral deposition, and in cell modulus. GIXD and EDXS analysis confirmed early deposition of crystalline hydroxyapatite. Previous studies on the effects of moderate SMF had focused on cellular gene and protein expression, but did not consider the organization of the ECM fibers. Our ability to form these fibers has allowed us explore this additional effect and highlight its significance in the initiation of the biomineralization process.

  7. Characterization of interfaces between metals and organic thin films by electron and ion spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Schmid, Martin


    In this thesis, interfaces between metals and organic thin films have been characterized with photoelectron and ion-scattering spectroscopies. Two different classes of metal/organic interfaces were examined in detail. First, interfaces which can be mainly characterized by relatively weak coordinative interactions between substrate and adsorbate. Second, interfaces which are mostly determined, or even created, by chemical reactions between different adsorbates or between adsorbates and substrate. Typical examples from the first class are metalated tetrapyrrole monolayers on Ag(111) and Au(111) single-crystal substrates. In this study, a focus was set to the interaction between iron and cobalt tetrapyrroles with Ag(111) or Au(111) substrates. A detailed examination of the corresponding photoelectron spectra revealed that the adsorbatesubstrate interaction is associated with a charge transfer from the metallic substrate to the Fe(II) or Co(II) ions within the tetrapyrrole units. The examination of cobalt(II) phthalocyanine monolayers further led to the conclusion that the magnetic moment, as present in unperturbed CoPc molecules, is efficiently quenched by the contact to the Ag(111) surface and the associated charge transfer. Similar investigations on Au(111) substrates gave evidence for possible adsorption site effects, further complicating the adsorbate/substrate interaction. Furthermore the formation of two-dimensional structures of poly(p-phenylene-terephthalamide) (PPTA, trademark Kevlar) on Ag(111) was closely examined. The Ag(111) surface does not only provide the geometrical boundary for the formation of the 2D covalent structures, but, moreover, actively participates in the reaction; after the adsorption of TPC molecules, a scission of the C-Cl bond, in particular at temperatures above 120 K, was evident. The resulting radical fragments appear stable and can act as reaction partners for the co-adsorbed PPD units. The chlorine atoms reside on the surface even

  8. Plasma polymer-functionalized silica particles for heavy metals removal. (United States)

    Akhavan, Behnam; Jarvis, Karyn; Majewski, Peter


    Highly negatively charged particles were fabricated via an innovative plasma-assisted approach for the removal of heavy metal ions. Thiophene plasma polymerization was used to deposit sulfur-rich films onto silica particles followed by the introduction of oxidized sulfur functionalities, such as sulfonate and sulfonic acid, via water-plasma treatments. Surface chemistry analyses were conducted by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. Electrokinetic measurements quantified the zeta potentials and isoelectric points (IEPs) of modified particles and indicated significant decreases of zeta potentials and IEPs upon plasma modification of particles. Plasma polymerized thiophene-coated particles treated with water plasma for 10 min exhibited an IEP of less than 3.5. The effectiveness of developed surfaces in the adsorption of heavy metal ions was demonstrated through copper (Cu) and zinc (Zn) removal experiments. The removal of metal ions was examined through changing initial pH of solution, removal time, and mass of particles. Increasing the water plasma treatment time to 20 min significantly increased the metal removal efficiency (MRE) of modified particles, whereas further increasing the plasma treatment time reduced the MRE due to the influence of an ablation mechanism. The developed particulate surfaces were capable of removing more than 96.7% of both Cu and Zn ions in 1 h. The combination of plasma polymerization and oxidative plasma treatment is an effective method for the fabrication of new adsorbents for the removal of heavy metals.

  9. Indole alkaloid sulfonic acids from an aqueous extract of Isatis indigotica roots and their antiviral activity

    Directory of Open Access Journals (Sweden)

    Lingjie Meng


    Full Text Available Six new indole alkaloid sulfonic acids (1–6, together with two analogues (7 and 8 that were previously reported as synthetic products, were isolated from an aqueous extract of the Isatis indigotica root. Their structures including the absolute configurations were determined by spectroscopic data analysis, combined with enzyme hydrolysis and comparison of experimental circular dichroism and calculated electronic circular dichroism spectra. In the preliminary assay, compounds 2 and 4 showed antiviral activity against Coxsackie virus B3 and influenza virus A/Hanfang/359/95 (H3N2, respectively.

  10. Influence of halogen atoms and protonation on the photophysical properties of sulfonated porphyrins (United States)

    De Boni, L.; Monteiro, C. J. P.; Mendonça, C. R.; Zílio, S. C.; Gonçalves, P. J.


    This work employs UV/vis absorption and Z-scan techniques to investigate how the presence of one or two halogens atoms and the macrocycle protonation affect the photophysical characteristics of sulfonated porphyrins. The results are relevant to photomedicine and photonics because they show that: (i) the insertion of halogen atoms increases the intersystem crossing quantum yield, a useful feature for photodynamic therapy, (ii) the fluorescence observed in fluorinated porphyrins shows desired characteristics for theranostics, which combine therapy and diagnostics in the same platform, and (iii) the protonation enhances the excited-state absorption in the visible region, an important feature for optical limiting.

  11. Electrodeposition of polypyrrole films on aluminum surfaces from a p-toluene sulfonic acid medium

    Directory of Open Access Journals (Sweden)

    Andréa Santos Liu


    Full Text Available Electrodeposition of polypyrrole films on aluminum from aqueous solutions containing p-toluene sulfonic acid and pyrrole was performed by cyclic voltammetry and galvanostatic technique. The influence of applied current density on the morphology of the films was studied by Scanning Electron Microscopy. The films displayed a cauliflower-like structure consisting of micro-spherical grains. This structure is related to dopand intercalation in the polymeric chain. Films deposited at higher current density were more susceptible to the formation of pores and defects along the polymeric chain than films deposited at lower current density. These pores allow the penetration of aggressive species, thereby favoring the corrosion process.

  12. Ileocolic Perforation Secondary to Sodium Polystyrene Sulfonate in Sorbitol Use: A Case Report

    Directory of Open Access Journals (Sweden)

    Vincent Trottier


    Full Text Available Hyperkalemia is a common condition encountered in medical and surgical patients. It can lead to various complications including cardiac arrhythmias. Sodium polystyrene sulfonate (SPS in sorbitol is an ion-exchange resin that can be used to treat hyperkalemia. It can be used in enema or in oral form. The present article describes the case of an intensive care unit patient who experienced severe, diffuse, intestinal perforation induced by the use of SPS-sorbitol, requiring multiple laparotomies, followed by a brief review of the relevant literature and recommendations regarding the use of SPS-sorbitol.


    Directory of Open Access Journals (Sweden)

    I Made Sudarma


    Full Text Available The aim of this research was to prove theoretical mechanism reaction on the sulfonation of papaverine alkaloid and the result could be used as a reference on the transformation of these alkaloid to the other derivatives. Theoriticaly sulfonation of papaverine (1 by HO-SO2Cl could produced papaverine sulfonyl chloride (1a. The formation of this product was analyzed by analytical thin layer chromatography GC-MS, and FT-IR. These analysis showed the formation of product (1a more favorable than the other. Tlc showed product (1a less polar than papaverine, and supported by GC-MS and infrared which showed molecular ion at m/z 412 due to the presence of -SO2Cl and vibration at 1153,4 dan 1265,2 Cm-1 due to absorption of sulfonyl group.   Keywords: reaction mechanism, sulfonation, papaverine alkaloid.

  14. Reaction of lithium diethylamide with an alkyl bromide and alkyl benzenesulfonate: origins of alkylation, elimination, and sulfonation. (United States)

    Gupta, Lekha; Ramírez, Antonio; Collum, David B


    A combination of NMR, kinetic, and computational methods are used to examine reactions of lithium diethylamide in tetrahydrofuran (THF) with n-dodecyl bromide and n-octyl benzenesulfonate. The alkyl bromide undergoes competitive S(N)2 substitution and E2 elimination in proportions independent of all concentrations except for a minor medium effect. Rate studies show that both reactions occur via trisolvated-monomer-based transition structures. The alkyl benzenesulfonate undergoes competitive S(N)2 substitution (minor) and N-sulfonation (major) with N-sulfonation promoted at low THF concentrations. The S(N)2 substitution is shown to proceed via a disolvated monomer suggested computationally to involve a cyclic transition structure. The dominant N-sulfonation follows a disolvated-dimer-based transition structure suggested computationally to be a bicyclo[3.1.1] form. The differing THF and lithium diethylamide orders for the two reactions explain the observed concentration-dependent chemoselectivities.

  15. Molecular evolution of Fome lignosus laccase by ethyl methane sulfonate-based random mutagenesis in vitro. (United States)

    Hu, Mei-Rong; Chao, Ya-Peng; Zhang, Guo-Qing; Yang, Xiu-Qing; Xue, Zhi-Quan; Qian, Shi-Jun


    In order to improve the laccase activity, mutant libraries are constructed through ethyl methane sulfonate-based (EMS) random mutagenesis. Mutagenesis improved expression 3.7-fold to 144 mgl(-1) laccase in yeast, together with a 1.4-fold increase in K(cat). Thus, the total activity is enhanced 5-fold for 2,2'-azino-bis 3-ethylbenzothiaoline-6-sulfonic acid (ABTS). In the presence of 0.6mM copper, the highest activity value reached 30 Uml(-1) after a 3-day cultivation at a temperature of 30 degrees C(.) In comparison with the wild type, the best mutant enzymatic properties (K(m) for ABTS and guaiacol, thermo- and pH stability, optimal pH) are not changed. Moreover, amino acid sequence analysis indicates that there are four substitutions in the best mutant laccase (Gly160Asp, Ala167Thr, Gly174Asp, and Glu234Gly). The best mutant laccase model showed that the Gly160 and Ala167 are to be found near the water channel; especially the distance of Ala167 to the Cu3a is 14.46 A. This implies that it is likely involved in the formation of water channel and that it helps facilitate the easy incoming and outgoing of water.

  16. Modification of the cellulosic component of hemp fibers using sulfonic acid derivatives: Surface and thermal characterization. (United States)

    George, Michael; Mussone, Paolo G; Bressler, David C


    The aim of this study was to characterize the surface, morphological, and thermal properties of hemp fibers treated with two commercially available, inexpensive, and water soluble sulfonic acid derivatives. Specifically, the cellulosic component of the fibers were targeted, because cellulose is not easily removed during chemical treatment. These acids have the potential to selectively transform the surfaces of natural fibers for composite applications. The proposed method proceeds in the absence of conventional organic solvents and high reaction temperatures. Surface chemical composition and signature were measured using gravimetric analysis, X-ray photoelectron spectroscopy (XPS) and Fourier transform infra-red spectroscopy (FTIR). XPS data from the treated hemp fibers were characterized by measuring the reduction in O/C ratio and an increase in abundance of the C-C-O signature. FTIR confirmed the reaction with the emergence of peaks characteristic of disubstituted benzene and amino groups. Grafting of the sulfonic derivatives resulted in lower surface polarity. Thermogravimetric analysis revealed that treated fibers were characterized by lower percent degradation between 200 and 300 °C, and a higher initial degradation temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. A novel sulfonated poly(ether ether ketone) and cross-linked membranes for fuel cells (United States)

    Li, Hongtao; Zhang, Gang; Wu, Jing; Zhao, Chengji; Zhang, Yang; Shao, Ke; Han, Miaomiao; Lin, Haidan; Zhu, Jing; Na, Hui

    A novel poly(ether ether ketone) (PEEK) containing pendant carboxyl groups has been synthesized by a nucleophilic polycondensation reaction. Sulfonated polymers (SPEEKs) with different ion exchange capacity are then obtained by post-sulfonation process. The structures of PEEK and SPEEKs are characterized by both FT-IR and 1H NMR. The properties of SPEEKs as candidates for proton exchange membranes are studied. The cross-linking reaction is performed at 140 °C using poly(vinyl alcohol) (PVA) as the cross-linker. In comparison with the non-cross-linked membranes, some properties of the cross-linked membranes are significantly improved, such as water uptake, methanol resistance, mechanical and oxidative stabilities, while the proton conductivity decreases. The effect of PVA content on proton conductivity, water uptake, swelling ratio, and methanol permeability is also investigated. Among all the membranes, SPEEK-C-8 shows the highest selectivity of 50.5 × 10 4 S s cm -3, which indicates that it is a suitable candidate for applications in direct methanol fuel cells.

  18. A highly aromatic and sulfonated ionomer for high elastic modulus ionic polymer membrane micro-actuators (United States)

    Hatipoglu, Gokhan; Liu, Yang; Zhao, Ran; Yoonessi, Mitra; Tigelaar, Dean M.; Tadigadapa, Srinivas; Zhang, Q. M.


    A high modulus, sulfonated ionomer synthesized from 4,6-bis(4-hydroxyphenyl)-N,N-diphenyl-1,3,5-triazin-2-amine and 4,4‧-biphenol with bis(4-fluorophenyl)sulfone (DPA-PS:BP) is investigated for ionic polymer actuators. The uniqueness of DPA-PS:BP is that it can have a high ionic liquid (IL) uptake and consequently generates a high intrinsic strain response, which is >1.1% under 1.6 V while maintaining a high elastic modulus (i.e. 600 MPa for 65 vol% IL uptake). Moreover, such a high modulus of the active ionomer, originating from the highly aromatic backbone and side-chain-free structure, allows for the fabrication of free-standing thin film micro-actuators (down to 5 µm thickness) via the solution cast method and focused-ion-beam milling, which exhibits a much higher bending actuation, i.e. 43 µm tip displacement and 180 kPa blocking stress for a 200 µm long and 5 µm thick cantilever actuator, compared with the ionic actuators based on traditional ionomers such as Nafion, which has a much lower elastic modulus (50 MPa) and actuation strain.

  19. Hierarchical Porous Interlocked Polymeric Microcapsules: Sulfonic Acid Functionalization as Acid Catalysts (United States)

    Wang, Xiaomei; Gu, Jinyan; Tian, Lei; Zhang, Xu


    Owing to their unique structural and surface properties, mesoporous microspheres are widely applied in the catalytic field. Generally, increasing the surface area of the specific active phase of the catalyst is a good method, which can achieve a higher catalytic activity through the fabrication of the corresponding catalytic microspheres with the smaller size and hollow structure. However, one of the major challenges in the use of hollow microspheres (microcapsules) as catalysts is their chemical and structural stability. Herein, the grape-like hypercrosslinked polystyrene hierarchical porous interlocked microcapsule (HPIM-HCL-PS) is fabricated by SiO2 colloidal crystals templates, whose structure is the combination of open mouthed structure, mesoporous nanostructure and interlocked architecture. Numerous microcapsules assembling together and forming the roughly grape-like microcapsule aggregates can enhance the structural stability and recyclability of these microcapsules. After undergoing the sulfonation, the sulfonated HPIM-HCL-PS is served as recyclable acid catalyst for condensation reaction between benzaldehyde and ethylene glycol (TOF = 793 h-1), moreover, exhibits superior activity, selectivity and recyclability.

  20. Bioseparation of papain from Carica papaya latex by precipitation of papain-poly (vinyl sulfonate) complexes. (United States)

    Braia, Mauricio; Ferrero, Maximiliano; Rocha, María Victoria; Loureiro, Dana; Tubio, Gisela; Romanini, Diana


    The formation of insoluble complexes between enzymes and polyelectrolytes is a suitable technique for isolating these biomolecules from natural sources, because it is a simple and rapid technique that allows the concentration of the protein. This technique can be used in most purification protocols at the beginning of the downstream process. The aim of this investigation is to isolate papain from Carica papaya latex by precipitation of insoluble complexes between this enzyme and poly (vinyl sulfonate). The papain-poly (vinyl sulfonate) complex was insoluble at pH lower than 6, with a PVS/PAP stoichiometric ratio of 1:279. Ionic strength affected the complex formation. The presence of the polymer increased the enzymatic activity and protected the enzyme from autodegradation. The optimal conditions for the formation of insoluble papain-polyelectrolyte complex formation were applied to C. papaya latex and a high recovery was obtained (around 86%) and a purification factor around 2. This method can be applied as an isolation method of papain from C. papaya latex or as a first step in a larger purification strategy. Copyright © 2013 Elsevier Inc. All rights reserved.

  1. Animated sulfonated or sulformethylated lignins as cement fluid loss control additives

    Energy Technology Data Exchange (ETDEWEB)

    Schilling, P.


    This patent describes a method of cementing a zone in a well penetrating a subterranean formation comprising injecting down the well and positioning in the zone to be cemented a hydraulic aqueous cement slurry composition. It comprises: a hydraulic cement, and the following expressed as parts by weight per 100 parts of the hydraulic cement, water from about 25 to 105 parts, and a fluid loss control additive comprising from about 0.5 to 2.5 parts of a compound selected from the group consisting of a sulfonated lignin and a sulfomethylated lignin, wherein the lignin has been aminated by reacting it with between about 2-5 moles of a polyamine and 2-5 moles of an aldehyde per 1,000g of the lignin, and 0.1 to 1.5 parts of a compound selected from the group consisting of sodium carbonate, sodium metasilicate, sodium phosphate, sodium sulfite and sodium naphthalene sulfonate and a combination thereof.

  2. Sulfonation of polyester fabrics by gaseous sulfur oxide activated by UV irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Kordoghli, Bessem [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); Textile Research Laboratory (LRT) - ISET Kasr Hellal, University of Monastir (Tunisia); Khiari, Ramzi, E-mail: [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); LGP2 - Laboratory of Pulp and Paper Science, 461, Rue de la Papeterie - BP 65, 38402 Saint Martin d' Heres Cedex (France); Mhenni, Mohamed Farouk [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); Sakli, Faouzi [Textile Research Laboratory (LRT) - ISET Kasr Hellal, University of Monastir (Tunisia); Belgacem, Mohamed Naceur [LGP2 - Laboratory of Pulp and Paper Science, 461, Rue de la Papeterie - BP 65, 38402 Saint Martin d' Heres Cedex (France)


    Highlights: Black-Right-Pointing-Pointer In this paper, an original technique was present to improve the hydrophilic properties of polyester fibres. Black-Right-Pointing-Pointer The modification of PET fabric was carried out using gaseous sulfur trioxide activated by UV irradiations. Black-Right-Pointing-Pointer We fully characterized the modified and untreated fabrics. - Abstract: This paper describes an original technique aiming to improve the hydrophilic properties of polyester fibres. In this method, the sulfonation of the aromatic rings is carried out using gaseous sulfur trioxide activated by UV irradiations. Thus, exposing the polyester textile fabric to the UVC light (wavelength around 254 nm) under a stream of sulfur trioxide leads to the fixation of -SO{sub 3}H groups. The amounts of the fixed sulfonate groups depended on the reaction conditions. Evidence of grafting deduced from the measurements of hygroscopic properties was carried out by contact angle measurement, moisture regain as well as by measuring the rate of retention. SEM and FT-IR analysis, DSC and DTA/TGA thermograms showed that no significant modifications have occurred in the bulk of the treated PET fabrics.

  3. Quantitative structure–reactivity study on sulfonation of amines, alcohols and phenols

    Directory of Open Access Journals (Sweden)

    Abolghasem Beheshti


    Full Text Available Quantitative structure–reactivity relationship (QSRR can be considered as a variant of quantitative structure property relationship (QSPR studies, where the chemical reactivity of reactants in a specified chemical reaction is related to chemical structure. As follows, the sulfonation reaction yield of 24 amines, alcohols and phenols with sulfonyl chloride was studied by QSRR. Quantum chemical calculations (b3lyp/6-31+g (d were carried out to obtain the optimized geometry. The suitable set of molecular descriptors was calculated to represent the molecular structures of compounds, such as constitutional, topological, geometrical, electrostatic and quantum-chemical descriptors. The genetic algorithm (GA was applied to select the variables that resulted in the best-fitted models. After the variable selection, multiple linear regression (MLR was utilized to construct linear QSRR models. The maximum relative error in prediction (5.26 showed that the predictive ability of the model was satisfactory and it can be used for designing similar reactants with efficient sulfonation reaction.

  4. Virucidal effects of bleach activators, sodium alkyl acyloxybenzene sulfonate and acyloxybenzoic acid, against Feline calicivirus. (United States)

    Tobe, Seiichi; Hoshi, Marika; Iizuka, Kinue; Tadenuma, Hirohiko; Takaoka, Hiromitsu; Komoriya, Tomoe; Kohno, Hideki


    Noroviruses (NVs) are major causative pathogens of gastroenteritis. The disinfection of contaminated clothing during common household washing is desirable. The virucidal effects of 2 bleach activators, sodium alkyl acyloxybenzene sulfonate (OBS) and alkyl acyloxybenzoic acid (OBC), were studied using Feline calicivirus (FCV) as a surrogate for NVs. FCV was added to solutions containing either OBS or OBC and sodium percarbonate at various temperatures and for varying lengths of time. OBS and OBC, which generate long carbon chain peroxy acids, enhanced the virucidal effect of sodium percarbonate (PC). In particular, sodium lauroyloxybenzene sulfonate (OBS-12) and decanoyloxybenzoic acid (OBC-10) showed superior virucidal effects. Although the virucidal effect of 38-200 mg/L OBS-12 was maintained with 2-5% (v/v) horse serum, there was less of an effect with the same concentration of available chlorine. OBS and OBC have been used as ingredients in some laundry products to increase bleaching activity. It is expected that the use of OBS and OBC is also effective for the inactivation of NVs under common household washing conditions.

  5. Well-Shaped Sulfonic Organosilica Nanotubes with High Activity for Hydrolysis of Cellobiose

    Directory of Open Access Journals (Sweden)

    Jing Sun


    Full Text Available Sulfonic organosilica nanotubes with different acidity densities could be synthesized through the co-condensation of ethenyl- or phenylene-bridged organosilane and 3-mercaptopropyltrimethoxysilane followed by sulfhydryl (–SH oxidation. Transmission electron microscopy (TEM analysis and nitrogen adsorption-desorption experiment clearly exhibit the hollow nanotube structures with the diameters of about 5 nm. The compositions of the nanotube frameworks are confirmed by solid state 13C nuclear magnetic resonance (NMR while X-ray photoelectron spectroscopy (XPS shows that about 60–80% of SH groups were oxidized to sulfonic acid (SO3H. The acid contents were measured by both elemental analysis (CHNS mode and acid-base titration experiment, which revealed that the acid density was in the range of 0.74 to 4.37 μmol·m−2 on the solid. These nanotube-based acid catalysts exhibited excellent performances in the hydrolysis of cellobiose with the highest conversion of 92% and glucose selectivity of 96%. In addition, the catalysts could maintain high activity (65% conversion with 92% selectivity even after six recycles.

  6. Carbon nanotubes-blended poly(phenylene sulfone) membranes for ultrafiltration applications (United States)

    Lawrence Arockiasamy, D.; Alam, Javed; Alhoshan, Mansour


    Multi-walled carbon nanotubes (MWCNT) were carboxylated by a chemical method. Poly(phenylene sulfone) (PPSU), MWCNT and functionalized (carboxylated) MWCNT/poly(phenylene sulfone) (PPSU) blend membranes were synthesized via the phase-inversion method. The resultant membranes were then characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM) and contact angle. The FMWCNT blend membranes appeared to be more hydrophilic, with higher pure water flux than did the pure PPSU and MWCNT/PPSU blend membranes. It was also found that the presence of multi-walled carbon nanotubes (MWCNTs) in the blend membranes was an important factor affecting the morphology and permeation properties of the membranes. The model proteins such as trypsin (20 kDa), pepsin (35 kDa), egg albumin (45 kDa) and bovine serum albumin (69 kDa) rejection experiments were carried out under identical operational conditions employing both PPSU and blend membranes. The membranes were also subjected to the determination of molecular weight cut-off (MWCO) using different molecular weights of proteins. During trypsin ultrafiltration, PPSU/MWCNT and PPSU/FMWCNT membranes showed a slower flux decline rate than did the PPSU membrane.

  7. Calcium carbonate phase transformations during the carbonation reaction of calcium heavy alkylbenzene sulfonate overbased nanodetergents preparation. (United States)

    Chen, Zhaocong; Xiao, Shan; Chen, Feng; Chen, Dongzhong; Fang, Jianglin; Zhao, Min


    The preparation and application of overbased nanodetergents with excess alkaline calcium carbonate is a good example of nanotechnology in practice. The phase transformation of calcium carbonate is of extensive concern since CaCO(3) serves both as an important industrial filling material and as the most abundant biomineral in nature. Industrially valuable overbased nanodetergents have been prepared based on calcium salts of heavy alkylbenzene sulfonate by a one-step process under ambient pressure, the carbonation reaction has been monitored by the instantaneous temperature changes and total base number (TBN). A number of analytical techniques such as TGA, DLS, SLS, TEM, FTIR, and XRD have been utilized to explore the carbonation reaction process and phase transformation mechanism of calcium carbonate. An enhanced understanding on the phase transformation of calcium carbonate involved in calcium sulfonate nanodetergents has been achieved and it has been unambiguously demonstrated that amorphous calcium carbonate (ACC) transforms into the vaterite polymorph rather than calcite, which would be of crucial importance for the preparation and quality control of lubricant additives and greases. Our results also show that a certain amount of residual Ca(OH)(2) prevents the phase transformation from ACC to crystalline polymorphs. Moreover, a vaterite nanodetergent has been prepared for the first time with low viscosity, high base number, and uniform particle size, nevertheless a notable improvement on its thermal stability is required for potential applications. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. Controlled Solution Self-Assembly of a Midblock-Sulfonated Pentablock Copolymer (United States)

    Mineart, Kenneth; Gradzielski, Michael; Spontak, Richard

    The solution self-assembly of midblock-sulfonated block ionomers (SBIs) has been shown to translate to their bulk, solution-cast morphology, which can further impact their function in applications such as desalination, fuel cell, and photovoltaic membranes. Previous studies have identified that increasing the degree of sulfonation (DOS) in SBIs dispersed in a nonpolar solvent results in the growth of micellar aggregates due to increased interfacial energy. However, these works have not attempted to control the assembly at a given DOS by tuning the solvent environment. The current study probes the tunability of SBI aggregation behavior using a nonpolar/polar solvent mixture varying in composition. A combination of light scattering (SLS and DLS) and small angle X-ray scattering (SAXS) independently confirm that SBI micelles grow larger, both in core and corona, as the solvent environment becomes more nonpolar. The increases in both core and corona size will be explained using polymer thermodynamics and further supported through presentation of small angle neutron scattering (SANS) data. In addition, these results will be compared with SBI self-assembly in a single solvent, which is expected to distribute between the micelle cores and bulk solvent environment. We would like to acknowledge funding from NSF IRES (App #1065466) and MANN+HUMMEL GmbH.

  9. Preparation of sulfonic acid-containing rubbers from natural rubber vulcanizates (United States)

    Poonsawat, Worapong; Poompradub, Sirilux; Ngamcharussrivichai, Chawalit


    In this work, a series of sulfonic acid-containing rubbers were prepared by aqueous phase oxidation of natural rubber vulcanizates in the presence of hydrogen peroxide (H2O2) and formic acid (HCOOH). The starting vulcanizates were neatly prepared via an efficient vulcanization (EV) system by varying mass ratio of N-cyclohexyl-2-benzothiazole sulfonamide (CBS), as an accelerator, to sulfur. The oxidation conditions were controlled at the molar ratio of H2O2: HCOOH = 1:1, the concentration of H2O2 = 15 wt.%, the temperature = 50 °C, and the reaction time = 3 h. The rubber materials before and after the oxidation were characterized for their physicochemical properties by using Fourier transform infrared spectroscopy, bomb calorimetry, acid-base titration and swelling measurements. The results indicated the presence of sulfonic acid group in the oxidized rubbers, generated by the oxidative cleaves of sulfide crosslinks in the rubber vulcanizates. The oxidation decreased the sulfur content of the rubber in which the level of sulfur loss was determined by the CBS/sulfur ratio. Moreover, the acidity of the oxidized products was correlated with the amount of sulfur remaining.

  10. Competitive Adsorption of Three Human Plasma Proteins onto Sulfhydryl-to-sulfonate Gradient Surfaces† (United States)

    Ding, Yong-Xue; Hlady, Vladimir


    Competitive adsorption of three human plasma proteins: albumin (HSA), fibrinogen (Fgn), and immunoglobulin G (IgG) from their ternary solution mixtures onto a sulfhydryl-to-sulfonate gradient surface was investigated using spatially-resolved total internal reflection fluorescence (TIRF) and autoradiography. The concentration of each protein in the ternary solution mixture was kept at an equivalent of 1/100 of its physiological concentration in blood plasma. The three proteins displayed different adsorption and desorption characteristics. Each protein adsorbed less to the sulfonate region than to the sulfhydryl region of the gradient. The adsorption-desorption kinetics revealed large differences in the adsorption and desorption rates of three proteins. By fitting the experimental data to a simple model of competitive protein adsorption, the affinity of each protein to the surface at the gradient center position was ranked as: Fgn > HSA ≫ IgG. Competitive exchange of adsorbed proteins was related to the magnitude of desorption rate constants. Such competitive adsorption of the three major human plasma proteins illustrates the complex dynamics of blood proteins – biomaterials interactions. PMID:22279244

  11. Silica-supported sulfonic acids as recyclable catalyst for esterification of levulinic acid with stoichiometric amounts of alcohols

    Directory of Open Access Journals (Sweden)

    Raimondo Maggi


    Full Text Available Converting biomass into value-added chemicals holds the key to sustainable long-term carbon resource management. In this context, levulinic acid, which is easily obtained from cellulose, is valuable since it can be transformed into a variety of industrially relevant fine chemicals. Here we present a simple protocol for the selective esterification of levulinic acid using solid acid catalysts. Silica supported sulfonic acid catalysts operate under mild conditions and give good conversion and selectivity with stoichiometric amounts of alcohols. The sulfonic acid groups are tethered to the support using organic tethers. These tethers may help in preventing the deactivation of the active sites in the presence of water.

  12. Preparation of Highly Sulfonated Ultra-Thin Proton-Exchange Polymer Membranes for Proton Exchange Membrane Fuel Cells (United States)

    Jiang, Zhongqing; Meng, Yuedong; Jiang, Zhong-Jie; Shi, Yicai

    Sulfonated ultra-thin proton-exchange polymer membrane carrying pyridine groups was made from a plasma polymerization of styrene, 2-vinylpyridine, and trifluoromethanesulfonic acid by after-glow capacitively coupled discharge technique. Pyridine groups tethered to the polymer backbone acts as a medium through the basic nitrogen for transfer of protons between the sulfonic acid groups of proton exchange membrane. It shows that the method using present technology could effectively depress the degradation of monomers during the plasma polymerization. Spectroscopic analyses reveal that the obtained membranes are highly functionalized with proton exchange groups and have higher proton conductivity. Thus, the membranes are expected to be used in direct methanol fuel cells.

  13. Design and synthesis of polycyclic sulfones via Diels–Alder reaction and ring-rearrangement metathesis as key steps

    Directory of Open Access Journals (Sweden)

    Sambasivarao Kotha


    Full Text Available Here, we describe a new and simple synthetic strategy to various polycyclic sulfones via Diels–Alder reaction and ring-rearrangement metathesis (RRM as the key steps. This approach delivers tri- and tetracyclic sulfones with six (n = 1, seven (n = 2 or eight-membered (n = 3 fused-ring systems containing trans-ring junctions unlike the conventional all cis-ring junctions generally obtained during the RRM sequence. Interestingly the starting materials used are simple and commercially available.

  14. Use of sodium polystyrene sulfonate in an acute-on-chronic lithium poisoned patient: A case report

    Directory of Open Access Journals (Sweden)

    Chakroun-Walha Olfa


    Full Text Available A 35-year-old woman with an acute-on-chronic lithium overdose received multiple oral doses of sodium polystyrene sulfonate totaling 120 g over a 24-h period. During the 72 h after the institution of therapy, the serum lithium level decreased from 3.80 to 0.42 mEq/L. Multiple doses of sodium polystyrene sulfonate may be useful in lowering the serum lithium level in severely ill patients with acute renal failure, and can substitute hemodialysis.

  15. Membranes of polyindene sulfonated and PVA for use as polymer electrolyte; Membranas mistas de poli(indeno) sulfonado e PVA para uso como eletrolito polimerico

    Energy Technology Data Exchange (ETDEWEB)

    Loser, N.; Silva, B.B.R. da; Brum, F.J.B.; Forte, M.M.C. [Universidade Federal do Rio Grande do Sul - Escola de Engenharia, Porto Alegre, RS (Brazil)


    This study is focused on developing polymer poly electrolytes for fuel cell PEM and aims to evaluate the efficiency of sulfonated polyindene as A polymer electrolyte in blends with poly (vinyl alcohol) (PVA). For this, polyindene synthesized in the lab was functionalized with sulfonic groups (-SO{sub 3}H), using as sulfonation agent acetyl sulfate in 1,2-dichloroethane. The membranes of sulfonated polyindene (SPInd) and PVA were prepared in aqueous medium, using glutaraldehyde as a PVA cross linker. The membranes SPInd/PVA were evaluated on the content of sulfonic groups, ion exchange capacity (IEC), degree of swelling in water and thermal stability (TGA). Electrochemical impedance analysis was used for ionic conductivity evaluation and DMA for the mechanical strength of the membranes. Preliminary results show that the membranes showed ion exchange capacity about 3.2 m equiv/g and degree of swelling in water of 550%. (author)

  16. Synthesis and characterization of sulfonated polymers for ionomeric membranes based on styrene copolymers; Sintese e caracterizacao de precursores sulfonados para membranas polimericas a base de copolimeros estirenicos

    Energy Technology Data Exchange (ETDEWEB)

    Becker, C.M.; Forte, M.M.C.; Amico, S.C. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Escola de Engenharia. Lab. de Materiais Polimericos (LAPOL)], e-mail:, e-mail:, e-mail:; Vargas, J.V.C. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Engenharia Mecanica], e-mail:


    Polymer electrolyte membrane fuel cell (PEMFC) have emerged strongly as a viable alternative for power source owing to their high energy efficiency and environmental friendliness. Currently, Nafion is the most frequently used membrane even though it has a high cost. The objective of this work is to synthesize sulfonated polymers, based on styrene copolymers, with different sulfonation degrees as an alternative material for fuel cell membranes. Acetyl sulfate was used to carry out the sulfonation and the resulting polymers were characterized by Fourier Transform Infra-red (FTIR), thermogravimetric analysis (TGA) and degree of substitution or sulfonation (DS). The polyelectrolytes were evaluated regarding their ion exchange capacity (IEC) and conductivity. The results demonstrated that increasing the sulfonic acid content of the polymer results in higher IEC, conductivity and water uptake. (author)

  17. Sulfonated Holey Graphene Oxide (SHGO) Filled Sulfonated Poly(ether ether ketone) Membrane: The Role of Holes in the SHGO in Improving Its Performance as Proton Exchange Membrane for Direct Methanol Fuel Cells. (United States)

    Jiang, Zhong-Jie; Jiang, Zhongqing; Tian, Xiaoning; Luo, Lijuan; Liu, Meilin


    Sulfonated holey graphene oxides (SHGOs) have been synthesized by the etching of sulfonated graphene oxides with concentrated HNO 3 under the assistance of ultrasonication. These SHGOs could be used as fillers for the sulfonated aromatic poly(ether ether ketone) (SPEEK) membrane. The obtained SHGO-incorporated SPEEK membrane has a uniform and dense structure, exhibiting higher performance as proton exchange membranes (PEMs), for instance, higher proton conductivity, lower activation energy for proton conduction, and comparable methanol permeability, as compared to Nafion 112. The sulfonated graphitic structure of the SHGOs is believed to be one of the crucial factors resulting in the higher performance of the SPEEK/SHGO membrane, since it could increase the local density of the -SO 3 H groups in the membrane and induce a strong interfacial interaction between SHGO and the SPEEK matrix, which improve the proton conductivity and lower the swelling ratio of the membrane, respectively. Additionally, the proton conductivity of the membrane could be further enhanced by the presence of the holes in the graphitic planes of the SHGOs, since it provides an additional channel for transport of the protons. When used, direct methanol fuel cell with the SPEEK/SHGO membrane is found to exhibit much higher performance than that with Nafion 112, suggesting potential use of the SPEEK/SHGO membrane as the PEMs.

  18. Improvement of the chromatographic separation performance of an imidazolium ionic liquid functionalized silica column by in situ anion-exchange with dodecyl sulfonate and dodecylbenzene sulfonate anions. (United States)

    Sun, Min; Feng, Juanjuan; Chen, Wenjie; Li, Leilei; Duan, Huimin; Luo, Chuannan


    The anionic part of ionic liquids can provide additional interactions during chromatographic separations. In this work, the chromatographic separation performance of a silica column functionalized with 1-propyl-3-methylimidazolium chloride ionic liquid was improved by in situ anion-exchange from chloride anions to dodecyl sulfonate anions and dodecylbenzene sulfonate anions. The separation performances of these ionic liquid functionalized phases were investigated and compared with each other using polycyclic aromatic hydrocarbons, phthalates, parabens, and phenols as model compounds. Results indicated that the new columns presented a better chromatographic separation than the original one. This was ascribed retention mechanism from organic anions. The introduction of dodecyl sulfonate anions increased the hydrophobicity of stationary phase. Furthermore, the phenyl groups of dodecylbenzene sulfonate anions could provide an enhanced selectivity to aromatic compounds such as polycyclic aromatic hydrocarbons by π-π interactions. Analysis repeatability of the new columns was satisfactory (RSD of retention time, 0.10-0.40%; RSD of peak area, 0.66-0.84%). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene

    Energy Technology Data Exchange (ETDEWEB)

    Lohrasbi, Elaheh [Department of Chemistry, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Javanbakht, Mehran, E-mail: [Department of Chemistry, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Fuel and Solar Cell Lab, Renewable Energy Research Center, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Mozaffari, Sayed Ahmad [Fuel and Solar Cell Lab, Renewable Energy Research Center, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Thin Layer and Nanotechnology Laboratory, Department of Chemical Technology, Iranian Research Organization for Science and Technology (IROST), Tehran (Iran, Islamic Republic of)


    Highlights: • SO{sub 3}H-graphene supported PtFeCo alloy nanoparticles were prepared. • Co:Fe atomic ratio plays important role in the electrocatalytic performance. • PtCoFe/SG with 7:3 Co:Fe atomic ratio is optimized for PEMFCs. • Power density of 530 mW cm{sup −2} with 0.1 mg cm{sup −2} Pt loading was obtained at 75 °C. - Abstract: The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO{sub 3}− groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm{sup −2} Pt) reaches to a maximum of 530 mW cm{sup −2} at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

  20. PCB and DDE methyl sulfones in mammals from Canada and Sweden

    Energy Technology Data Exchange (ETDEWEB)

    Bergman, A.; Kuroki, Hiroaki (Stockholm Univ. (Sweden). Environmental Chemistry); Norstrom, R.J. (National Research Centre, Hull, Quebec (Canada). Environment Canada); Haraguchi, Koichi (Daiichi Coll. of Pharmaceutical Sciences, Fukuoka (Japan)); Beland, P. (Inst. National d' Ecotoxicologie du Saint-Laurent, Montreal, Quebec (Canada))


    Levels of PCB methyl sulfones (MeSO[sub 2]-CBs) and DDE methyl sulfones (MeSO[sub 2]-DDEs) have been determined in tissues from polar bear (Ursus martimus), beluga whale (Delphinapterus leucas), and false killer whale (Pseudorca crassidens) from the Canadian environment, and grey seal (Halichoerus grypus), otter (Lutra lutra), and wild mink (Mustela vison) from the Swedish environment. Up to 30 MeSO[sub 2]-CB congeners and three MeSO[sub 2]-DdE isomers were shown to be present in the analyzed tissues. The concentration of total MeSO[sub 2]-CBs ranged from 0.1 to 21 [mu]g/g extracted lipids. 3-MeSO[sub 2]-2,5,2[prime],4[prime],5[prime]-penta-CB is the dominating MeSO[sub 2]-CB congener in all the analyzed samples, but the corresponding 4-MeSO[sub 2]-CB also is present in high concentrations. A smaller number of MeSO[sub 2]-CBs, always dominated by the meta-substituted MeSO[sub 2]-CBs, were present in livers of grey seal, otter, and mink than in adipose tissue or muscle. In all studied mammals the concentration of MeSO[sub 2]-CBs were higher in liver than in blubber or muscle. Seven PCB congeners were identified as precursors of the PCB methyl sulfones: 2,4,2[prime],5[prime]-tetra-CB (CB-49),2,5,3[prime],4[prime]-tetra-CB (CB-70), 2,4,5,2[prime],5[prime]-penta-CB (CB-101),2,3,4,5,2[prime],5[prime]-penta-CB (CB-87),2,3,6,2[prime],4[prime],5[prime]-hexa-CB (CB-149),2,3,4,2[prime],3[prime],6[prime]-hexa-CB (CB-132), and 2,3,4,2[prime],5[prime]-hexa-CB (CB-141). All species except beluga whale contained 3-MeSO[sub 2]-4,4[prime]-DDE, but at a much lower concentration in mink and otter than in the other mammals. Polar bear and grey seal liver also contained 2-MeSO[sub 2]-4,4[prime]-DDE. The concentration of 2- and 3-MeSo[sub 2]-DDE ranged from 0.01 to 1.3 [mu]g/g extracted lipids.

  1. Improved oral absorption of cilostazol via sulfonate salt formation with mesylate and besylate

    Directory of Open Access Journals (Sweden)

    Seo JH


    Full Text Available Jae Hong Seo, Jung Bae Park, Woong-Kee Choi, Sunhwa Park, Yun Jin Sung, Euichaul Oh, Soo Kyung Bae College of Pharmacy and Integrated Research Institute of Pharmaceutical Sciences, The Catholic University of Korea, Bucheon, South Korea Objective: Cilostazol is a Biopharmaceutical Classification System class II drug with low solubility and high permeability, so its oral absorption is variable and incomplete. The aim of this study was to prepare two sulfonate salts of cilostazol to increase the dissolution and hence the oral bioavailability of cilostazol.Methods: Cilostazol mesylate and cilostazol besylate were synthesized from cilostazol by acid addition reaction with methane sulfonic acid and benzene sulfonic acid, respectively. The salt preparations were characterized by nuclear magnetic resonance spectroscopy. The water contents, hygroscopicity, stress stability, and photostability of the two cilostazol salts were also determined. The dissolution profiles in various pH conditions and pharmacokinetic studies in rats were compared with those of cilostazol-free base.Results: The two cilostazol salts exhibited good physicochemical properties, such as nonhygroscopicity, stress stability, and photostability, which make it suitable for the preparation of pharmaceutical formulations. Both cilostazol mesylate and cilostazol besylate showed significantly improved dissolution rate and extent of drug release in the pH range 1.2–6.8 compared to the cilostazol-free base. In addition, after oral administration to rats, cilostazol mesylate and cilostazol besylate showed increases in Cmax and AUCt of approximately 3.65- and 2.87-fold and 3.88- and 2.94-fold, respectively, compared to cilostazol-free base.Conclusion: This study showed that two novel salts of cilostazol, such as cilostazol mesylate and cilostazol besylate, could be used to enhance its oral absorption. The findings warrant further preclinical and clinical studies on cilostazol mesylate and

  2. Sulfonated amphiphilic block copolymers : synthesis, self-assembly in water, and application as stabilizer in emulsion polymerization (United States)

    Jiguang Zhang; Matthew R. Dubay; Carl J. Houtman; Steven J. Severtson


    Described is the synthesis of diblock copolymers generated via sequential atom transfer radical polymerization (ATRP) of poly(n-butyl acrylate) (PnBA) followed by chain augmentation with either sulfonated poly(2-hydroxyethyl methacrylate) (PHEMA) or poly(2-hydroxyethyl acrylate) (PHEA) blocks. ATRP of PHEMA or PHEA from PnBA macroinitiator was conducted in acetone/...

  3. Formation of metabolites during biodegradation of linear alkylbenzene sulfonate in an upflow anaerobic sludge bed reactor under thermophilic conditions

    DEFF Research Database (Denmark)

    Mogensen, Anders Skibsted; Ahring, Birgitte Kiær


    Biodegradation of linear alkylbenzene sulfonate (LAS) was shown in an upflow anaerobic sludge blanket reactor under thermophilic conditions. The reactor was inoculated with granular biomass and fed with a synthetic medium and 3 mumol/L of a mixture of LAS with alkylchain length of 10 to 13 carbon...

  4. Synthesis and properties of novel photosensitive poly(arylene ether sulfone) containing chalcone moiety in the main chain

    Energy Technology Data Exchange (ETDEWEB)

    Wen Pushan [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, Hubei Province, South-Central University for Nationalities, Wuhan 430074 (China); Wang Lei [Department of Materials Physics and Chemistry, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Zhang Aiqing [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, Hubei Province, South-Central University for Nationalities, Wuhan 430074 (China); Li Xiangdan, E-mail: [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, Hubei Province, South-Central University for Nationalities, Wuhan 430074 (China); Lee, Myong-Hoon, E-mail: [Department of Polymer/Nano Science and Technology, Chonbuk National University, Jeonju 561-756 (Korea, Republic of)


    Research highlights: {yields} A series of novel photosensitive poly(arylene ether sulfone)s (PAESs) containing chalcone moiety in the main chain have been successfully synthesized. {yields} The photo-crosslinking of polymer film was carried out under UV irradiation without photoinitiator. {yields} The resulting polymers showed good thermal stability and excellent chemical stability after crosslinking. - Abstract: A new series of photosensitive poly(arylene ether sulfone)s containing chalcone moiety in the main chain were synthesized from 4,4'-dihydroxychalcone (4DHC), 4,4'-difluorodiphenylsulfone (DFDPS) and bisphenol A (BPA). This series of polymers were characterized by {sup 1}H NMR, FT-IR, UV spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The polymers were stable up to 400 deg. C, which indicates that the polymers possess good thermal properties. The polymers were found to be soluble in polar solvents and chlorinated solvents. However, the polymers were insoluble in hydrocarbons and in hydroxyl group-containing solvents. After the irradiation of UV light, the thin polymer film was crosslinked to give an insoluble film in the absence of a photoinitiator or sensitizers. The rate of photocrosslinking was also examined and discussed.

  5. Self-assembled monolayers of sulfonate-terminated alkanethiols investigated by frequency modulation atomic force microscopy in liquid (United States)

    Asakawa, Hitoshi; Inada, Natsumi; Hirata, Kaito; Matsui, Sayaka; Igarashi, Takumi; Oku, Norihisa; Yoshikawa, Norinobu; Fukuma, Takeshi


    A molecular-scale understanding of self-assembled monolayers (SAMs) of sulfonate-terminated alkanethiols is crucial for interfacial studies of functionalized SAMs and their various applications. However, such an understanding has been difficult to achieve because of the lack of direct information on these molecular-scale structures in real space. In this study, we investigated the structures of sulfonate SAMs of sodium 11-mercapto-1-undecanesulfonate (MUS) by frequency modulation atomic force microscopy (FM-AFM) in liquid. The subnanometer-resolution FM-AFM images showed that the single-component MUS SAM prepared in pure water had random surface structures. In contrast, the MUS SAM prepared in a water-ethanol mixed solvent showed periodic striped structures with a flat-lying conformation. The results suggest a significant solvent effect on molecular-scale structures of long-chain sulfonate SAMs. In addition, we investigated the molecular-scale structures of mixed SAMs of MUS and 11-mercapto-1-undecanol (MUO) with alkane chains of the same length. The FM-AFM images of the mixed SAMs showed clear phase separation between MUS SAM and MUO SAM domains. In the MUO SAM domains, the incorporated MUS molecules appeared as protrusions. The results obtained in this study provide direct structural information on long-chain sulfonate and mixed SAMs.

  6. Partially Fluorinated Sulfonated Poly(ether amide Fuel Cell Membranes: Influence of Chemical Structure on Membrane Properties

    Directory of Open Access Journals (Sweden)

    Chulsung Bae


    Full Text Available A series of fluorinated sulfonated poly (ether amides (SPAs were synthesized for proton exchange membrane fuel cell applications. A polycondensation reaction of 4,4’-oxydianiline, 2-sulfoterephthalic acid monosodium salt, and tetrafluorophenylene dicarboxylic acids (terephthalic and isophthalic or fluoroaliphatic dicarboxylic acids produced SPAs with sulfonation degrees of 80–90%. Controlling the feed ratio of the sulfonated and unsulfonated dicarboxylic acid monomers afforded random SPAs with ion exchange capacities between 1.7 and 2.2 meq/g and good solubility in polar aprotic solvents. Their structures were characterized using NMR and FT IR spectroscopies. Tough, flexible, and transparent films were obtained with dimethylsulfoxide using a solution casting method. Most SPA membranes with 90% sulfonation degree showed high proton conductivity (>100 mS/cm at 80 °C and 100% relative humidity. Among them, two outstanding ionomers (ODA-STA-TPA-90 and ODA-STA-IPA-90 showed proton conductivity comparable to that of Nafion 117 between 40 and 80 °C. The influence of chemical structure on the membrane properties was systematically investigated by comparing the fluorinated polymers to their hydrogenated counterparts. The results suggest that the incorporation of fluorinated moieties in the polymer backbone of the membrane reduces water absorption. High molecular weight and the resulting physical entanglement of the polymers chains played a more important role in improving stability in water, however.

  7. Long-term effects of a binary mixture of perfluorooctane sulfonate (PFOS) and bisphenol A (BPA) in zebrafish (Danio rerio)

    DEFF Research Database (Denmark)

    Keiter, Susanne; Baumann, Lisa; Farber, H


    Previous in vitro studies have reported the potential of perfluorooctane sulfonate (PFOS) to increase the toxicity of other compounds. Given the complex nature of mixtures of environmental pollutants in aquatic systems together with the persistent and bioaccumulative properties of PFOS, this study...

  8. Modified nanocrystal cellulose/fluorene-containing sulfonated poly(ether ether ketone ketone) composites for proton exchange membranes (United States)

    Wei, Yingcong; Shang, Yabei; Ni, Chuangjiang; Zhang, Hanyu; Li, Xiaobai; Liu, Baijun; Men, Yongfeng; Zhang, Mingyao; Hu, Wei


    Highly sulfonated poly(ether ether ketone ketone)s (SFPEEKKs) with sulfonation degrees of 2.34 (SFPEEKK5) and 2.48 (SFPEEKK10) were synthesized through the direct sulfonation of a fluorene-containing poly(ether ether ketone ketone) under a relatively mild reaction condition. Using the solution blending method, sulfonated nanocrystal cellulose (sNCC)-enhanced SFPEEKK composites (SFPEEKK/sNCC) were successfully prepared for investigation as proton exchange membranes. Transmission electron microscopy showed that sNCC was uniformly distributed in the composite membranes. The properties of the composite membranes, including thermal stability, mechanical properties, water uptake, swelling ratio, oxidative stability and proton conductivity were thoroughly evaluated. Results indicated that the insertion of sNCC could contribute to water management and improve the mechanical performance of the membranes. Notably, the proton conductivity of SFPEEKK5/sNCC-5 was as high as 0.242 S cm-1 at 80 °C. All data proved the potential of SFPEEKK/sNCC composites for proton exchange membranes in medium-temperature fuel cells.


    An easy solvent-free method is described for the conversion of ketones into β-keto sulfones in high yields that involves in situ generation of α-tosyloxyketones followed by nucleophilic substitution with sodium arene sulfinate in presence of tetra-butylammonium bromide at ...

  10. Disruption of the Electrical Conductivity of Highly Conductive Poly(3,4-ethylenedioxythiophene) : Poly(styrene sulfonate) by Hypochlorite

    NARCIS (Netherlands)

    Oostra, A. Jolt; Bos, Karel H.W. van den; Blom, Paul W.M.; Michels, Jasper J.


    The effect of hypochlorite treatment on the layer thickness and conductivity of a state-of-the-art high conducting poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is investigated as a function of exposure time and hypochlorite concentration. Because of overoxidation by the

  11. Transport Properties of Sulfonated Poly (Styrene-b-isobutylene-b-styrene) Triblock Copolymers at High Ion-Exchange Capacities

    National Research Council Canada - National Science Library

    Winey, Karen I; Elabd, Yossef A; Napadensky, Eugene; Walker, Charles W


    ... (IEC), specifically at high IECs (up to -2 mequiv/g). The proton conductivity of S-SIBS was -1 order of magnitude higher than sulfonated polystyrene at similar IECs and 3-fold higher than Nafion 117 at an IEC of 2 mequiv/g...

  12. Analysis of recycled poly (styrene-co-butadiene) sulfonation: a new approach in solid catalysts for biodiesel production. (United States)

    Aguilar-Garnica, Efrén; Paredes-Casillas, Mario; Herrera-Larrasilla, Tito E; Rodríguez-Palomera, Felicia; Ramírez-Arreola, Daniel E


    The disposal of solid waste is a serious problem worldwide that is made worse in developing countries due to inadequate planning and unsustainable solid waste management. In Mexico, only 2% of total urban solid waste is recycled. One non-recyclable material is poly (styrene-co-butadiene), which is commonly used in consumer products (like components of appliances and toys), in the automotive industry (in instrument panels) and in food services (e.g. hot and cold drinking cups and glasses). In this paper, a lab-scale strategy is proposed for recycling poly (styrene-co-butadiene) waste by sulfonation with fuming sulfuric acid. Tests of the sulfonation strategy were carried out at various reaction conditions. The results show that 75°C and 2.5 h are the operating conditions that maximize the sulfonation level expressed as number of acid sites. The modified resin is tested as a heterogeneous catalyst in the first step (known as esterification) of biodiesel production from a mixture containing tallow fat and canola oil with 59% of free fatty acids. The preliminary results show that esterification can reach 91% conversion in the presence of the sulfonated polymeric catalyst compared with 67% conversion when the reaction is performed without catalyst.

  13. 40 CFR 417.100 - Applicability; description of the air-SO3 sulfation and sulfonation subcategory. (United States)


    ... 40 Protection of Environment 28 2010-07-01 2010-07-01 true Applicability; description of the air-SO3 sulfation and sulfonation subcategory. 417.100 Section 417.100 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS SOAP AND DETERGENT MANUFACTURING...

  14. Perfluorooctane sulfonate plasma half-life determination and long term tissue distribution in beef cattle (Bos taurus) (United States)

    Perfluorooctane sulfonate (PFOS) is used in consumer products as a surfactant and is found in industrial and consumer waste which ends up in wastewater treatment plants (WWTPs). PFOS does not breakdown during WWTP processes and accumulates in the biosolids. Common practices include application of bi...

  15. Effect of electric permittivity of the solvent on aggregation process of the water-soluble sulfonated metal phthalocyanines

    Czech Academy of Sciences Publication Activity Database

    Palewska, K.; Sworakowski, J.; Lipinski, J.; Nešpůrek, Stanislav


    Roč. 223, 2/3 (2011), s. 149-156 ISSN 1010-6030 R&D Projects: GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z40500505 Keywords : electronic spectra * absorption * fluorescence Subject RIV: CA - Inorganic Chemistry Impact factor: 2.421, year: 2011

  16. Demarcation of mutant-carrying regions in barley plants after ethylmethane-sulfonate seed treatment

    DEFF Research Database (Denmark)

    Jacobsen, P.


    The branching pattern of the barley plant is analyzed and the anatomical structure of the resting barley embryo studied in longitudinal and cross-sections as well as by dissection techniques. The frequency and distribution of ethylmethane-sulfonate induced chloroplast and morphological seedling...... mutants were analyzed in spikes classified according to their ontogenetic relationship. The frequency with which two spikes segregated identical mutants was determined by pairwise comparisons of all spikes in each plant. In this way the frequency of mutant cluster sharing between spikes and spike groups...... was obtained.The absence of cluster sharing allows the recognition in the barley plant of 8 mutually exclusive mutant sectors which never had a mutant cluster in common. The anatomical analysis proves that the barley embryo contains at least 6 separate shoot meristems or prospective shoot meristems, which...

  17. Spectrophotometric Determination of Zinc Using 7-(4-Nitrophenylazo-8-Hydroxyquinoline-5-Sulfonic Acid

    Directory of Open Access Journals (Sweden)

    Korn Maria das Graças Andrade


    Full Text Available A sensitive and selective spectrophotometric method is proposed for the rapid determination of zinc(II using an 8-hydroxyquinoline derivative, 7-(4-nitrophenylazo-8-hydroxyquinoline-5-sulfonic acid (p-NIAZOXS, as a new spectrophotometric reagent. The reaction between the p-NIAZOXS and zinc(II is instantaneous at pH 9.2 (borax buffer and the absorbance remains stable for over 24 h. The method allows the determination of zinc over the range of 0.05-1.0 mug mL-1 with a molar absorptivity of 3.75x10(4 L mol-1 cm-1 and features a detection limit of 15 ng mL-1. The proposed method has been successfully applied to the determination of zinc in several pharmaceutical preparations and copper alloys. The precision (R.S.D. < 2% and the accuracy obtained were satisfactory.

  18. Passive sampling of perfluorinated acids and sulfonates using polar organic chemical integrative samplers. (United States)

    Fedorova, Ganna; Golovko, Oksana; Randak, Tomas; Grabic, Roman


    The applicability of a polar organic chemical integrative sampler (POCIS) for detection and determination of perfluorinated acids and sulfonates in water was studied under field conditions. Standard POCIS configurations (i.e., pharmaceutical and pesticide) were deployed in effluent from a wastewater treatment plant for 1, 2, and 3 weeks. Ten of 15 target compounds were found in POCIS, five of which were quantified in wastewater. Pest-POCIS appeared more effective for the sampling, while Pharm-POCIS had a more rapid uptake kinetic, which leads to faster saturation or equilibrium. The results showed that the pesticide configuration is probably more suitable for the sampling of this class of compounds. Based on average concentration in water over the sampling period and amount of compound adsorbed in the POCIS, we calculated sampling rates for five studied compounds and obtained values of 0.034 to 0.222 L day(-1).

  19. Synthesis and photopolymerization kinetics of a novel oxime ester sulfonic acid photoacid generator (United States)

    Pang, Yu-Lian; Zou, Ying-Quan


    On the basis of the chemical structure of (5-Hydroxyimino-5H-thiophen-2-ylidene)-phenylacetonitrile, we synthesized a novel sulfonic oxime ester photoacid generator named (5-Ptoluenesulfonyloxyimino- 5H-thiophen-2-ylidene)-phenyl-acetonitrile (TTPA),which was an efficient Photoacid generator (PAG) for 405nm violet laser imaging system.It was synthesized from 2- Nitrothiophen ,Phenylqceto-nitrile and P-toluenesulfonyl chloride.TTPA was characterized by FTIR1HNMR and UV absorption spectra. Real time infrared spectroscopy(RTIR) was used to investigate the effect of different monomers system and different concentrations of TTPA on the polymerization kinetics. The results showed that with the concentration of TTPA increase, with limits, the rate of photopolymerization(Rp) and final double bond conversion increased and the induction period shortened.

  20. Interactions between halloysite nanotubes and poly(styrene sulfonate) in solution

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jae Heon; Ryu, Jung Ju; Shin, Joo Huei; Lee, Hoik; Sohn, Dae Won [Dept. of Chemistry and Research Institute for Convergence of Basic Science, Hanyang University, Seoul (Korea, Republic of); Kim, Ick Soo [Nano Fusion Technology Research Lab, Division of Frontier Fibers, Institute for Fiber Engineering (IFES), Interdisciplinary Cluster for Cutting Edge Research (ICCER), Shinshu University, Nagano (Japan)


    The interaction between halloysite nanotubes (HNT) and poly(styrene sulfonate) (PSS) in aqueous solution was investigated by dynamic light scattering. Dynamic behavior of HNT/PSS was observed with different salt, HNT, and PSS concentrations. The HNT colloids were stabilized by PSS over a wide range of HNT concentrations, and HNT suspension in dilute solution formed stable HNT/PSS particles. On the other hand, HNT particles aggregated as sediments at higher concentrations due to strong attraction among HNT rods, and HNT aggregates were stabilized by additional PSS. The interactions between HNT and PSS are described by the van der Waals–London force (VDWL). The stabilization process of HNT/PSS particles in salt solution was proposed by comparing the hydrodynamic radii and apparent intensities of samples. The results demonstrate that electrostatic, steric, and depletion stabilization processes are responsible for the stable dispersion of HNT even at high concentration.

  1. Pulsed-field capillary electrophoresis: optimizing separation parameters with model mixtures of sulfonated polystyrenes. (United States)

    Sudor, J; Novotny, M V


    The electrophoretic transport of high molecular weight charged solutes, both flexible and stiff polymers, has been studied by capillary electrophoresis under constant-field and pulsed-field conditions. Sulfonated polystyrenes were used as model solutes in different entangled polymer solutions. First, changes of the end-to-end distance vectors of flexible polymers were examined through the mobility/potential-gradient curves. Under pulsed-field conditions, the influence of different pulse shapes, frequencies, and amplitudes of forward and backward pulses on the electrophoretic mobilities of model solutes was studied. Resolution of the mixture components was strongly affected by changes in frequency of both sine-wave and square-wave pulses. The experimental results obtained under pulse-field conditions are roughly in agreement with the existing theories of electrophoretic transport.

  2. Evaluation of sodium lignin sulfonate as draw solute in forward osmosis for desert restoration

    KAUST Repository

    Duan, Jintang


    Sodium lignin sulfonate (NaLS), an abundant waste product of paper manufacturing, can be used in desert restoration. Combined with water and applied on arid land, NaLS has been shown to stabilize sand and provide a medium for plant growth. Here, we demonstrate that NaLS is an efficient draw solute in forward osmosis (FO) to extract water from impaired sources. The osmotic pressure of a 600. g. NaLS/kg water solution is 78. bar (7.8 MPa) as measured by freezing point depression. The FO performance using NaLS draw solute was evaluated with commercial FO membranes under various test conditions. The effects of draw solute concentration, feed salinity and membrane orientation were systematically investigated. Potential ways to optimize the process, e.g. combining fertilizer draw solutes and NaLS, are proposed. © 2013 Elsevier B.V.

  3. Floral mutation in anthurium cv. valentino after induction by ethylmethane sulfonate

    Directory of Open Access Journals (Sweden)

    Susanon, T.


    Full Text Available Meristematic nodular calli of anthurium cv. valentino were treated with ethylmethane sulfonate (EMS at various concentrations for 90 min in order to find the optimum concentration (LD50. Plantlets regenerated from treated calli were grown in the field until flowering. During this period morphological characteristics of the flower were investigated. The results revealed that EMS at concentration 0.5 and 0.75% gave survival percentages of the calli of 60 and 34%, respectively (LD50 = 0.62%. Treatment with EMS at 0.75% gave smaller size of spathe compare with the control having 14.2% yellow spadix. EMS at 1% gave 60% yellow spadix, whereas the control treatment gave pink spadix. Moreover, spadices from those treated with EMS were shorter with more erect angle (45-90º than the control treatment (25º. Development of female flower was 0-50% (control treatment produced 100% female flower.

  4. Sawdust Ash as Powder Material for Self-Compacting Concrete Containing Naphthalene Sulfonate

    Directory of Open Access Journals (Sweden)

    Augustine U. Elinwa


    Full Text Available Tests are carried out to determine the fluidity of Ashaka Portland cement paste and its compatibility with sawdust ash (SDA as powder material for self-compacting cement (SCC mixtures. Results of the investigation showed that saturation was achieved at w/c ratios of 0.4 and 0.42, at dosages of naphthalene sulfonate superplasticizers of 3.5% and 2%, respectively. The optimum replacement level for the SCC mixture was 10 wt.% of cement by SDA and 2% of the superplasticizer dosage. The achieved spread and flow time were 26 cm and 8 seconds and are within the specified range of 24 cm to 26 cm and 7 to 11 seconds, respectively. Statistical inference showed that the mix, w/c, and the interaction between the mix and w/c ratio are significant.

  5. High electrokinetic energy conversion efficiency in charged nanoporous nitrocellulose/sulfonated polystyrene membranes. (United States)

    Haldrup, Sofie; Catalano, Jacopo; Hansen, Michael Ryan; Wagner, Manfred; Jensen, Grethe Vestergaard; Pedersen, Jan Skov; Bentien, Anders


    The synthesis, characterization, and electrokinetic energy conversion performance have been investigated experimentally in a charged polymeric membrane based on a blend of nitrocellulose and sulfonated polystyrene. The membrane is characterized by a moderate ion exchange capacity and a relatively porous structure with average pore diameter of 11 nm. With electrokinetic energy conversion, pressure can be converted directly into electric energy and vice versa. From the electrokinetic transport properties, a remarkably large intrinsic maximum efficiency of 46% is found. It is anticipated that the results are an experimental verification of theoretical models that predict high electrokinetic energy conversion efficiency in pores with high permselectivity and hydrodynamic slip flow. Furthermore, the result is a promising step for obtaining efficient low-cost electrokinetic generators and pumps for small or microscale applications.

  6. Crystal structure of bis[bis(4-azaniumylphenyl sulfone] tetranitrate monohydrate

    Directory of Open Access Journals (Sweden)

    Amani Hind Benahsene


    Full Text Available In the title compound, the hydrated tetra(nitrate salt of dapsone (4,4′-diaminodiphenylsulfone, 2C12H14N2O2S2+·4NO3−·H2O {alternative name: bis[bis(4,4′-diazaniumylphenyl sulfone] tetranitrate monohydrate}, the cations are conformationally similar, with comparable dihedral angles between the two benzene rings in each of 70.03 (18 and 69.69 (19°. In the crystal, mixed cation–anion–water molecule layers lying parallel to the (001 plane are formed through N—H...O, O—H...O and C—H...O hydrogen-bonding interactions and these layers are further extended into an overall three-dimensional supramolecular network structure. Inter-ring π–π interactions are also present [minimum ring centroid separation = 3.693 (3 Å].

  7. Selective Preparation of Furfural from Xylose over Sulfonic Acid Functionalized Mesoporous Sba-15 Materials

    Directory of Open Access Journals (Sweden)

    Panpan Li


    Full Text Available Sulfonic acid functionalized mesoporous SBA-15 materials were prepared using the co-condensation and grafting methods, respectively, and their catalytic performance in the dehydration of xylose to furfural was examined. SBA-15-SO3H(C prepared by the co-condensation method showed 92–95% xylose conversion and 74% furfural selectivity, and 68–70% furfural yield under the given reaction conditions. The deactivation and regeneration of the SBA-15-SO3H(C catalyst for the dehydration of xylose was also investigated. The results indicate that the used and regeneration catalysts retained the SBA-15 mesoporous structure, and the S content of SBA-15-SO3H(C almost did not change. The deactivation of the catalysts is proposed to be associated with the accumulation of byproducts, which is caused by the loss reaction of furfural. After regeneration by H2O2, the catalytic activity of the catalyst almost recovered.

  8. Carbon nanoparticle surface functionalisation: converting negatively charged sulfonate to positively charged sulfonamide. (United States)

    Watkins, John D; Lawrence, Ruth; Taylor, James E; Bull, Steven D; Nelson, Geoffrey W; Foord, John S; Wolverson, Daniel; Rassaei, Liza; Evans, Nick D M; Gascon, Silvia Antón; Marken, Frank


    The surface functionalities of commercial sulfonate-modified carbon nanoparticles (ca. 9-18 nm diameter, Emperor 2000) have been converted from negatively charged to positively charged via sulfonylchloride formation followed by reaction with amines to give suphonamides. With ethylenediamine, the resulting positively charged carbon nanoparticles exhibit water solubility (in the absence of added electrolyte), a positive zeta-potential, and the ability to assemble into insoluble porous carbon films via layer-by-layer deposition employing alternating positive and negative carbon nanoparticles. Sulfonamide-functionalised carbon nanoparticles are characterised by Raman, AFM, XPS, and voltammetric methods. Stable thin film deposits are formed on 3 mm diameter glassy carbon electrodes and cyclic voltammetry is used to characterise capacitive background currents and the adsorption of the negatively charged redox probe indigo carmine. The Langmuirian binding constant K = 4000 mol(-1)dm(3) is estimated and the number of positively charged binding sites per particle determined as a function of pH.

  9. Re-evaluation of turbidimetry of proteins by use of aromatic sulfonic acids and chloroacetic acids. (United States)

    Ebina, S; Nagai, Y


    From studies on 11 different proteins (including native albumin and albumin with reduced disulfide-bridges) treated with sulfosalicylic, 2-naphthalenesulfonic, toluenesulfonic, dichloroacetic, or trichloroacetic acids, we elucidate the interactions determining the resulting turbidities and other factors affecting turbidities, and we discuss the clinical utility of such turbidimetry. At least three interactions are important in determining turbidity: reduction of positive charges on the protein, hydrogen bonding of the non-ionized chloroacetic acids with the protein, and hydrophobic interaction of the aromatic sulfonic acids with albumin. Turbidity varies appreciably with the species of acid and protein, concentrations of acid, temperature, and standing time after acid is added. We conclude that this technique should be restricted to confirming proteinuria.

  10. [Resonance scattering spectral assay of papain enzymatic activity with sodium dodecyl benzene sulfonate]. (United States)

    Huang, Guo-xia; Jiang, Zhi-liang; Liang, Ai-hui; Deng, Ye-cheng


    In pH 6.5 phosphate buffer solutions, dodecyl benzene sulfonate (SDBS) was combined with casein to form association particles, which exhibited five Rayleigh scattering peaks at 470, 360, 400, 420 and 520 nm, respectively. Under suitable conditions, papain has catalytic effect on the hydrolysis of casein, and SDBS can stop the catalytic reaction and be combined with the excess casein to form association particles. The scattering peak at 470 nm decreased with the activity of papain. The delta I470 value was linear with the papain activity in the range of 0.048-4.8 USP x mL(-1). Its regress equation is delta I(SDBS) = 1.972c + 2.31, with a related coefficient of 0.9999 and detection limit of 0.020 USP x mL(-1). This new assay has been applied to the assay of the papain activity in food additive with satisfactory results.

  11. Fluorescence enhancement of the protein-curcumin-sodium dodecyl benzene sulfonate system and protein determination. (United States)

    Wang, Feng; Yang, Jinghe; Wu, Xia; Wang, Fei; Liu, Shufang


    Protein can greatly enhance the fluorescence of curcumin (CU) in the presence of sodium dodecyl benzene sulfonate (SDBS). Experiments indicate that under the optimum conditions, the enhanced intensity of fluorescence is proportional to the concentration of proteins in the range of 0.0050-20.0 microg mL(-1) for bovine serum albumin (BSA), 0.080-20.0 microg mL(-1) for human serum albumin (HSA), and 0.040-28.0 microg mL(-1) for egg albumin (EA). Their detection limits (S/N = 3) are 1.4 ng mL(-1), 20 ng mL(-1), and 16 ng mL(-1), respectively. The method has been satisfactorily used for the determination of proteins in actual samples. In comparison with most of fluorimetric methods, this method is quick and simple, has high sensitivity and good stability. The interaction mechanism is also studied.

  12. Synthesis of Bioactive Fluorinated 10H-Phenothiazines and their Sulfone Derivatives

    Directory of Open Access Journals (Sweden)

    Yogesh Dixit


    Full Text Available The present communication deals with the synthesis of a series of fluorinated 10H-phenothiazines. 10H-phenothiazines is prepared by Smiles rearrangement of substituted 2-foramido-2´-nitrodiphenylsulfide. Substituted 2-foramido-2´-nitrodiphenylsulfide were obtained by the reaction of 2-amino-3-fluorobenzenethiol with o-halonitrobenzenes followed by formylation and 1-nitro/1-halo-10H-phenothiazines have been prepared by the reaction of substituted 2-aminobenzenethiols with reactive o-halonitrobenzene containing a nitro group or halogen atom at o-position to the reactive halogen atom directly yielded 1-nitro/1-halo-10H-phenothiazines in situ. 10H-phenothiazine sulfone derivatives have been synthesized by the oxidation of 10H-phenothiazines by 30% hydrogen peroxide in glacial acetic acid. The structure of the synthesized compounds has been characterized by spectroscopic data and elemental analysis. Antimicrobial studies of the synthesized compounds have also been included.

  13. Perfluorooctanoic acid and perfluorooctane sulfonate in the sediment of the Roter Main river, Bayreuth, Germany

    Energy Technology Data Exchange (ETDEWEB)

    Becker, Anna M.; Gerstmann, Silke [Environmental Chemistry and Ecotoxicology, University of Bayreuth, Universitaetsstr. 30, D-95440 Bayreuth (Germany); Frank, Hartmut [Environmental Chemistry and Ecotoxicology, University of Bayreuth, Universitaetsstr. 30, D-95440 Bayreuth (Germany)], E-mail:


    Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are widely distributed in aquatic ecosystems. Their sources are known but few studies about their accumulation potential in river sediments exist. The aim of this study is to assess the concentrations of PFOA and PFOS in sediments in relation to their levels in river water receiving effluent from a waste water treatment plant (WWTP). PFOS accumulates by a factor of about 40 relative to river water, PFOA only up to threefold. In contrast to previous suggestions, in this case the enrichment on sediment is not correlated to the total organic carbon contents. - River sediments constitute a sink of perfluorinated surfactants released from the waste water treatment plant.

  14. Occurrence of sulfonated steroids and ovarian expression of steroid sulfatase and SULT1E1 in cyclic cows. (United States)

    Blaschka, Carina; Schuler, Gerhard; Sánchez-Guijo, Alberto; Zimmer, Bettina; Feller, Sabine; Kotarski, Franziska; Wudy, Stefan A; Wrenzycki, Christine


    Historically sulfonated steroids were primarily considered as inactive metabolites destined for elimination. However, more recently they have been increasingly recognized as precursors for the production of bioactive steroids in target tissues and as functional molecules without preceding hydrolysis. In order to comprehensively characterize their occurrence in cyclic cows and their formation and hydrolysis in bovine ovarian steroidogenesis, ovaries from cyclic cows were screened for the expression of oestrogen sulfotransferase (SULTE1) and steroid sulfatase (STS) by Western blot and immunohistochemistry. Moreover, a broad spectrum of 13 sulfonated steroids was measured applying liquid chromatography-tandem mass spectrometry (LC-MS/MS) in blood samples collected from three cycling heifers during defined stages of the ovarian cycle and in fluid obtained from ovarian follicles of different size. SULT1E1 was undetectable in ovarian tissues. For STS only a weak immunostaining was found predominantly in granulosa cells of larger follicles. However, no specific band occurred in Western blot. In blood, concentrations of all sulfonated steroids investigated were below the limit of quantification (LOQ). In follicular fluid, only cholesterol sulfate was measured in considerable concentrations (328.3 ± 63.8 ng/ml). However, the role of cholesterol sulfate in bovine follicular steroidogenesis remains unclear as concentrations were obviously unrelated to follicular size. The remaining sulfonated steroids investigated were undetectable or only slightly exceeded LOQ in a minor proportion of samples. The results are clearly contrary to a role of sulfonated steroids as important precursors, intermediates or products of bovine ovarian steroidogenesis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Characterization of Polyethylene-Graft-Sulfonated Polyarylsulfone Proton Exchange Membranes for Direct Methanol Fuel Cell Applications. (United States)

    Kim, Hyung Kyu; Zhang, Gang; Nam, Changwoo; Chung, T C Mike


    This paper examines polymer film morphology and several important properties of polyethylene-graft-sulfonated polyarylene ether sulfone (PE-g-s-PAES) proton exchange membranes (PEMs) for direct methanol fuel cell applications. Due to the extreme surface energy differences between a semi-crystalline and hydrophobic PE backbone and several amorphous and hydrophilic s-PAES side chains, the PE-g-s-PAES membrane self-assembles into a unique morphology, with many proton conductive s-PAES channels embedded in the stable and tough PE matrix and a thin hydrophobic PE layer spontaneously formed on the membrane surfaces. In the bulk, these membranes show good mechanical properties (tensile strength >30 MPa, Young's modulus >1400 MPa) and low water swelling (λ 3 mmol/g in the s-PAES domains. On the surface, the thin hydrophobic and semi-crystalline PE layer shows some unusual barrier (protective) properties. In addition to exhibiting higher through-plane conductivity (up to 160 mS/cm) than in-plane conductivity, the PE surface layer minimizes methanol cross-over from anode to cathode with reduced fuel loss, and stops the HO• and HO₂• radicals, originally formed at the anode, entering into PEM matrix. Evidently, the thin PE surface layer provides a highly desirable protecting layer for PEMs to reduce fuel loss and increase chemical stability. Overall, the newly developed PE-g-s-PAES membranes offer a desirable set of PEM properties, including conductivity, selectivity, mechanical strength, stability, and cost-effectiveness for direct methanol fuel cell applications.

  16. Poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Mi-Lim; Choi, Jisun; Woo, Hyun-Su; Kumar, Vinod; Sohn, Joon-Yong; Shin, Junhwa, E-mail:


    Highlights: • PEEK-g-PVBSA, a polymer electrolyte membrane was prepared by a radiation grafting technique. • Poly(ether ether ketone) (PEEK), an aromatic hydrocarbon polymer was used as a grafting backbone film. • The water uptake, proton conductivity, and methanol permeability of the membranes were evaluated. • PEEK-g-PVBSA membranes show considerably lower methanol permeability compared to a Nafion membrane. -- Abstract: In this study, an aromatic hydrocarbon based polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) (PEEK-g-PVBSA), has been prepared by the simultaneous irradiation grafting of vinylbenzyl chloride (VBC) monomer onto a PEEK film and subsequent sulfonation. Each chemical conversion was monitored by FT-IR and SEM–EDX instruments. The physicochemical properties including IEC, water uptake, proton conductivity, and methanol permeability of the prepared membranes were also investigated and found that the values of these properties increase with the increase of degree of grafting. It was observed that the IEC values of the prepared PEEK-g-PVBSA membranes with 32%, 58%, and 80% DOG values were 0.50, 1.05, and 1.22 meq/g while the water uptakes were 14%, 20%, and 21%, respectively. The proton conductivities (0.0272–0.0721 S/cm at 70 °C) were found to be somewhat lower than Nafion 212 (0.126 S/cm at 70 °C) at a relative humidity of 90%. However, the prepared membranes showed a considerably lower methanol permeability (0.61–1.92 × 10{sup −7} cm{sup 2}/s) compared to a Nafion 212 membrane (5.37 × 10{sup −7} cm{sup 2}/s)

  17. Meso- and macroporous sulfonated starch solid acid catalyst for esterification of palm fatty acid

    Directory of Open Access Journals (Sweden)

    Ibrahim M. Lokman


    Full Text Available In the present work, a heterogeneous solid acid catalyst was successfully developed from starch. The catalyst was prepared by a significant two-step process; the initial step was incomplete carbonization of starch (ICS at 400 °C for 12 h and consequently followed by sulfonation process using concentrated H2SO4 to produce sulfonated-incomplete carbonized starch (ICS-SO3H. The characterization of the ICS-SO3H catalyst was done for chemical and physical properties such as X-ray diffraction (XRD, ammonia-temperature programmed desorption (NH3-TPD, surface area analysis, thermal gravimetric analysis (TGA, elemental analysis and morphology analysis by scanning electron microscope (SEM. BET results showed the structure of ICS-SO3H consists of meso- and macro-porous properties, which allowed high density of the SO3H group attached on its carbon networks. The catalytic activity of ICS-SO3H catalyst was determined by analyzing the catalyst performance to esterify palm fatty acid distillate (PFAD and sequentially produced methyl ester. The maximum free fatty acid (FFA conversion and FAME yield were as high as 94.6% and 90.4%, respectively, at 75 °C using 10:1 methanol-to-PFAD molar ratio and 2 wt.% of catalyst within 3 h. The catalyst has sufficient potential to recycle up to 6 reactions without reactivation step and any remarkable loss of catalytic activity. It revealed that the heterogeneous ICS-SO3H catalyst exhibits high stability, reusability and catalytic activity.

  18. Characterization of Polyethylene-Graft-Sulfonated Polyarylsulfone Proton Exchange Membranes for Direct Methanol Fuel Cell Applications

    Directory of Open Access Journals (Sweden)

    Hyung Kyu Kim


    Full Text Available This paper examines polymer film morphology and several important properties of polyethylene-graft-sulfonated polyarylene ether sulfone (PE-g-s-PAES proton exchange membranes (PEMs for direct methanol fuel cell applications. Due to the extreme surface energy differences between a semi-crystalline and hydrophobic PE backbone and several amorphous and hydrophilic s-PAES side chains, the PE-g-s-PAES membrane self-assembles into a unique morphology, with many proton conductive s-PAES channels embedded in the stable and tough PE matrix and a thin hydrophobic PE layer spontaneously formed on the membrane surfaces. In the bulk, these membranes show good mechanical properties (tensile strength >30 MPa, Young’s modulus >1400 MPa and low water swelling (λ < 15 even with high IEC >3 mmol/g in the s-PAES domains. On the surface, the thin hydrophobic and semi-crystalline PE layer shows some unusual barrier (protective properties. In addition to exhibiting higher through-plane conductivity (up to 160 mS/cm than in-plane conductivity, the PE surface layer minimizes methanol cross-over from anode to cathode with reduced fuel loss, and stops the HO• and HO2• radicals, originally formed at the anode, entering into PEM matrix. Evidently, the thin PE surface layer provides a highly desirable protecting layer for PEMs to reduce fuel loss and increase chemical stability. Overall, the newly developed PE-g-s-PAES membranes offer a desirable set of PEM properties, including conductivity, selectivity, mechanical strength, stability, and cost-effectiveness for direct methanol fuel cell applications.

  19. Investigations of crystallization and ionic interactions of sulfonated syndiotactic polystyrene ionomers (United States)

    Gummaraju, Raghuram


    Syndiotactic polystyrene (sPS) is a semicrystalline polymer that crystallizes rapidly and exhibits several polymorphic crystal structures. Crystallization of sPS from the melt results in an all-trans chain conformation comprised of alpha (hexagonal unit cell) and beta (orthorhombic unit cell) crystal forms. Crystallization of sPS from solution produces helical crystal structures. To ascertain the link between ionic aggregation and crystallization in semicrystalline ionomers, sulfonated syndiotactic polystyrene (SsPS) has been selected as a model system. 23Na SSNMR (Solid-state NMR) spectra have also been utilized to analyze the influence of a surfactant (i.e., dodecyl benzene sodium sulfonate (DBSNa)) on the state of ionic aggregation. Increasing the surfactant content within SsPS ionomers caused a downfield shift coupled with a decrease in width, for the peak corresponding to the ionic aggregates. Added DBSNa molecules can disrupt interactions within the ionic aggregates and consequently weaken the electrostatic network in SsPS. The influence of nonpolar/polar additives on syndiotactic polystyrene was also evaluated utilizing isothermal crystallization, 23Na SSNMR, 13C CPMAS (Cross-polarization Magic-angle spinning) NMR and WAXD (Wide-angle X-ray Diffraction) investigations. To evaluate the influence of crystallization on ionic aggregation in SsPS ionomers, 23Na and 13C SSNMR techniques have been utilized. Polymorphic nature was not significantly affected by the incorporation of ionic groups, as indicated by the identical 13C spectra for sPS and SsPS polymers. A densification of the crystalline domains is likely to affect the conformations of amorphous chains attached to the crystallite surfaces. This perturbation in chain conformation may then result in a disruption of the state of ionic aggregation. The retention of the state of ionic aggregation within SaPS upon annealing clearly indicates that the disruption in the ionic domains of the SsPS ionomer originates

  20. Perfluorooctanoic acid and perfluorooctane sulfonate in Michigan and New York waters

    Energy Technology Data Exchange (ETDEWEB)

    Sinclair, E.; Kannan, K. [Wadsworth Center, Albany, NY (United States); Taniyasu, Sachi; Yamashita, Nobuyoshi [National Institute of Advanced Industrial Science and Technology, Tsukuba (Japan)


    Perfluorooctane sulfonate (PFOS), a perfluorinated organic contaminant, has become the subject of many recent investigations. PFOS and its precursor compounds have been used in a wide variety of consumer and industrial products. Other related perfluorinated compounds have also been reported to occur in the environment. For example, perfluorohexane sulfonate (PFHxS) is an impurity associated with PFOS. Perfluorooctanoic acid (PFOA) has found widespread use as an emulsifier for polymerization of fluoropolymers. These perfluorinated alkylated substances (PASs) are known to be resistant to degradation. Water analysis of PFOS and PFOA has been carried out with several methods. The most commonly used methods involve solid phase extraction (SPE) followed by HPLC-MS-MS. Method detection limits for PFOS and PFOA varied between 5 and 17 ng/L and 9 and 25 ng/L respectively. Generally PFOS and PFOA concentrations in ambient waters, with no point source of pollution, are less than 5 ng/L. We have developed a method using the Oasis HLB solid phase cartridge to achieve the required method detection limits. We have measured PFOS and PFOA concentration in surface waters collected from Michigan and New York. PFOS and PFOA have been detected in the blood and liver of fish at {mu}g/L concentrations both in Japan and the USA. The current ion-pairing, liquid/liquid extraction method is suitable for these concentrations and we have measured PFOS and PFOA in the livers of fish from Michigan and New York waters. We have compared the data for fish and water concentrations and calculated bioaccumulation factors.

  1. Improving the Efficacy of Conventional Therapy by Adding Andrographolide Sulfonate in the Treatment of Severe Hand, Foot, and Mouth Disease: A Randomized Controlled Trial

    Directory of Open Access Journals (Sweden)

    Xiuhui Li


    Full Text Available Background. Herb-derived compound andrographolide sulfonate (called Xiyanping injection recommended control measure for severe hand, foot, and mouth disease (HFMD by the Ministry of Health (China during the 2010 epidemic. However, there is a lack of good quality evidence directly comparing the efficacy of Andrographolide Sulfonate combination therapy with conventional therapy. Methods. 230 patients were randomly assigned to 7–10 days of Andrographolide Sulfonate 5–10 mg/Kg/day and conventional therapy, or conventional therapy alone. Results. The major complications occurred less often after Andrographolide Sulfonate (2.6% versus 12.1%; risk difference [RD], 0.94; 95% CI, 0.28–1.61; P=0.006. Median fever clearance times were 96 hours (CI, 80 to 126 for conventional therapy recipients and 48 hours (CI, 36 to 54 for Andrographolide Sulfonate combination-treated patients (χ2=16.57, P<0.001. The two groups did not differ in terms of HFMD-cause mortality (P=1.00 and duration of hospitalization (P=0.70. There was one death in conventional therapy group. No important adverse event was found in Andrographolide Sulfonate combination therapy group. Conclusions. The addition of Andrographolide Sulfonate to conventional therapy reduced the occurrence of major complications, fever clearance time, and the healing time of typical skin or oral mucosa lesions in children with severe HFMD.

  2. Enhancement of cadmium ion sorption capacity of lignocellulosic bio-sorbent by sulfonation (United States)

    Eun W. Shin; James S. Han; Roger M. Rowell; Soo-Hong Min; James O. Peterson


    Water contaminated by heavy metals remains a serious environmental and public health problem. Cadmium is a toxic heavy metal that not only causes choking, abdominal pain, anemia, renal dysfunction, and diarrhea, but also has been listed as a carcinogen by the EPA (Gaballah and Kibertus, 1998). Among current technologies used to reduce the amount of heavy metals in...

  3. Molecular Supertetrahedron Decorated with Exposed Sulfonate Groups Built from Mixed-Valence Tetranuclear Fe[subscript 3 superscript 3+]Fe[superscript 2+]([mu subscript 3]-Ο)([mu subscript 3]-SO[subscript 4])[subscript 3](−CO[subscript 2])[subscript 3] Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Papadaki, Ioanna; Malliakas, Christos D.; Bakas, Thomas; Trikalitis, Pantelis N.; (Crete); (NWU); (Ioannina)


    We present the synthesis and characterization of a novel metal-organic molecular solid using the ligand 4,8-disulfonaphthalene-2,6-dicarboxylic acid. The solid features a sulfonated, isolated supertetrahedra, [Fe{sub 16}O{sub 4}(SO{sub 4}){sub 12}(L2){sub 6}], built from mixed-valence [Fe{sub 3}{sup 3+}Fe{sup 2+}({mu}{sub 3}-O)({mu}{sub 3}-SO{sub 4}){sub 3}(-CO{sub 2}){sub 3}] clusters.

  4. Process for producing metal oxide superconductor-polymer composites and composites thereby formed

    Energy Technology Data Exchange (ETDEWEB)

    Chien, J.C.W.


    This patent describes a process for producing copper based metal oxide superconductors having continuous foam-like morphology. It comprises: co-dissolving solutions other than metal oxides containing metal ions with a polymer or copolymer in an organic solvent in which the solutions and polymer or copolymer are soluble and of a polar organic solvent type selected from the group consisting of dimethyl formamide, dimethacetamide N-methyl pyrolidone and sulfolan, the the polymer or copolymer being selected from the group consisting of (poly)acrylic acid, (poly)methacrylic acid (poly)styrene sulfonic acid, and copolymers of malonic acid, citraconic acid, acrylonitriles, E-caprolactam, cyclic ethers and cyclic acetals having metal complexing or chelating functional pendant substituents, and a copolymer of vinyl acetate and acrylic acid, and the metals being of the type susceptible of forming high transition temperature metal oxide superconductors with at least some selected from the group consisting of Y, Ba, La and Sr.

  5. Metallization failures (United States)

    Beatty, R.


    Metallization-related failure mechanisms were shown to be a major cause of integrated circuit failures under accelerated stress conditions, as well as in actual use under field operation. The integrated circuit industry is aware of the problem and is attempting to solve it in one of two ways: (1) better understanding of the aluminum system, which is the most widely used metallization material for silicon integrated circuits both as a single level and multilevel metallization, or (2) evaluating alternative metal systems. Aluminum metallization offers many advantages, but also has limitations particularly at elevated temperatures and high current densities. As an alternative, multilayer systems of the general form, silicon device-metal-inorganic insulator-metal, are being considered to produce large scale integrated arrays. The merits and restrictions of metallization systems in current usage and systems under development are defined.

  6. Electrophilic Metal Alkyl Chemistry in New Ligand Environments

    Energy Technology Data Exchange (ETDEWEB)

    Jordan, Richard F. [University of Chicago


    The goals of this project were to design new electrophilic metal alkyl complexes and to exploit these systems in fundamental studies of olefin polymerization and other important and new catalytic reactions. A key target reaction is insertion copolymerization of olefins and polar CH2=CHX vinyl monomers such as vinyl halides and vinyl ethers. During the period covered by this report we (i) investigated the properties of ortho-alkoxy-arylphosphine ligands in Ni-based olefin polymerization catalysts, (ii) studied the synthesis of double-end-capped polyethylene using group 4 metal catalysts that contain tris-pyrazolylborate ligands, (iii) explored the ethylene insertion reactivity of group 4 metal tris-pyrazolyl-borate complexes, (iv) showed that (α-diimine)PdMe{sup +} species undergo multiple insertion of silyl vinyl ethers, (v) synthesized and explored the reactivity of base-free Ni benzyl complexes that contain ortho-phosphino-arene sulfonate ligands, (vi) established the mechanism of the reaction of vinyl chloride with (α-diimine)PdMe{sup +} catalysts, (vii) explored the role of cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (α-diimine)PdMe{sup +} species, (viii) discovered a new class of self-assembled tetranuclear Pd catalysts that produce high molecular weight linear polyethylene and copolymerize ethylene and vinyl fluoride, and (ix) developed model systems that enabled investigation of cis-trans isomerization of {phosphine-sulfonate}Pd(II) complexes.

  7. Electron Capture Dissociation of Divalent Metal-adducted Sulfated N-Glycans Released from Bovine Thyroid Stimulating Hormone (United States)

    Zhou, Wen; Håkansson, Kristina


    Sulfated N-glycans released from bovine thyroid stimulating hormone (bTSH) were ionized with the divalent metal cations Ca2+, Mg2+, and Co by electrospray ionization (ESI). These metal-adducted species were subjected to infrared multiphoton dissociation (IRMPD) and electron capture dissociation (ECD) and the corresponding fragmentation patterns were compared. IRMPD generated extensive glycosidic and cross-ring cleavages, but most product ions suffered from sulfonate loss. Internal fragments were also observed, which complicated the spectra. ECD provided complementary structural information compared with IRMPD, and all observed product ions retained the sulfonate group, allowing sulfonate localization. To our knowledge, this work represents the first application of ECD towards metal-adducted sulfated N-glycans released from a glycoprotein. Due to the ability of IRMPD and ECD to provide complementary structural information, the combination of the two strategies is a promising and valuable tool for glycan structural characterization. The influence of different metal ions was also examined. Calcium adducts appeared to be the most promising species because of high sensitivity and ability to provide extensive structural information.

  8. Corrigendum to "Preparation of Nafion-sulfonated clay nanocomposite membrane for direct menthol fuel cells via a film coating process" [J. Power Sources 165 (2007) 1-2 (United States)

    Kim, Tae Kyoung; Kang, Myeongsoon; Choi, Yeong Suk; Kim, Hae Kyung; Lee, Wonmok; Chang, Hyuk; Seung, Doyoung

    The author regrets that the above paper was printed with an error in the title. The correct title reads: "Preparation of Nafion-sulfonated clay nanocomposite membrane for direct methanol fuel cells via a film coating process".

  9. Review on Modification of Sulfonated Poly (-ether-ether-ketone Membranes Used as Proton Exchange Membranes

    Directory of Open Access Journals (Sweden)

    Xiaomin GAO


    Full Text Available The proton exchange membrane fuel cell (PEMFC is a type of modern power, but the traditional proton exchange membranes (PEM of PEMFC are limited by high methanol permeability and water uptake. Poly-ether-ether-ketone (PEEK is a widely used thermoplastic with good cost-effective property. Sulfonated poly (-ether-ether-ketone (SPEEK has high electric conductivity and low methanol permeability, as well as comprehensive property, which is expected to be used as PEMs. However, the proton exchange ability, methanol resistance, mechanical property and thermal stability of SPEEK are closely related to the degree of sulfonation (DS of SPEEK membranes. Additionally, the proton conductivity, methanol permeability, and stability of SPEEK membranes applied in various conditions need to be further improved. In this paper, the research into modification of SPEEK membranes made by SPEEK and other polymers, inorganic materials are introduced. The properties and modification situation of the SPEEK and the composite membranes, as well as the advantages and disadvantages of membranes prepared by different materials are summarized. From the results we know that, the methanol permeability of SPEEK/PES-C membranes is within the order of magnitude, 10-7cm2/s. The proton conductivity of the SPPESK/SPEEK blend membrane reaches 0.212 S cm-1 at 80 °C. The cross-linked SPEEK membranes have raised thermal and dimensional stability. The non-solvent caused aggregation of the SPEEK ionomers. The proton conductivity of SPEEK/50%BMIMPF6/4.6PA membrane maintains stable as 2.0 x 10-2S cm-1 after 600 h at 160 °C. Incorporation of aligned CNT into SPEEK increases the proton conductivity and reduces the methanol permeability of the composite membranes. The PANI improves the hydrothermal stability. More proton transfer sites lead to a more compact structure in the composite membranes. According to the results, the proton exchange capacity, water uptake, and conductivity of

  10. Sodium dodecyl benzene sulfonate-assisted synthesis through a hydrothermal reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sobhani, Azam [Department of Inorganic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, P.O. Box 87317–51167, Islamic Republic of Iran (Iran, Islamic Republic of); Salavati-Niasari, Masoud, E-mail: [Department of Inorganic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, P.O. Box 87317–51167, Islamic Republic of Iran (Iran, Islamic Republic of); Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317–51167, Islamic Republic of Iran (Iran, Islamic Republic of)


    Graphical abstract: Reaction of a SeCl{sub 4} aqueous solution with a NiCl{sub 2}·6H{sub 2}O aqueous solution in presence of sodium dodecyl benzene sulfonate (SDBS) as capping agent and hydrazine (N{sub 2}H{sub 4}·H{sub 2}O) as reductant, produces nanosized nickel selenide through a hydrothermal method. The effect of temperature, reaction time and amounts of reductant on the morphology, particle sizes of NiSe nanostructures has been investigated. Highlights: ► NiSe nanostructures were synthesized by hydrothermal method. ► A novel Se source was used to synthesize NiSe. ► SDBS as capping agent plays a crucial role on the morphology of products. ► A mixture of Ni{sub 3}Se{sub 2} and NiSe was prepared in the presence of 2 ml hydrazine. ► A pure phase of NiSe was prepared in the presence of 4 or 6 ml hydrazine. -- Abstract: The effects of the anionic surfactant on the morphology, size and crystallization of NiSe precipitated from NiCl{sub 2}·6H{sub 2}O and SeCl{sub 4} in presence of hydrazine (N{sub 2}H{sub 4}·H{sub 2}O) as reductant were investigated. The products have been successfully synthesized in presence of sodium dodecyl benzene sulfonate (SDBS) as surfactant via an improved hydrothermal route. A variety of synthesis parameters, such as reaction time and temperature, capping agent and amount of reducing agent have a significant effect on the particle size, phase purity and morphology of the obtained products. The sample size became bigger with decreasing reaction temperature and increasing reaction time. In the presence of 2 ml hydrazine, the samples were found to be the mixture of Ni{sub 3}Se{sub 2} and NiSe. With increasing the reaction time and amount of hydrazine a pure phase of hexagonal NiSe was obtained. X-ray diffraction analysis (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) images indicate phase, particle size and morphology of the products. Chemical composition and purity of the products were

  11. Sulfonate Ionic Liquid as a Stable and Active Catalyst for Levoglucosenone Production from Saccharides via Catalytic Pyrolysis

    Directory of Open Access Journals (Sweden)

    Jun-ichiro Hayashi


    Full Text Available In this study, various types of ionic liquids (ILs were examined for catalytic activity in the pyrolysis of cellulose for the production of levoglucosenone, which is a valuable and versatile compound for the synthesis of a variety of novel compounds. Cellulose was simply mixed with the ILs and subjected for the pyrolysis, typically at 300 °C, to produce volatile products, including levoglucosenone, separated from the ILs phase. The type of IL anion significantly affected the catalysis, and the use of ILs bearing sulfonate anion resulted in distinguished yields of levoglucosenone and IL recoveries for the reutilization. Detailed thermogravimetric analysis and discussion on properties of ILs revealed the active and thermally stable nature of the sulfonate ILs. Catalytic pyrolysis with those ILs was applied to the conversion of other saccharides composed of glucose molecules, resulting in a preferential formation of levoglucosenone but at low yields as compared to that from cellulose.

  12. Electroactive self-doped poly(amic acid) with oligoaniline and sulfonic acid groups: synthesis and electrochemical properties. (United States)

    Chi, Maoqiang; Wang, Shutao; Liang, Yuan; Chao, Danming; Wang, Ce


    A novel poly(amic acid) with pendant aniline tetramer and sulfonic acid groups (ESPAA) was synthesized by ternary polymerization and characterized by Fourier-transform infrared spectra, ((1))H NMR and gel permeation chromatography. The polymer showed good thermal stability and excellent solubility in the common organic solvents. The electrochemical properties were investigated carefully on a CHI 660A Electrochemical Workstation. The polymer displayed good electroactivity in acid, neutral and even in alkaline solutions (pH=1-10) due to the self-doping effect between aniline tetramer and sulfonic/carboxylic acid groups. It also exhibited satisfactory electrochromic performance with high contrast value, acceptable coloration efficiency and fast switching time in the range of pH=1-9. Copyright © 2014 Elsevier Inc. All rights reserved.

  13. Synthesis and properties of poly(aryl sulfone benzimidazole) and its copolymers for high temperature membrane electrolytes for fuel cells

    DEFF Research Database (Denmark)

    Yang, Jingshuai; Li, Qingfeng; Cleemann, Lars Nilausen


    Poly(aryl sulfone benzimidazole) (SO2PBI) and its copolymers with poly[2,2′-p-(phenylene)-5,5′-bibenzimidazole] (pPBI), termed as Co-SO2PBI, were synthesized with varied feeding ratios of 4,4′-sulfonyldibenzoic acid (SDBA) to terephthalic acid (TPA). Incorporation of the stiff para-phenylene and ......Poly(aryl sulfone benzimidazole) (SO2PBI) and its copolymers with poly[2,2′-p-(phenylene)-5,5′-bibenzimidazole] (pPBI), termed as Co-SO2PBI, were synthesized with varied feeding ratios of 4,4′-sulfonyldibenzoic acid (SDBA) to terephthalic acid (TPA). Incorporation of the stiff para...

  14. Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation. (United States)

    Mirza-Aghayan, Maryam; Tavana, Mahdieh Molaee; Boukherroub, Rabah


    Sulfonated reduced graphene oxide nanosheets (rGO-SO3H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO3H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO3H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56-95%) the corresponding amides in short reaction times. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Highly Efficient Sulfonic/Carboxylic Dual-Acid Synergistic Catalysis for Esterification Enabled by Sulfur-Rich Graphene Oxide. (United States)

    Zhang, Honglei; Luo, Xiang; Shi, Kaiqi; Wu, Tao; He, Feng; Zhou, Shoubin; Chen, George Z; Peng, Chuang


    A new sulfonic/carboxylic dual-acid catalyst based on sulfur-rich graphene oxide (GO-S) was readily prepared and used as a highly efficient and reusable solid acid catalyst toward the esterification of oleic acid with methanol for biodiesel production. Higher yields of methyl oleate (98 %) and over 3 times higher turnover frequencies (TOFs) were observed for the GO-S dual-acid catalyst, compared to liquid sulfuric acid or other carbon-based solid acid catalysts. The "acidity" of sulfonic acid groups was enhanced by the addition of carboxylic acid groups as the combination of the two acids enhances their inherent activity by associative interaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Effects of Concentration of Organically Modified Nanoclay on Properties of Sulfonated Poly(vinyl alcohol Nanocomposite Membranes

    Directory of Open Access Journals (Sweden)

    Apiradee Sanglimsuwan


    Full Text Available Electrolyte nanocomposite membranes for proton exchange membrane fuel cells and direct methanol fuel cells were prepared by carrying out a sulfonation of poly(vinyl alcohol with sulfosuccinic acid and adding a type of organically modified montmorillonite (layered silicate nanoclay commercially known as Cloisite 93A. The effects of the different concentrations (0, 2, 4, 6, 8 wt. % of the organoclay in the membranes on water uptake, ion exchange capacity (IEC, proton conductivity, and methanol permeability were measured, respectively, via gravimetry, titration, impedance analysis, and gas chromatography techniques. The IEC values remained constant for all concentrations. Water uptakes and proton conductivities of the nanocomposite membranes changed with the clay content in a nonlinear fashion. While all the nanocomposite membranes had lower methanol permeability than Nafion115, the 6% concentration of Cloisite 93A in sulfonated poly(vinyl alcohol membrane displayed the greatest proton conductivity to methanol permeability ratio.

  17. Influence of Ligand Backbone Structure and Connectivity on the Properties of Phosphine-Sulfonate Pd(II/Ni(II Catalysts

    Directory of Open Access Journals (Sweden)

    Zixia Wu


    Full Text Available Phosphine-sulfonate based palladium and nickel catalysts have been extensively studied in ethylene polymerization and copolymerization reactions. Previously, the majority of the research works focused on the modifications of the substituents on the phosphorous atom. In this contribution, we systematically demonstrated that the change of the ligand backbone from benzene to naphthalene could greatly improve the properties of this class of catalysts. In the palladium system, this change could increase catalyst stability and polyethylene molecular weights. In the nickel system, this change could dramatically increase the polyethylene molecular weights. Most interestingly, the change in the connectivity of phosphine and sulfonate moieties to the naphthalene backbone could also significantly influence the catalyst properties.

  18. Degradation and desulfurization of dibenzothiophene sulfone and other sulfur compounds by Agrobacterium MC501 and a mixed culture

    Energy Technology Data Exchange (ETDEWEB)

    Constanti, M.; Giralt, J.; Bordons, A. [Universidad de Rovira y Virgili, Tarragona (Spain). Dept. de Bioquimia y Biotecnologia


    Agrobacterium MC501 and the mixed culture composed of Agrobacterium MC501, Xanthomonas MC701, Corynebacterium sp. MC401, and Corynebacterium sp. MC402, all previously isolated from a coal mine area by an enrichment culture with dibenzothiophene (DBT), were used to study DBT sulfone desulfurization. Both cultures were able to use DBT sulfone as a sole source of sulfur for growth. This compound was metabolized to 2-hydroxybiphenyl (2PP) and sulfate. Agrobacterium MC501 and the mixed culture could also utilize a wide range of organic and inorganic sulfur compounds as sources of sulfur such as DBT, thianthrene, diphenylsulfide, thiophene-2-carboxylate, dibutilsulfide, methionine, cysteine, sulfate, and sulfite. Based on these results, the above-mentioned strains can be used to characterize and study coal desulfurization.


    Directory of Open Access Journals (Sweden)

    Jignasa N. Solanki


    Full Text Available Organic/inorganic membranes based on sulfonated poly(vinyl alcohol (SPVA and in situ prepared TiO2 nanoparticles nanocomposite membranes with various compositions were prepared to use as proton exchange membranes in direct membrane fuel cells. Poly(vinyl alcohol (PVA was sulfonated and cross-linked separately by 4-formylbenzene-1,3-disulfonic acid disodium salt hydrate and glutaraldehyde. The ion exchange capacity and proton conductivity of the membranes increased with increasing amount of TiO2 nanoparticles. The composite membranes with 15 wt% TiO2 exhibited excellent proton conductivity of 0.0822 S cm-1, as well as remarkably low methanol permeability of 1.11×10-9 cm2 s-1. The thermal stability and durability were also superior and performance in methanol fuel cell was also reasonably good

  20. Hydrocarbon-based fuel cell membranes: Sulfonated crosslinked poly(1,3-cyclohexadiene) membranes for high temperature polymer electrolyte fuel cells


    Deng, Suxiang; Hassan, Mohammad K.; Kenneth A. Mauritz; Mays, Jimmy W.


    High temperature fuel cell membranes based on poly(1,3-cyclohexadiene) were prepared by a Polymerization-Crosslinking-Sulfonation (PCS) approach, and a broad range of membrane compositions were achieved using various sulfonating reagents and reaction conditions. Membranes were characterized for their proton conductivity and thermal degradation behavior. Some of the membranes showed up to a 68% increase in proton conductivity as compared to Nafion under the same conditions (100% relative humid...

  1. Paeonifiorin sulfonate as a characteristic marker for specifically inspecting Chinese patent medicine Liu-Wei-Di-Huang-Wan contained sulfur-fumigated Moutan Cortex. (United States)

    Li, Xiu-Yang; Long, Fang; Xu, Jin-Di; Shen, Hong; Kong, Ming; Zhu, He; Zhang, Ye-Qing; Li, Song-Lin


    Sulfur fumigation can induce chemical transformation of bioactive components, consequently the alteration of bioactivities or even toxicities of medicinal herbs. Inspecting Chinese patent medicines (CPM) contained sulfur-fumigated constituent herbs is crucial for ensuring the safety and efficacy of CPM. Paeonifiorin sulfonate is a sulfur-fumigation induced compound of Moutan Cortex (MC), one of the main constituent herbs of a commonly used CPM Liu-Wei-Di-Huang-Wan (LWDHW). Herein, we investigated the approach of paeonifiorin sulfonate as a characteristic marker for specifically inspecting LWDHW potentially contained sulfur-fumigated MC (SFMC). First, mimic LWDHW samples contained SFMC (SFMC-LWDHW) and non-fumigated MC (NFMC-LWDHW) were prepared respectively. Second, an LC-MS method was developed and validated to qualitatively and quantitatively determine paeonifiorin sulfonate in the mimic LWDHW samples. Third, the established method was applied to analyze the commercial LWDHW samples. The results showed that paeoniflorin sulfonate could only be detectable in SFMC-LWDHW, but not in NFMC-LWDHW samples. The CPM matrix could enhance the response of paeoniflorin sulfonate in mass spectrometry analysis. In addition, the LOQ, linearity, precision, accuracy and stability were also demonstrated to be acceptable for quantifying paeoniflorin sulfonate in LWDHW. Commercial samples analysis indicated that paeoniflorin sulfonate were detectable in 9 of 10 commercial LWDHW samples, with the content varied between 105.53μg/g and 438.61μg/g. All the results suggested that paeoniflorin sulfonate could be used as a characteristic and reliable chemical marker for specifically inspecting commercial LWDHW contained SFMC. This study also provides a new strategy for the quality control of other CPMs potentially produced from sulfur-fumigated constituent herbs. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Ag nanoparticle/melamine sulfonic acid supported on silica gel as an efficient catalytic system for synthesis of dihydropyrimidinthiones

    Directory of Open Access Journals (Sweden)

    Parya Nasehi


    Full Text Available 3,4-Dihydropyrimidin-2(1H-thiones were synthesized in the presence of Ag nanoparticle/melamine sulfonic acid (MSA supported on silica gel. The reactionwas carried out at 110 oC for 20 min under solvent free conditions. This method hassome advantages such as good yield, mild reaction conditions, ease of operation and work up, short reaction time and high product purity.

  3. Determination of polyamines in Arabidopsis thaliana by capillary electrophoresis using salicylaldehyde-5-sulfonate as a derivatizing reagent


    Inoue, Genki; Kaneta, Takashi; TAKAYANAGI, TOSHIO; Kakehi, Junichi; Motose, Hiroyasu; Takahashi, Taku


    Herein, we report a novel method for the determination of polyamines in a sample extracted from Arabidopsis thaliana by capillary electrophoresis (CE) using salicylaldehyde-5-sulfonate (SAS) as a derivatizing reagent. An aldehyde group of SAS forms a Schiff base with amino groups of aliphatic polyamines, resulting in an anionic species with an absorption band in the ultraviolet region. The derivatization method was straightforward since the derivatives were formed by mixing a sample with the ...

  4. Effect of Linear Alkylbenzene Sulfonate on Mortality, Hatching Rate of Eggs and Abnormality of Catfish (Pangasius hypophthalmus Sauvage Larvae

    Directory of Open Access Journals (Sweden)

    E. Supriyono


    Full Text Available Linear alkylbenzene sulfonate (LAS surfactant in the water can affecting fish in all developmental stages.  This study was aimed to observe the effect of LAS on mortality, hatching rate of eggs, and abnormality of patin catfish (Pangasius hypophthalmus Sauvage larvae.   Fertilized eggs were incubated in water containing LAS at the dosages of 0.0, 0.5, 1.5, 3.0, 9.0, and 18.0 mg/L.  Eggs mortality was observed every 6 hours until larvae hatched (24 hours.  The results of study showed that the exposure of 18.0 mg LAS per liter water could put to death all the fertilized eggs and larvae be abnormal.  The exposure of LAS at concentration of 9.0 mg/L could kill 98% of eggs and hatching rate was only 2%.  The abnormality in larvae was bending in the body and tails. Keywords: patin catfish, Pangasius, Linear Alkylbenzene Sulfonate, LAS, abnormality   ABSTRAK Surfaktan Linear Alkylbenzene Sulfonate (LAS yang masuk ke dalam perairan sangat berpengaruh terhadap ikan dari stadia awal hidup ikan sampai dewasa. Penelitian ini bertujuan untuk mengetahui pengaruh LAS terhadap mortalitas, daya tetas telur dan abnormalitas larva ikan patin (Pangasius hypophthalmus Sauvage.  Telur ikan patin yang telah dibuahi di rendam dalam air yang mengandung LAS dengan konsentrasi 0,0; 0,5; 1,5; 3,0; 9,0 dan 18,0 mg/L.  Mortalitas telur dicatat setiap 6 jam sampai menetas (24 jam.  Hasil penelitian menunjukkan bahwa konsentrasi LAS sebesar 18,0 mg/L dapat mengakibatkan mortalitas telur dan abnormalitas pada larva secara total.  Konsentrasi LAS sebesar 9,0 mg/L dapat mematikan telur hingga 98% dan hanya menghasilkan daya tetas sebanyak 2%. Abnormalitas pada larva berupa pembengkokan pada tubuh dan ekor. Kata kunci: ikan patin, Pangasius, Linear Alkylbenzene Sulfonate, LAS dan abnormalitas

  5. Esterification of oil adsorbed on palm decanter cake into methyl ester using sulfonated rice husk ash as heterogeneous acid catalyst (United States)

    Hindryawati, Noor; Erwin, Maniam, Gaanty Pragas


    Palm Decanter cake (PDC) which is categorized as the waste from palm oil mill has been found to contain residual crude palm oil. The oil adsorbed on the PDC (PDC-oil) can be extracted and potentially used as feedstock for biodiesel production. Feedstock from waste like PDC-oil is burdened with high free fatty acids (FFAs) which make the feedstock difficult to be converted into biodiesel using basic catalyst. Therefore, in this study, a solid acid, RHA-SO3H catalyst was synthesized by sulfonating rice husk ash (RHA) with concentrated sulfuric acid. The RHA-SO3H prepared was characterized with TGA, FTIR, BET, XRD, FE-SEM, and Hammett indicators (methyl red, bromophenol blue, and crystal violet). PDC was found to have about 11.3 wt. % oil recovered after 1 hour extraction using ultrasound method. The presence of sulfonate group was observed in IR spectrum, and the surface area of RHA-SO3H was reduced to 37 m2.g-1 after impregnation of sulfonate group. The RHA-SO3H catalyst showed that it can work for both esterification of free fatty acid which is present in PDC-oil, and transesterification of triglycerides into methyl ester. The results showed highest methyl ester content of 70.2 wt.% at optimal conditions, which was 6 wt.% catalyst amount, methanol to oil molar ratio of 17:1 for 5 hours at 120 °C.

  6. Biotechnological strategies for phytoremediation of the sulfonated azo dye Direct Red 5B using Blumea malcolmii Hook. (United States)

    Kagalkar, Anuradha N; Jagtap, Umesh B; Jadhav, Jyoti P; Bapat, Vishwas A; Govindwar, Sanjay P


    Tissue cultured shrub plants of Blumea malcolmii were found to decolorize Malachite green, Red HE8B, Methyl orange, Reactive Red 2 and Direct Red 5B at 20 mg L(-1) concentration to varying extent within three days. A significant induction in the activities of lignin peroxidase, tyrosinase, DCIP (2,6-dichlorophenol-indophenol) reductase, azoreductase and riboflavin reductase in the roots was observed during the decolorization of Direct Red 5B, which indicated their crucial role in the metabolism of the dye. HPLC (High Performance Liquid Chromatography) and FTIR (Fourier Transform Infrared Spectroscopy) analysis of the samples before and after decolorization of the dye confirmed the phytotransformation of Direct Red 5B. The GC-MS (Gas Chromatography Mass Spectroscopy) analysis of the products led us to the identification of three metabolites formed after phytotransformation of the dye as 4-(4-amino-phenylazo)-benzene sulfonic acid, 3-amino-7-carboxyamino-4-hydroxy-naphthalene-2-sulfonic acid and 7-carboxyamino-naphthalene-2-sulfonic acid.

  7. Synthesis of methyl ester sulfonate surfactant from crude palm oil as an active substance of laundry liquid detergent (United States)

    Slamet, Ibadurrohman, Muhammad; Wulandari, Pangiastika Putri


    Liquid detergent with combination of MES surfactant and TiO2 nanoparticles to remove and degrade the dirt in the form of methylene blue and produce waste with the lowest surfactant residual concentration has been done. The formation of MES is carried out by esterification and transesterification of crude palm oil, sulfonation, refining, and neutralization. The photocatalyst TiO2 nanoparticles is added as an additive to improve surfactant performance in removing dirt and degrading organic compounds. MES formation is performed by varying the mole ratio of the reactants in the esterification and transesterification reactions, and the mole ratios between methyl esters and NaHSO3 during the sulfonation reaction. Variations of MES surfactant and TiO2 nanoparticles compositions were performed to obtain detergent stability. Data analysis technique in this research is characterization of methyl ester, MES surfactant, and detergent using UV-Vis spectrophotometer instrument, FTIR, GC-MS, and LC-MS. The optimum conditions in the esterification and transesterification process were each mole ratio of 1: 6 between CPO and methanol based on the highest conversion, 99%. The optimum condition of the sulfonation process is the 1: 1.5 mole ratio between methyl ester and NaHSO3 based on the lowest surface tension value, which is about 36 dyne/cm.

  8. Synthesis and Characterization of Sulfonated Poly(Phenylene Containing a Non-Planar Structure and Dibenzoyl Groups

    Directory of Open Access Journals (Sweden)

    Hohyoun Jang


    Full Text Available Polymers for application as sulfonated polyphenylene membranes were prepared by nickel-catalyzed carbon-carbon coupling reaction of bis(4-chlorophenyl-1,2-diphenylethylene (BCD and 1,4-dichloro-2,5-dibenzoylbenzene (DCBP. Conjugated cis/trans isomer (BCD had a non-planar conformation containing four peripheral aromatic rings that facilitate the formation of π–π interactions. 1,4-Dichloro-2,5-dibenzoylbenzene was synthesized from the oxidation reaction of 2,5-dichloro-p-xylene, followed by Friedel-Crafts reaction with benzene. DCBP monomer had good reactivity in polymerization affecting the activity of benzophenone as an electron-withdrawing group. The polyphenylene was sulfonated using concentrated sulfuric acid. These polymers without any ether linkages on the polymer backbone were protected from nucleophilic attack by hydrogen peroxide, hydroxide anion, and radicals generated by polymer electrolyte membrane fuel cell (PEMFC operation systems. The mole fraction of the sulfonic acid groups was controlled by varying the mole ratio of bis(4-chlorophenyl-1,2-diphenylethylene in the copolymer. In comparison with Nafion 211® membrane, these SBCDCBP membranes showed ion exchange capacity (IEC ranging from 1.04 to 2.07 meq./g, water uptake from 36.5% to 69.4%, proton conductivity from 58.7 to 101.9 mS/cm, and high thermal stability.

  9. Determination of methiocarb and its degradation products, methiocarb sulfoxide and methiocarb sulfone, in bananas using QuEChERS extraction. (United States)

    Plácido, Alexandra; Paíga, Paula; Lopes, David H; Correia, Manuela; Delerue-Matos, Cristina


    The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LC-PAD). Calibration curves were linear in the range of 0.5-10 mg L⁻¹ for all compounds studied. The average recoveries, measured at 0.1 mg kg⁻¹ wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

  10. The Use of Heterogeneous Catalysts of Chitosan Sulfonate Bead on the Esterification Reaction of Oleic Acid and Methanol (United States)

    Chamidy, H. N.; Riniati


    Biodiesel is one of the ester compounds with physical properties closer to a biodiesel which can be produced by the esterification reaction between methanol and oleic acid (one of major components present in Palm Fatty Acid Distillate, PFAD). The purpose of this study was to obtain an optimum condition of esterification reaction by using chitosan sulfonate bead as heterogeneous catalysts. Chitosan sulfonate bead was made from chitosan undergo sulfonation process using acidic reagents cross-linked with sulfosalicylic and glutaraldehyde with a high enough value of ion exchange capacity. The stage of esterification reactions was carried by varying the amount of catalyst being added (4, 6, 8, 10, 12% by oleic acid), the operating temperature was varied of 40, 50 and 60 °C, and the reaction time of 1, 2, 3, 4 and 5 hours. Conversion determination of the products was done by analysing the free fatty acids content in each sample. Having obtained from the optimum amount of catalyst being added, temperature, and time, it was found that the catalyst was at 8%, 50 °C, during 5 hours in operation. The maximum conversion of oleic acid into biodiesel was 73.12%.

  11. Functionalized carbon nanotube-poly(arylene sulfone) composite membranes for direct methanol fuel cells with enhanced performance

    Energy Technology Data Exchange (ETDEWEB)

    Joo, Sang Hoon; Pak, Chanho; Kim, Eun Ah; Lee, Yoon Hoi; Chang, Hyuk; Seung, Doyoung; Choi, Yeong Suk [Energy and Environment Laboratory, Samsung Advanced Institute of Technology, P.O. Box 111, Suwon, 440-600 (Korea); Park, Jong-Bong [Analytical Engineering Center, Samsung Advanced Institute of Technology, P.O. Box 111, Suwon, 440-600 (Korea); Kim, Tae Kyoung [Research Institute of Chemical and Electronic Materials, Cheil Industries Inc., Uiwang-si, 437-711 (Korea)


    A new type of composite membrane, consisting of functionalized carbon nanotubes (CNTs) and sulfonated poly(arylene sulfone) (sPAS), is prepared for direct methanol fuel cell (DMFC) applications. The CNTs modified with sulfonic acid or PtRu nanoparticles are dispersed within the sPAS matrix by a solution casting method to afford SO{sub 3}CNT-sPAS or PtRu/CNT-sPAS composite membranes, respectively. Characterization of the composite membranes reveals that the functionalized CNTs are homogeneously distributed within the sPAS matrix and the composite membranes contain smaller ion clusters than the neat sPAS. The composite membranes exhibit enhanced mechanical properties in terms of tensile strength, strain and toughness, which leads to improvements in ion conductivity and methanol permeability compared with the neat sPAS membrane. In DMFC performance tests, the use of a PtRu/CNT-sPAS membrane yields high power density compared with the neat sPAS membrane, which demonstrates that the improved properties of the composite membranes induce an increase in power density. The strategy for CNT-sPAS composite membranes presented in this work can potentially be extended to other CNT-polymer composite systems. (author)

  12. Hybrid proton conducting membranes based on sulfonated cross-linked polysiloxane network for direct methanol fuel cell (United States)

    Zhu, Jing; Zhang, Gang; Shao, Ke; Zhao, Chengji; Li, Hongtao; Zhang, Yang; Han, Miaomiao; Lin, Haidan; Li, Mu; Na, Hui

    A series of novel hybrid membranes based on sulfonated poly(arylene ether ketone)s (SNPAEKs), polysiloxane (KH-560) and sulfonated curing agent (BDSA) has been prepared by sol-gel and cross-linking reaction for direct methanol fuel cells (DMFCs). All the hybrid membranes (SKB- xx) show high thermal properties and improved oxidative stability compared with the pristine SNPAEK membrane. The sulfonated cross-linked polysiloxanes networks in the hybrid membranes enhance the mechanical properties and reduce the swelling ratio. The swelling ratio of SKB-20 is 22%, which is much lower than that of the pristine SNPAEK (37%) at 80 °C. Meanwhile, SKB- xx membranes with greatly reduced methanol permeabilities show comparative proton conductivities to pristine SNPAEK membranes. Notably, the proton conductivities of SKB-5 and SKB-10 reach to 0.192 S cm -1 and 0.179 S cm -1 at 80 °C, respectively, which are even higher than the 0.175 S cm -1 of SNPAEK.

  13. Identification of alkylbenzene sulfonate surfactants leaching from an acrylonitrile butadiene rubber as novel inhibitors of calcineurin activity. (United States)

    Ito, Noboru; Shibuguchi, Nao; Ishikawa, Ryoki; Tanaka, Susumu; Tokita, Yoshiharu; Nakajima-Shimada, Junko; Hosaka, Kohei


    Calcineurin (CN) is a Ca(2+)/calmodulin (CaM) dependent serine/threonine protein phosphatase and plays important role in several cellular functions in both higher and lower eukaryotes. Here we report inhibition of CN by linear alkylbenzene sulfonate. The clue to the finding was obtained while identifying the inhibitory material leaching from acrylonitrile butadiene rubber used for packing. Using standard dodecylbenzene sulfonate (C12-LAS), we obtained strong inhibition of CN with a half maximal inhibitory concentration of 9.3 µM, whereas analogs such as p-octylbenzene sulfonate and SDS hardly or only slightly affected CN activity. Three alkaline phosphatases, derived from shrimp, bacteria, and calf-intestine, which exhibit similar enzymatic activities to CN, were not inhibited by C12-LAS at concentrations of up to 100 µM. Furthermore, C12-LAS did not inhibit Ca(2+)/CaM-dependent myosin light chain kinase activity when tested at concentrations of up to 36 µM. The results indicate that C12-LAS is a potent selective inhibitor of CN activity.

  14. Esterification free fatty acid in palm fatty acid distillate using sulfonated rice husk ash catalyst (United States)

    Hidayat, Arif; Sutrisno, Bachrun


    Indonesia, as one of the biggest palm oil producers and exporters in the world, is producing large amounts of low-grade oil such as Palm Fatty Acid Distillate (PFAD) from palm oil industries. The use of PFAD can reduce the cost of biodiesel production significantly, which makes PFAD a highly potential alternative feedstock for biodiesel production. In this paper, the esterification of free fatty acid (FFA) on PFAD was studied using rice husk ash (RHA) as heterogeneous catalyst. The rice husk ash catalyst was synthesized by sulfonation using concentrated sulfuric acid. The RHA catalyst were characterized by using different techniques, such as porosity analysis, Fourier transform infrared (FT-IR) spectroscopy, total number of acid sites and elemental analysis. The effects of the molar ratio of methanol to PFAD (1-10%), the molar ratio of methanol to PFAD (4:1-10:1), and the reaction temperature (40-60°C) were studied for the conversion of FFA to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 10:1, the catalyst amount of 10 wt% of PFAD, and reaction temperature of 60°C.

  15. Structural and magnetic characterization of copper sulfonated phthalocyanine grafted onto treated polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Reznickova, A., E-mail: [Department of Solid State Engineering, University of Chemistry and Technology, 166 28, Prague 6 (Czech Republic); Kolska, Z. [Department of Solid State Engineering, University of Chemistry and Technology, 166 28, Prague 6 (Czech Republic); Faculty of Science, J.E. Purkyne University, 400 96 Usti nad Labem (Czech Republic); Orendac, M.; Cizmar, E. [Faculty of Science, P.J. Safarik University, Park Angelinum 9, 04013 Kosice (Slovakia); Sajdl, P. [Department of Power Engineering, University of Chemistry and Technology, 166 28, Prague 6 (Czech Republic); Svorcik, V. [Department of Solid State Engineering, University of Chemistry and Technology, 166 28, Prague 6 (Czech Republic)


    Highlights: • Polyethylene (PE) surface was activated by argon plasma discharge. • Monolayer of copper phthalocyanine was achieved. • ESR proved that CuPc coated PE surface exhibits magnetic properties. • The studied structures may have potential application in spintronics and data storage. - Abstract: This study focuses on high density polyethylene (HDPE) activated by Ar plasma treatment, subsequently grafted with copper sulfonated phthalocyanine (CuPc) especially pointing out to the surface and magnetic properties of those composites. Properties of pristine PE and their plasma treated counterparts were studied by different experimental techniques: X-ray photoelectron spectroscopy (XPS), UV–vis spectroscopy, zeta potential and by electron spin resonance (ESR). XPS analysis confirmed the successful grafting of phthalocyanine. The highest absorption was found for the sample grafted with {sup b}CuPc for 1 h. Electrokinetic analysis also confirmed the plasma treatment and also subsequent CuPc grafting influence significantly the surface chemistry and charge. These results correspond well with XPS determination. ESR studies confirmed the presence of CuPc grafted on HDPE. It was found, that grafting is mediated by magnetically inactive functional groups, rather than radicals. Magnetic properties of CuPc do not seem to change significantly after grafting CuPc on polyethylene surface.

  16. Enhanced adsorption of perfluorooctane sulfonate and perfluorooctanoate by bamboo-derived granular activated carbon. (United States)

    Deng, Shubo; Nie, Yao; Du, Ziwen; Huang, Qian; Meng, Pingping; Wang, Bin; Huang, Jun; Yu, Gang


    A bamboo-derived granular activated carbon with large pores was successfully prepared by KOH activation, and used to remove perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) from aqueous solution. The granular activated carbon prepared at the KOH/C mass ratio of 4 and activation temperature of 900°C had fast and high adsorption for PFOS and PFOA. Their adsorption equilibrium was achieved within 24h, which was attributed to their fast diffusion in the micron-sized pores of activated carbon. This granular activated carbon exhibited the maximum adsorbed amount of 2.32mmol/g for PFOS and 1.15mmol/g for PFOA at pH 5.0, much higher than other granular and powdered activated carbons reported. The activated carbon prepared under the severe activation condition contained many enlarged pores, favorable for the adsorption of PFOS and PFOA. In addition, the spent activated carbon was hardly regenerated in NaOH/NaCl solution, while the regeneration efficiency was significantly enhanced in hot water and methanol/ethanol solution, indicating that hydrophobic interaction was mainly responsible for the adsorption. The regeneration percent was up to 98% using 50% ethanol solution at 45°C. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Fatty liver disease induced by perfluorooctane sulfonate: Novel insight from transcriptome analysis. (United States)

    Fai Tse, William Ka; Li, Jing Woei; Kwan Tse, Anna Chung; Chan, Ting Fung; Hin Ho, Jeff Cheuk; Sun Wu, Rudolf Shiu; Chu Wong, Chris Kong; Lai, Keng Po


    Perfluorooctane sulfonate (PFOS), a hepato-toxicant and potential non-genotoxic carcinogen, was widely used in industrial and commercial products. Recent studies have revealed the ubiquitous occurrence of PFOS in the environment and in humans worldwide. The widespread contamination of PFOS in human serum raised concerns about its long-term toxic effects and its potential risks to human health. Using fatty liver mutant foie gras (fgr(-/-))/transport protein particle complex 11 (trappc11(-/-)) and PFOS-exposed wild-type zebrafish embryos as the study model, together with RNA sequencing and comparative transcriptomic analysis, we identified 499 and 1414 differential expressed genes (DEGs) in PFOS-exposed wild-type and trappc11 mutant zebrafish, respectively. Also, the gene ontology analysis on common deregulated genes was found to be associated with different metabolic processes such as the carbohydrate metabolic process, glycerol ether metabolic process, mannose biosynthetic process, de novo' (Guanosine diphosphate) GDP-l-fucose biosynthetic process, GDP-mannose metabolic process and galactose metabolic process. Ingenuity Pathway Analysis further highlighted that these deregulated gene clusters are closely related to hepatitis, inflammation, fibrosis and cirrhosis of liver cells, suggesting that PFOS can cause liver pathogenesis and non-alcoholic fatty liver disease in zebrafish. The transcriptomic alterations revealed may serve as biomarkers for the hepatotoxic effect of PFOS. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Non-classical azoreductase secretion in Clostridium perfringens in response to sulfonated azo dye exposure. (United States)

    Morrison, Jessica M; John, Gilbert H


    Clostridium perfringens, a strictly anaerobic microorganism and inhabitant of the human intestine, has been shown to produce an azoreductase enzyme (AzoC), an NADH-dependent flavin oxidoreductase. This enzyme reduces azo dyes into aromatic amines, which can be carcinogenic. A significant amount of work has been completed on the activity of AzoC. Despite this, much is still unknown, including whether azoreduction of these dyes occurs intracellularly or extracellulary. A physiological study of C. perfringens involving the effect of azo dye exposure was completed to answer this question. Through exposure studies, azo dyes were found to cause cytoplasmic protein release, including AzoC, from C. perfringens in dividing and non-dividing cells. Sulfonation (negative charge) of azo dyes proved to be the key to facilitating protein release of AzoC and was found to be azo-dye-concentration-dependent. Additionally, AzoC was found to localize to the Gram-positive periplasmic region. Using a ΔazoC knockout mutant, the presence of additional azoreductases in C. perfringens was suggested. These results support the notion that the azoreduction of these dyes may occur extracellularly for the commensal C. perfringens in the intestine. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Effect of the molecular weight of sodium polystyrene sulfonate on the properties of coal water slurry

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Y.; Gao, F.; Li, Y. [Ningxia University, Yinchuan (China)


    Three sodium polystyrene sulfonate (PSS) additives with different molecular weight and 8 coals are selected to evaluate the effect of molecular weight of PSS on the properties of coal water slurry (CWS). The range of weight average molecular weight of PSS for preparing coal water slurry is from 53400 to 333900. The results indicate that the slurryability of CWS of 8 coals decreases as the molecular weight of PSS increases. The relation between slurry ability of CWS and molecular weight of PSS is attributed to the adsorption of PSS on the coal particles. The adsorption quantity of PSS with low molecular weight on the coal particles is larger than that of PSS with high molecular weight. On the other hand, the rheological behavior of CWS of 8 coals is changed from dilatant flow to pseudoplastic one as the increase of molecular weight of PSS. The static stability of CWS is also improved with increasing molecular weight of PSS. 9 refs., 3 figs., 3 tabs.

  20. Reactive phase inversion for manufacture of asymmetric poly (ether imide sulfone) membranes

    KAUST Repository

    Jalal, Taghreed


    Poly (ether imide sulfone) membranes were manufactured by combining phase inversion and functionalization reaction between epoxy groups and amine modified polyether oligomers (Jeffamine) or TiO2 nanoparticles. Polysilsesquioxanes containing epoxy functionalities were in-situ grown in the casting solution and made available for further reaction with amines in the coagulation/annealing baths. The membranes were characterized by field emission scanning electron microscopy, porosimetry and water flux measurements. Water permeances up to 1500 l m-2 h-1 bar-1 were obtained with sharp pore size distribution and a pore diameter peak at 66 nm, confirmed by porosimetry, which allowed 99.2% rejection of γ-globulin. Water flux recovery of 77.5% was achieved after filtration with proteins. The membranes were stable in 50:50 dimethylformamide/water, 50:50 N-methyl pyrrolidone/water and 100% tetrahydrofuran. The possibility of using similar concept for homogeneous and stable attachment of nanoparticles on the membrane surface was demonstrated.

  1. Exposure to perfluorooctane sulfonate in utero reduces testosterone production in rat fetal Leydig cells. (United States)

    Zhao, Binghai; Li, Li; Liu, Jieting; Li, Hongzhi; Zhang, Chunlei; Han, Pengfei; Zhang, Yufei; Yuan, Xiaohuan; Ge, Ren Shan; Chu, Yanhui


    Perfluorooctane sulfonate (PFOS) is a synthetic material that has been widely used in industrial applications for decades. Exposure to PFOS has been associated with decreased adult testosterone level, and Leydig cell impairment during the time of adulthood. However, little is known about PFOS effects in utero on fetal Leydig cells (FLC). The present study investigated effects of PFOS on FLC function. Pregnant Sprague Dawley female rats received vehicle (0.05% Tween20) or PFOS (5, 20 mg/kg) by oral gavage from gestational day (GD) 11-19. At GD20, testosterone (T) production, FLC numbers and ultrastructure, testicular gene and protein expression levels were examined. The results indicate that exposures to PFOS have affected FLC function as evidenced by decreased T production, impaired FLC, reduced FLC number, and decreased steroidogenic capacity and cholesterol level in utero. The present study shows that PFOS is an endocrine disruptor of male reproductive system as it causes reduction of T production and impairment of rat fetal Leydig cells.

  2. Gastroprotective effect of 2-mercaptoethane sulfonate against acute gastric mucosal damage induced by ethanol. (United States)

    Amirshahrokhi, Keyvan; Khalili, Ali-Reza


    Gastric mucosal damage induced by ethanol is a serious medical problem. Recent evidences suggest that reactive oxygen species and inflammatory mediators play a key role in the destruction of gastric mucosa. The present study was aimed to evaluate the potential beneficial effect of MESNA (2-mercaptoethane sulfonate) against ethanol-induced gastric mucosal damage in mice. The animals were orally pretreated with vehicle or MESNA and then treated with acidified ethanol to induce gastric mucosal damage. One hour after ethanol ingestion mice were euthanized and stomach samples were collected for biochemical analysis. Macroscopic and histopathological evaluation of gastric mucosa showed that pretreatment with MESNA attenuated gastric lesions induced by ethanol. Administration of MESNA significantly increased glutathione content and superoxide dismutase and catalase activity in the gastric tissues. In addition, MESNA markedly reduced ethanol-induced lipid peroxidation, myeloperoxidase activity, tumor necrosis factor-alpha, interleukin (IL)-1β, IL-6, and monocyte chemotactic protein-1 levels. These findings suggest that the thiol-containing compound MESNA is able to decrease alcohol-induced oxidative stress and inflammation in the gastric tissue. It seems that MESNA may have a protective effect against ethanol-induced gastric mucosal damage. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Growth kinetics and toxicity of Enterobacter cloacae grown on linear alkylbenzene sulfonate as sole carbon source. (United States)

    Khleifat, Khaled M; Tarawneh, Khaled A; Ali Wedyan, Mohammad; Al-Tarawneh, Amjad A; Al Sharafa, Khalid


    A successful attempt was made to isolate linear alkylbenzene sulfonate (LAS)-degrading bacteria from soil irrigated with wastewater. The isolated bacteria were able to use LAS as sole carbon and energy source. Maximum growth rates on LAS reached only 0.27 h(-1). 16S-rRNA sequencing and fatty-acid analysis placed the bacteria in the genus Enterobacter cloacae. The growth curves of E. cloacae both in the presence of and the absence of LAS were monitored using measurements of optical density at 600 nm in two different media, nutrient broth and M9 minimal medium, and were modeled mathematically. Growth in NB fit the Riccati and Voltera models, indicating that LAS is not toxic to E. cloacae cells. However, growth of E. cloacae in LAS-containing MM fit the Riccati and Voltera models, whereas growth in LAS-free MM fit the Riccati model only. Furthermore, the kinetic data shown were modeled by Monod's, Andrew's, and Tessier's specific growth rate equations, coupled with the rate of consumption of different concentrations of LAS as sole carbon and energy source, and we determined that Andrew's model best fit these data adequately as a result of the cell-inhibitory effect.

  4. Perfluorooctane sulfonate (PFOS) contamination of fish in urban lakes: a prioritization methodology for lake management. (United States)

    Xiao, Feng; Gulliver, John S; Simcik, Matt F


    The contamination of urban lakes by anthropogenic pollutants such as perfluorooctane sulfonate (PFOS) is a worldwide environmental problem. Large-scale, long-term monitoring of urban lakes requires careful prioritization of available resources, focusing efforts on potentially impaired lakes. Herein, a database of PFOS concentrations in 304 fish caught from 28 urban lakes was used for development of an urban-lake prioritization framework by means of exploratory data analysis (EDA) with the aid of a geographical information system. The prioritization scheme consists of three main tiers: preliminary classification, carried out by hierarchical cluster analysis; predictor screening, fulfilled by a regression tree method; and model development by means of a neural network. The predictive performance of the newly developed model was assessed using a training/validation splitting method and determined by an external validation set. The application of the model in the U.S. state of Minnesota identified 40 urban lakes that may contain elevated levels of PFOS; these lakes were not previously considered in PFOS monitoring programs. The model results also highlight ongoing industrial/commercial activities as a principal determinant of PFOS pollution in urban lakes, and suggest vehicular traffic as an important source and surface runoff as a primary pollution carrier. In addition, the EDA approach was further compared to a spatial interpolation method (kriging), and their advantages and disadvantages were discussed. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Acute toxicity effects of perfluorooctane sulfonate on sperm vitality, kinematics and fertilization success in zebrafish (United States)

    Xia, Jigang; Niu, Cuijuan


    Perfluorooctane sulfonate (PFOS) has emerged as one of the most concerning contaminants in recent years. This study aimed to investigate the acute toxicity effect of PFOS on sperm viability, kinematics and fertilization success in zebrafish ( Danio rerio). Sperm were activated in aqueous media containing a range of PFOS concentrations (0, 0.09, 0.9 and 9 mg/L). Viabilities and kinematics of the sperm exposed to different PFOS treatments were assessed via computer-assisted sperm analysis (CASA) at 20, 40, 60, and 80 s after activation. PFOS exposure decreased the percentage of motile sperm, the curvilinear velocity (VCL), and the mean angular displacement (MAD) of spermatozoa, but showed no influence on the straight-line velocity (VSL) or the angular path velocity (VAP). Furthermore, a significant decrease in fertilization success was observed in spermatozoa that were exposed to 0.9 mg/L PFOS or more. These findings indicate that PFOS pollution in natural aquatic environment may be a potential threaten to successful reproduction of fish.

  6. Surface modification of polyamide reverse osmosis membrane with sulfonated polyvinyl alcohol for antifouling (United States)

    Zhang, Yang; Wan, Ying; Pan, Guoyuan; Shi, Hongwei; Yan, Hao; Xu, Jian; Guo, Min; Wang, Zhe; Liu, Yiqun


    Sulfonated polyvinyl alcohol (SPVA) was synthesized by esterification reaction of PVA and sulfuric acid, and the structure was characterized by FTIR spectrum. Then a series of TFC membranes modified with cross-linked SPVA layer were fabricated by coating method, with glutaraldehyde as the cross-linker. The resulting TFC membranes were characterized by SEM, AFM, ATR-FTIR, XPS, streaming potential as well as static contact angle. The TFC membranes modified with SPVA exhibit decreased water flux and increased NaCl rejection with SPVA content increasing in the coating aqueous solution. The optimal PA-SPVA-0.5 sample exhibits a NaCl rejection of 99.18%, which is higher than the 98.32% of the virgin PA membrane. More importantly, the PA-SPVA-0.5 membrane shows much more improved fouling resistance to BSA and CTAB than virgin PA membrane and the TFC sample modified with PVA (PA-PVA-0.5). PA-SPVA-0.5 membrane loses about 8% of the initial flux after BSA fouling for 12 h, which is much lower than those of virgin PA and PA-PVA-0.5 membranes (28% and 15%, respectively). Furthermore, the flux recovery of the PA-SPVA-0.5 membrane reaches above 95% after cleaning. Thus, the PA-SPVA-0.5 membrane shows potential applications as antifouling RO membrane for desalination and purification.

  7. Treatment of Sulfonated Azo Dye Reactive Red 198 by UV/H2O2

    Directory of Open Access Journals (Sweden)

    Jefferson P. Ribeiro


    Full Text Available UV/H2O2 system was tested on the color removal of sulfonated azo dye Reactive Red 198 (RR, which is widely used in textile process. The effects of hydrogen peroxide concentration, temperature, pH, and the in-line addition of hydrogen peroxide on high color and chemical oxygen demand (COD removals were investigated. The kinetic of dye decolorization was also determined. The results showed that 2% H2O2 decreased the process efficiency, while 1% H2O2 solution led to a better performance of the system. Despite the fact that the pH increase had small effect on color removal, it affects positively COD removals. The same behavior was found for temperature increase. A high temperature resulted in a slight decrease in color removal and a sharp decrease for COD removal. In addition the H2O2 in-line provided a small improvement in both color and COD removals. UV/1% H2O2 treatment was the most efficient, the good performance was linked to higher amount of hydroxyl radicals formed.

  8. Chronic Exposure to Perfluorooctane Sulfonate Reduces Lifespan of Caenorhabditis elegans Through Insulin/IGF-1 Signaling. (United States)

    Xu, Tiantian; Li, Ping; Wu, Siyu; Li, Dan; Wu, Jingxuan; Raley-Susman, Kathleen M; He, Defu


    Perfluorooctane sulfonate (PFOS) is a persistent organic pollutant. Although multiple adverse effects of PFOS have been demonstrated, whether PFOS can accelerate aging and affect animal longevity remains unknown. In Caenorhabditis elegans, we found that a 50 h exposure to 0.2-200 µM PFOS reduced lifespan in a concentration dependent manner. In transgenic nematodes, lifespans are affected by mutations of daf-16, daf-2 or age-1 genes, which are related to the Insulin/IGF-1 Signaling pathway (IIS). PFOS exposure caused an additional reduction in average lifespan in daf-2(e1370) and daf-16b(KO) nematodes. In contrast, daf-16(mu86) nematodes showed no additional reduction with PFOS exposure and age-1(hx546) mutants did not exhibit a reduction in lifespan with PFOS exposure, compared with wildtype nematodes. Overall, our findings demonstrate that PFOS exposure accelerates aging and shortens longevity of animals. The PFOS-induced effect may involve genes of the IIS pathway, particularly daf-16 and age-1.

  9. Methionine sulfone-containing orbitides, good indicators to evaluate oxidation process of flaxseed oil. (United States)

    Zou, Xian-Guo; Hu, Jiang-Ning; Zhu, Xue-Mei; Wang, Yu-Fu; Deng, Ze-Yuan


    This study aimed to explore the possibility of using methionine sulfone (Msn)-containing orbitides as indicators to evaluate the oxidation process of flaxseed oils. Results showed that after 4 days' heating, oxidation values slightly increased (p > .05) with significant decrease in methionine (Met)-containing peptides (p  .05). However, as oxidation time continues increasing, oxidation values significantly increased (p oxidized compared with γ-tocopherol and showed certain antioxidant activity. Besides, high logarithmic correlations were found between oxidation values and Msn-containing orbitides (0.94-1.00), such as between total carbonyl compounds and orbitide [1-8-NαC],[1-MetO 2 ]-CLE (64.95 lnx - 52.14, R 2  = 0.99, Dingya23 oil). Therefore, in comparison with common oxidation indices, Msn-containing orbitides may be better indicators for evaluating the oxidation process of flaxseed oil with superior separation efficiency, specific information and high stability. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Efficient Polymer Solar Cells by Lithium Sulfonated Polystyrene as a Charge Transport Interfacial Layer. (United States)

    Wang, Kai; Zhang, Zhan; Liu, Chang; Fu, Qiang; Xu, Wenzhan; Huang, Chongwen; Weiss, R A; Gong, Xiong


    In this paper, we report the highly efficient bulk heterojunction (BHJ) polymer solar cells (PSCs) with an inverted device structure via utilizing an ultrathin layer of lithium sulfonated polystyrene (LiSPS) ionomer to reengineer the surface of the solution-processed zinc oxide (ZnO) electron extraction layer (EEL). The unique lithium-ionic conductive LiSPS contributes to enhanced electrical conductivity of the ZnO/LiSPS EEL, which not only facilitates charge extraction from the BHJ active layer but also minimizes the energy loss within the charge transport processes. In addition, the organic-inorganic LiSPS ionomer well circumvents the coherence issue of the organic BHJ photoactive layer on the ZnO EEL. Consequently, the enhanced charge transport and the lowered internal resistance between the BHJ photoactive layer and the ZnO/LiSPS EEL give rise to a dramatically reduced dark saturation current density and significantly minimized charge carrier recombination. As a result, the inverted BHJ PSCs with the ZnO/LiSPS EEL exhibit an approximatively 25% increase in power conversion efficiency. These results indicate our strategy provides an easy, but effective, approach to reach high performance inverted PSCs.

  11. Poly(p-Phenylene Sulfonic Acids). PEMs with frozen-in free volume

    Energy Technology Data Exchange (ETDEWEB)

    Litt, Morton [Case Western Reserve Univ., Cleveland, OH (United States)


    Early work with rigid rod aromatic polyelectrolytes implied that steric hindrance in packing of the rigid rods left unoccupied volumes that could absorb and hold water molecules strongly. We called this “frozen in free volume). It is illustrated and contrasted with the packing of flexible backbone polyelectrolytes (Reference 5 of this report). This was quantified for poly(biphenylene disulfonic acid) (PBDSA) and poly(phenylene disulfonic acid) (PPDSA). We found that PPDSA held three water molecules per acid group down to 11% relative humidity (RH) and had very high conductivity even at these low RHs. (Reference 1 of report.) The frozen-in free volume was calculated to be equivalent to a λ of 3.5. The work reported below concentrated on studying these polymers and their copolymers with biphenylene disulfonic acid. As expected, the polyelectrolytes are water soluble. Several approaches towards making water stable films were studied. Grafting alkyl benzene substituents on sulfonic acid groups had worked for PBPDSA (1) so it was tried with PPDSA and a 20%/80% copolymer of BPDSA and PDSA (B20P80). T-butyl, n-octyl and n-dodecyl benzene were grafted. Good films could be made. Water absorption and conductivity were studied as a function of RH and temperature (Reference 2). When less than 20% of the sulfonic acid groups were grafted, conductivity was much higher than that of Nafion NR212 at all RHs. At low graft levels, conductivity was ten times higher. Mechanical properties and swelling were acceptable below 90% RH. However, all the films were unstable in water and slowly disintegrated. The proposed explanation was that the molecules formed nano-aggregates in solution held together by hydrophobic bonding. Their cast films disintegrated when placed in water since hydrophobic bonding between the nano-aggregates was poor. We then shifted to crosslinking as a method to produce water stable films (References 3 and 4). Biphenyl could easily be reacted with the polymer

  12. Alteration to Dopaminergic Synapses Following Exposure to Perfluorooctane Sulfonate (PFOS, in Vitro and in Vivo

    Directory of Open Access Journals (Sweden)

    Rahul Patel


    Full Text Available Our understanding of the contribution exposure to environmental toxicants has on neurological disease continues to evolve. Of these, Parkinson’s disease (PD has been shown to have a strong environmental component to its etiopathogenesis. However, work is still needed to identify and characterize environmental chemicals that could alter the expression and function of the nigrostriatal dopamine system. Of particular interest is the neurotoxicological effect of perfluorinated compounds, such as perfluorooctane sulfonate (PFOS, which has been demonstrated to alter aspects of dopamine signaling. Using in vitro approaches, we have elaborated these initial findings to demonstrate the neurotoxicity of PFOS to the SH-SY5Y neuroblastoma cell line and dopaminergic primary cultured neurons. Using an in vivo model, we did not observe a deficit to dopaminergic terminals in the striatum of mice exposed to 10 mg/kg PFOS for 14 days. However, subsequent exposure to the selective dopaminergic neurotoxin, 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP significantly reduced the expression of dopamine transporter (DAT and tyrosine hydroxylase (TH, and resulted in an even greater reduction in DAT expression in animals previously exposed to PFOS. These findings suggest that PFOS is neurotoxic to the nigrostriatal dopamine circuit and this neurotoxicity could prime the dopamine terminal to more extensive damage following additional toxicological insults.

  13. Improved antifouling potential of polyether sulfone polymeric membrane containing silver nanoparticles: self-cleaning membranes. (United States)

    Rana, Sidra; Nazar, Umair; Ali, Jafar; Ali, Qurat Ul Ain; Ahmad, Nasir M; Sarwar, Fiza; Waseem, Hassan; Jamil, Syed Umair Ullah


    A new strategy to enhance the antifouling potential of polyether sulfone (PES) membrane is presented. Chemically synthesized silver nanoparticles (AgNPs) were used to prepare a mixed-matrix PES membrane by the phase inversion technique. Primarily, AgNPs synthesis was confirmed by surface plasmon resonance at 410-430 nm using UV-Visible spectroscopy. X-ray diffraction analysis revealed that AgNPs were crystalline with a diameter of 21 ± 2 nm. Furthermore, PES membranes were characterized by energy dispersive X-ray spectroscopy to confirm the incorporation of AgNPs in membranes. Hydrophilicity of the membranes was enhanced, whereas roughness, mechanical strength and biofouling were relatively reduced after embedding the AgNPs. Antibacterial potential of AgNPs was evaluated for E. coli in the disc diffusion and colony-forming unit (CFU) count method. All of the membranes were assessed for antifouling activity by filtering a control dilution (10(6) CFU/ml) of E. coli and by counting CFU. Anti-biofouling activity of the membrane was observed with different concentrations of AgNPs. Maximum reduction (66%) was observed in membrane containing 1.5% of AgNPs. The addition of antibiotic ceftriaxone enhanced the antibacterial effect of AgNPs in PES membranes. Our practicable antifouling strategy may be applied to other polymeric membranes which may pave the new way to achieve sustainable and self-cleaning membrane reactors on large scale.

  14. Sodium Tanshinone IIA Sulfonate Attenuates Scopolamine-Induced Cognitive Dysfunctions via Improving Cholinergic System

    Directory of Open Access Journals (Sweden)

    Qing-Qing Xu


    Full Text Available Sodium Tanshinone IIA sulfonate (STS is a derivative of Tanshinone IIA (Tan IIA. Tan IIA has been reported to possess neuroprotective effects against Alzheimer’s disease (AD. However, whether STS possesses effect on AD remains unclear. This study aims to estimate whether STS could protect against scopolamine- (SCOP- induced learning and memory deficit in Kunming mice. Morris water maze results showed that oral administration of STS (10 mg/kg and 20 mg/kg and Donepezil shortened escape latency, increased crossing times of the original position of the platform, and increased the time spent in the target quadrant. STS decreased the activity of acetylcholinesterase (AChE and increased the activity of choline acetyltransferase (ChAT in the hippocampus and cortex of SCOP-treated mice. Oxidative stress results showed that STS increased the activity of superoxide dismutase (SOD and decreased the levels of malondialdehyde (MDA and reactive oxygen species (ROS in hippocampus and cortex. In addition, western blot was carried out to detect the expression of apoptosis related proteins (Bcl-2, Bax, and Caspase-3. STS upregulated the protein expression of Bcl-2 and downregulated the proteins expression of Bax and Caspase-3. These results indicated that STS might become a promising therapeutic candidate for attenuating AD-like pathological dysfunction.

  15. Mechanism of photodynamic inactivation of hepatocarcinoma cells with sulfonated aluminum phthalocyanine (United States)

    Yu, Hong-Yu; Dong, Rong-Chun; Chen, Ji-Yao; Cai, Huai-Xin


    The mechanism of photodynamic therapy (PDT) with sulfonated aluminum phthalocyanine (AlSPC) studied with the human hepatocellular carcinoma cell line in culture is reported herein. Photofrin II (PII) was chosen as the control photosensitizer of AlSPC. Deuterium oxide (D2O), an enhancer of singlet oxygen (1O2); 1,3-diphenylisobenzofuran (DPBF), a quencher of 1O2: glycerol, a quencher of OH radical (OH(DOT)); superoxide dismutase (SOD), a quencher of O2- radical (O2-(DOT)); diethyldithiocarbamate (DDC), an inhibitor of SOD and glutathione peroxidase; were introduced into both the processes of photodynamic inactivation of human liver cancer cells in culture with AlSPC (AlSPC-PDT) and with PII (PII-PDT). The results suggest that: 1O2 is dominantly involved in both PII-PDT and AlSPC-PDT; O2-(DOT) is involved in AlSPC-PDT in a lower degree than 1O2, while almost not involved in PII-PDT; OH(DOT) is involved in PII-PDT in a lower degree than 1O2, while almost not involved in AlSPC-PDT.

  16. External surface area determination of lipid vesicles using trinitrobenzene sulfonate and ultraviolet/visible spectrophotometry. (United States)

    Engel, Helen; Rondeau, Elisabeth; Windhab, Erich J; Walde, Peter


    The lamellarity of liposomes is an important parameter to be controlled in liposomal delivery-release applications. A practical estimate of the degree of liposome lamellarity can be obtained by measuring the relative external surface area of the liposomes using a chemical assay. All such assays are based on a signal change caused by exposed marker lipids on reaction with a specific externally added reagent. However, a quantitative determination is often distorted by background reactions and contributions of internal lipid labeling. In the so-called TNBS assay, the marker lipid is phosphatidylethanolamine (PE) and the externally added reagent is TNBS (2,4,6-trinotrobenzene sulfonate). Mechanistic aspects of the TNBS assay were considered for improving the assay. Internal lipid labeling via PE flip-flop and/or TNBS permeation was minimal not only in cholesterol-containing liposomes but also in cholesterol-free liposomes if in the latter case membrane fluidity was decreased by slightly increasing the PE content. Compared with earlier versions of the TNBS assay, the amount of marker lipid and the time for analysis could be reduced considerably. The elaborated protocol was also applied to liposomes prepared from lipidic egg yolk isolates, offering a simple and inexpensive method for the development and in-process control of new liposome formation technologies. Copyright © 2013 Elsevier Inc. All rights reserved.

  17. Exposure to perfluorooctane sulfonate in utero reduces testosterone production in rat fetal Leydig cells.

    Directory of Open Access Journals (Sweden)

    Binghai Zhao

    Full Text Available Perfluorooctane sulfonate (PFOS is a synthetic material that has been widely used in industrial applications for decades. Exposure to PFOS has been associated with decreased adult testosterone level, and Leydig cell impairment during the time of adulthood. However, little is known about PFOS effects in utero on fetal Leydig cells (FLC.The present study investigated effects of PFOS on FLC function. Pregnant Sprague Dawley female rats received vehicle (0.05% Tween20 or PFOS (5, 20 mg/kg by oral gavage from gestational day (GD 11-19. At GD20, testosterone (T production, FLC numbers and ultrastructure, testicular gene and protein expression levels were examined. The results indicate that exposures to PFOS have affected FLC function as evidenced by decreased T production, impaired FLC, reduced FLC number, and decreased steroidogenic capacity and cholesterol level in utero.The present study shows that PFOS is an endocrine disruptor of male reproductive system as it causes reduction of T production and impairment of rat fetal Leydig cells.

  18. Removal of petroleum sulfonate from aqueous solutions using freshly generated magnesium hydroxide. (United States)

    Huang, Xinghai; Wu, Tao; Li, Yujiang; Sun, Dejun; Zhang, Guochen; Wang, Yan; Wang, Guopeng; Zhang, Miaoli


    Freshly generated magnesium hydroxide (FGMH), produced by adding water-soluble magnesium salts to highly alkaline solutions, was used to remove anionic surfactant petroleum sulfonate (PS) from aqueous solutions. Adsorption experiments were carried out to investigate the effects of pH, adsorbent dosage, contact time, PS concentration, and temperature. The results showed that FGMH displayed excellent treatment efficiency for PS in the pH range 12.0-13.0. The maximum PS removal efficiency was reached within 60 s. The best dosage of magnesium chloride was 2.0 g/L. The adsorption capacity of FGMH for PS decreased as the temperature increased from 303 K to 333 K. The adsorption process was exothermic. The removal mechanism of PS by FGMH may be a coagulation-adsorption process involving a combination of flocculation, adsorption, charge neutralization, and netting catch affection. The results of this study showed that FGMH can be effectively used to treat surfactant wastewaters. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Composite Electrolyte Membranes from Partially Fluorinated Polymer and Hyperbranched, Sulfonated Polysulfone

    Directory of Open Access Journals (Sweden)

    Surya Subianto


    Full Text Available Macromolecular modification of poly(vinylidene fluoride-co-hexafluoropropylene (PVDF was done with various proportions of sulfonic acid terminated, hyperbranched polysulfone (HPSU with a view to prepare ion conducting membranes. The PVDF-co-HFP was first chemically modified by dehydrofluorination and chlorosulfonation in order to make the membrane more hydrophilic as well as to introduce unsaturation, which would allow crosslinking of the PVDF-co-HFP matrix to improve the stability of the membrane. The modified samples were characterized for ion exchange capacity, morphology, and performance. The HPSU modified S-PVDF membrane shows good stability and ionic conductivity of 5.1 mS cm−1 at 80 °C and 100% RH for blends containing 20% HPSU, which is higher than the literature values for equivalent blend membranes using Nafion. SEM analysis of the blend membranes containing 15% or more HPSU shows the presence of spherical domains with a size range of 300–800 nm within the membranes, which are believed to be the HPSU-rich area.

  20. Sulfonated graphene oxide and its nanocomposites with electroactive conjugated polymer as effective pseudocapacitor electrode materials. (United States)

    Ehsani, A; Kowsari, E; Boorboor Ajdari, F; Safari, R; Mohammad Shiri, H


    In this work, we synthesized amine functionalized graphene oxide (GOA), by using of 1-methyl, 3-butyl Imidazole ionic liquid, triphenylphosphine, 1,6-diamino hexane in DMSO medium. Afterward, dried GOA used for sulfonated graphene oxide (GOS). For improving electrochemical properties of the poly ortho aminophenol (POAP), we fabricated POAP/GOS films by electro-polymerization of POAP in the presence of GOS to serve as the active electrode for electrochemical supercapacitor. Different electrochemical methods including galvanostatic charge-discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy are carried out in order to investigate the performance of the system. Finally, the local charge and energy transfer of the molecular system is calculated, using DFT/AIM theories. Results show that the oxygen and nitrogen atoms of phenyl (Ph)/(Ph-OH) rings and -Ph-CO-N-R-N-R″ -SO3H ended functional group, play domain role in intra-molecular charge and energy transfer. The major aim of this computational study method is to propose or effective design electro-chemical molecular systems having different atomic basins/functional groups response (sensitivities) to external voltage. This work introduces new most efficient materials for electrochemical redox capacitors with advantages including ease synthesis, high active surface area and stability in an aqueous electrolyte. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Electroacupuncture Improves Trinitrobenzene Sulfonic Acid-Induced Colitis, Evaluated by Transcriptomic Study

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    Tin-Yun Ho


    Full Text Available Inflammatory bowel disease is a chronic colonic inflammation that displays symptoms like diarrhea and weight loss. Acupuncture has been widely accepted by Western countries for the treatment of pain. Here, we analyzed efficacy and mechanism of electroacupuncture (EA on trinitrobenzene sulfonic acid- (TNBS- induced colitis in mice. Mice were intrarectally administered with 250 mg/kg TNBS and electroacupunctured at Quze (PC3 and Neiguan (PC6 acupoints, which have been applied for gastrointestinal disorders. Gene expression profiles in colons and spleens were analyzed by microarray for the elucidation of mechanism of EA. Our data showed that EA at PC3 and PC6 improved macroscopic and microscopic features of colitis and the improvement displayed a frequency-dependent manner. Administration of TNBS upregulated the expression of most cytokine genes in colons, while EA downregulated the expression of TNBS-induced cytokine genes. Pathway analysis showed that EA significantly affected inflammatory pathways in colons and immunity-associated pathway in spleens. Immunohistochemical staining further showed that EA decreased the expression of interleukin-1β and nuclear factor-κB. In conclusion, this is the first study reporting the global gene expression profiles of EA on TNBS-induced colitis. Our findings suggested that inflammatory and immunity pathways were involved in the anti-inflammatory mechanism of EA on colitis induced by TNBS.

  2. Electrospun sulfonated poly(ether ketone) nanofibers as proton conductive reinforcement for durable Nafion composite membranes (United States)

    Klose, Carolin; Breitwieser, Matthias; Vierrath, Severin; Klingele, Matthias; Cho, Hyeongrae; Büchler, Andreas; Kerres, Jochen; Thiele, Simon


    We show that the combination of direct membrane deposition with proton conductive nanofiber reinforcement yields highly durable and high power density fuel cells. Sulfonated poly(ether ketone) (SPEK) was directly electrospun onto gas diffusion electrodes and then filled with Nafion by inkjet-printing resulting in a 12 μm thin membrane. The ionic membrane resistance (30 mΩ*cm2) was well below that of a directly deposited membrane reinforced with chemically inert (PVDF-HFP) nanofibers (47 mΩ*cm2) of comparable thickness. The power density of the fuel cell with SPEK reinforced membrane (2.04 W/cm2) is 30% higher than that of the PVDF-HFP reinforced reference sample (1.57 W/cm2). During humidity cycling and open circuit voltage (OCV) hold, the SPEK reinforced Nafion membrane showed no measurable degradation in terms of H2 crossover current density, thus fulfilling the target of 2 mA/cm2 of the DOE after degradation. The chemical accelerated stress test (100 h OCV hold at 90 °C, 30% RH, H2/air, 50/50 kPa) revealed a degradation rate of about 0.8 mV/h for the fuel cell with SPEK reinforced membrane, compared to 1.0 mV/h for the PVDF-HFP reinforced membrane.

  3. Liquid Phase Micro-Extraction of Linear Alkylbenzene Sulfonate Anionic Surfactants in Aqueous Samples

    Directory of Open Access Journals (Sweden)

    Jan Åke Jönsson


    Full Text Available Hollow fiber liquid phase micro-extraction (LPME of linear alkylbenzene sulfonates (LAS from aqueous samples was studied. Ion pair extraction of C10, C11, C12 and C13 homologues was facilitated with trihexylamine as ion-pairing agent, using di-n-hexylether as solvent for the supported liquid membrane (SLM. Effects of extraction time, acceptor buffer concentration, stirring speed, sample volume, NaCl and humic acids were studied. At 10–50 µg L−1 linear R2-coefficients were 0.99 for C10 and C11 and 0.96 for C12. RSD was typically ~15%. Three observations were especially made. Firstly, LPME for these analytes was unusually slow with maximum enrichment observed after 15–24 h (depending on sample volume. Secondly, the enrichment depended on LAS sample concentration with 35–150 times enrichment below ~150 µg L−1 and 1850–4400 times enrichment at 1 mg L−1. Thirdly, lower homologues were enriched more than higher homologues at low sample concentrations, with reversed conditions at higher concentrations. These observations may be due to the fact that LAS and the amine counter ion themselves influence the mass transfer at the water-SLM interface. The observations on LPME of LAS may aid in LPME application to other compounds with surfactant properties or in surfactant enhanced membrane extraction of other compounds.

  4. Assessing the dynamic biofilm removal of sulfonated phenolics using CP-OCT (United States)

    Englund, K.; Nikrad, J.; Jones, R.


    Examining the physical mechanisms related to biofilm removal of sulfonated phenolics (SP) is difficult using conventional microscopy techniques. A custom flow cell system integrated with a real time cross polarization optical coherence tomography system investigated the dynamic speed of biofilm removal when oral multi-species biofilms are exposed to SP under sheer stress. The Near infrared 1310-nm CP-OCT system non-destructively imaged fluid immersed oral biofilms at nearly 30 frames/s. This dynamic imaging was able to determine the cohesive and adhesion related disruption of SP on oral biofilms adhering to tooth like surfaces. For multi-species biofilms that are initially grown without the presence of sucrose, the disruption of biofilms on saliva coated hydroxyapatite (HA) is dominated as a adhesive failure at the HA-biofilm interface. For multi-species biofilms that are grown in the presence of sucrose, the disruption is dominated by cohesive disruption followed by adhesive failure. This novel CP-OCT flow cell assay has the potential to examine rapid interactions between anti-biofilm agents and tooth like surfaces.

  5. Aqueous stability and mobility of C₆₀ complexed by sodium dodecyl benzene sulfonate surfactant. (United States)

    Peng, Xianjia; Yuan, Yue; Wang, Hongyu; Liang, Chuan


    Surfactant complexation may have significant effects on the environmental behavior of nano-particles. In order to understand the ecological exposure of nano-materials, it is important to determine the stability and mobility of surfactant-complexed nano-materials in aqueous systems. In this study, the aggregation and transport of C60 complexed by the surfactant sodium dodecyl benzene sulfonate (SDBS) were investigated. It was found that SDBS-complexed C60 had a ζ-potential of -49.5 mV under near-neutral pH conditions and remained stable during an aging period of 15 days. It had a critical coagulation concentration of 550 mmol/L for NaCl, which was higher than common natural colloids and many kinds of raw nano-materials, and was comparable to those of many kinds of surface-modified nano-materials. SDBS enhanced the stability of C60 colloid; however, at the same time, it also enhanced the colloidal particle aggregation rate. Much higher mobility was found for SDBS-complexed C60 than C60 colloid. Increase in ionic strength, Ca(2+) concentration or Al(3+) concentration decreased the mobility. In general, SDBS-complexed C60 had high stability and mobility. Copyright © 2015. Published by Elsevier B.V.

  6. Mixing behavior of the biosurfactant, rhamnolipid, with a conventional anionic surfactant, sodium dodecyl benzene sulfonate. (United States)

    Chen, M L; Penfold, J; Thomas, R K; Smyth, T J P; Perfumo, A; Marchant, R; Banat, I M; Stevenson, P; Parry, A; Tucker, I; Grillo, I


    The use of small angle neutron scattering, SANS, neutron reflectivity, NR, and surface tension to study the mixing properties of the biosurfactant rhamnolipid with a conventional anionic surfactant, sodium dodecyl 6-benzene sulfonate, LAS, is reported. The monorhamnose rhamnolipid, R1, mixes close to ideally with LAS at the air-water interface, whereas for mixtures of LAS with the dirhamnose rhamnolipid, R2, the LAS strongly partitions to the air-water interface relative to R2, probably because of the steric hindrance of the larger R2 headgroup. These trends in the binary mixtures are also reflected in the ternary R1/R2/LAS mixtures. However, for these ternary mixtures, there is also a pronounced synergy in the total adsorption, which reaches a maximum for a LAS/rhamnolipid mole ratio of about 0.6 and a R1/R2 mol ratio of about 0.5, an effect which is not observed in the binary mixtures. In solution, the R1/LAS mixtures form relatively small globular micelles, L(1), at low surfactant concentrations (80 mol % LAS) where more planar structures are formed. For the ternary mixtures, there is an evolution in the resulting phase behavior from one dominated by L(1) (R2 rich) to one dominated by planar structures, L(α), (R1, LAS rich), and which strongly depends upon the LAS/rhamnolipid and R1/R2 mole ratio.

  7. [Isolation and characterization of a sodium dodecyl benzene sulfonate degrading bacterial strain]. (United States)

    Wu, Chu


    A bacterial strain, designated as WZR-A, which could utilize sodium dodecyl benzene sulfonate (SDBS) as sole carbon and energy source for growth, was isolated from contaminated river. The strain was identified as Ochrobactrum anthropi based on its morphological and physiological properties, and 16S rDNA sequence analysis. The optimum pH and temperature for cell growth and SDBS degradation were 7.0 and 30 degrees U, respectively. The degradation rate of SDBS by strain WZR-A was higher than 80% when its concentration was lower than 400mg/L. The results of whole cell protein SDS-PAGE electrophoresis showed that there were very obvious differences in the total cell protein composition of the strain between before and after SDBS induction. The enzyme distribution experiment showed that the enzymes relative SDBS degradation in the bacterium was intracellular one. Results from the characterization of degradation substrates together with the detection of activities of relative catabolic enzymes in crude extracts indicated that the aromatic ring cracking of SDBS by the strain probably via the modified ortho cleavage pathway and the strain could use broader spectrum substrates. A large plasmid was detected by utilizing plasmid isolating and curing technique and it was found that the genes involved in SDBS degradation were likely located on the plasmid.

  8. Growth responses of Escherichia coli to the surfactant dodecyl benzene sulfonate. (United States)

    Pollack, V A; Anderson, D A


    When strains of Escherichia coli are grown in broth cultures containing the anionic surfactant sodium dodecyl benzene sulfonate (NaDDBS), they exhibit unique growth responses. After 20 to 24 hr of incubation, they become slimy and viscous, and an addition of ethanol to the supernatant liquid yields a distinctive white, fibrous precipitate. The production of this material was shown to be dependent on the presence of NaDDBS in the medium. This precipitate from E. coli ATCC 11303 was found to contain 41 to 53% protein, 10 to 11% deoxyribonucleic acid, 6.8 to 7.4% ribonucleic acid, 15 to 25% carbohydrate, and 9% lipid. It is distinctive from naturally occurring E. coli slimes in several respects. Our data suggest that its formation is the primary result of the leakage of intracellular components into the medium. However, the rate of cell proliferation indicates a partial but not complete or lethal lysis. A limited utilization of NaDDBS as a carbon source was also shown.

  9. Enhancement effect of sodium dodecyl benzene sulfonate (SDBS) and its application into voltammetric determination of telmisartan. (United States)

    Yi, Hongchao; Huang, Wensheng


    A sensitive and rapid electrochemical method was developed for the determination of telmisartan based on the enhancement effect of sodium dodecyl benzene sulfonate (SDBS). In 0.1 mol L(-1) HClO(4) and in the presence of 7.5x10(-5)mol L(-1) SDBS, a well-defined and sensitive oxidation peak was observed for telmisartan at the acetylene black (AB) paste electrode. However, the oxidation peak is poor-shaped and the peak current is very low in the absence of SDBS, suggesting that SDBS shows obvious enhancement effect for the determination of telmisartan. After all the experimental parameters were optimized, a sensitive and simple electrochemical method was developed for determining telmisartan. The oxidation peak current is proportional to the concentration of telmisartan over the range from 2.5x10(-7) to 2.0x10(-5)mol L(-1). The detection limit is 7.5x10(-8)mol L(-1) after 2 min of accumulation. This new voltammetric method was successfully used to detect telmisartan in drugs.

  10. Electromechanical properties of poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate) films. (United States)

    Okuzaki, Hidenori; Suzuki, Hiroki; Ito, Takamichi


    Free-standing films made of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrene sulfonate) (PEDOT/PSS) were prepared by casting water dispersion of its colloidal particles. Morphology, water vapor sorption, and electro-active polymer actuating behavior of the resulting films were investigated by means of atomic force microscopy, sorption isotherm, thermal mechanical analysis, and electromechanical analysis. It was found that the PEDOT/PSS film sorbed 60% of moisture at relative water vapor pressure of 0.95. Upon application of 10 V, the film underwent contraction of 2.4% in air at 50% relative humidity (RH) which significantly increased to 4.5% at 90% RH. The principle lay in desorption of water vapor sorbed in the film due to Joule heating, where electric field was capable of controlling the equilibrium of water vapor sorption. The film generated contractile stress as high as 17 MPa under isometric conditions and work capacity attained 174 kJ m(-3), where Young's modulus of the film increased from 1.8 to 2.6 GPa by application of 6 V at 50% RH.

  11. Removal of polyvinylamine sulfonate anthrapyridone dye by application of heterogeneous electro-Fenton process. (United States)

    Bouzayani, Bakhta; Meijide, Jessica; Pazos, Marta; Elaoud, Sourour Chaâbane; Sanroman, Maria Angeles


    Diversity and rapidly multiplication of the pollutants incite as to improve the conventional treatments wastewater methods. One of the bottlenecks often faced is the presence into wastewater of organic pollutants with complex structures that requests the design of efficient processes. Thus, this work investigates the removal of polyvinylamine sulfonate anthrapyridone (PSA) dye which complex structure makes difficult its degradation by conventional technologies. For that, a heterogeneous oxidative process using pyrite as sustainable catalyst was designed. Initially, the performance of the system BBD-carbon felt as anode and cathode, respectively for the production of H2O2 was determined in comparison with system boron-doped diamond nickel foam. The carbon felt electrode provided the highest oxidant production, and it was selected for the treatment of the polymeric dye. Several oxidative processes were evaluated, and the best degradation levels were obtained by application of electro-Fenton-pyrite process. In addition, it was determined that dye removal followed a kinetic model of pseudo-first-order achieving the highest efficiency by operation at optimum dosage of pyrite 2 g/L and 200 mA of current intensity. Depending on the optimal experimental conditions, these values lead to a nearly complete mineralization (total organic carbon removal of 95%) after 6 h. Furthermore, the reusability of pyrite was evaluated, by removal of PSA in four cycles.

  12. Assessment of perfluorooctane sulfonate and perfluorooctanoic acid exposure through fish consumption in Italy

    Directory of Open Access Journals (Sweden)

    Andrea Barbarossa


    Full Text Available Perfluoroalkyl and polyfluoroalkyl substances (PFASs are pollutants of anthropic origin with possible side effects on human health. Diet, and in particular fish and seafood, is considered the major intake pathway for humans. The present study investigated the levels of perfluorooctane sulfonate (PFOS and perfluorooctanoic acid (PFOA contamination in twenty-five samples of fresh fillet of five widely consumed fish species purchased from large retailers in Italy, to be used for an estimation of the Italian population exposure to these contaminants. PFOS and PFOA were found in all samples, at concentrations up to 1896 (mean=627 ng/kg and 487 ng/kg (mean=75 ng/kg, respectively, confirming the role of fish as high contributor to human exposure. However, a remarkable inter-species variability was observed, and multiple factors were suggested as potentially responsible for such differences, suggesting that the preferential consumption of certain species could likely increase the intake, and thus the exposure. The exposure estimates for both average and high fish consumers resulted far below the tolerable daily intakes for PFOS and PFOA in all age groups, confirming the outcomes of EFSA’s scientific report. In particular, the calculated total dietary exposure for the 95th percentile consumers belonging to the toddler age class, the most exposed group, resulted equal to 9.72 ng/kg body weight (BW/day for PFOS and 8.39 ng/kg BW/day for PFOA.

  13. Effects of perfluorooctanoate and perfluorooctane sulfonate exposure on hepatoma Hep G2 cells

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Xiao-Zhong; Hu, De-Cong [Technology Center of Hubei Entry-Exit Inspection and Quarantine Bureau, Wuhan (China)


    Perfluorinated compounds (PFCs) are emerging compounds of concern. They are widely distributed in the environment, wildlife and human. Concern has been raised over their possible adverse effects on human health. This study was designed to determine cytotoxic effects of two important PFCs, perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS), in a single and a mixture of them exposure to Hep G2 cells. The results showed that PFOA and PFOS (50-200 {mu}mol/l) induced production of reactive oxygen species (ROS), dissipation of mitochondria membrane potential and apoptosis of Hep G2 cells. Moreover, activities of superoxide dismutase, catalase and glutathione reductase were increased, whereas activities of glutathione-S-transferase and glutathione peroxidase were decreased. Glutathione content was reduced. Differential expression of genes, such as p53, Bcl-2, caspase-9, was evident in PFOA or PFOS exposure groups. The possible mechanism was that they could overwhelm homeostasis of antioxidative systems, boost ROS generation, impact mitochondria, and affect genes expression of apoptotic regulators, which resulted in start-ups of apoptosis program. Cells exposed to mixture of PFOA and PFOS and each of them showed non-apoptotic rate significant difference, which indicated that the combined effect of two compounds was summation effect, but neither synergistic nor antagonistic effect. (orig.)

  14. Evaluation of Linear Alkylbenzene Sulfonate (LAS) behaviour in agricultural soil through laboratory continuous studies. (United States)

    Oliver-Rodríguez, B; Zafra-Gómez, A; Reis, M S; Duarte, B P M; Verge, C; de Ferrer, J A; Pérez-Pascual, M; Vílchez, J L


    The behaviour of Linear Alkylbenzene Sulfonate (LAS) in agricultural soil is investigated in the laboratory using continuous-flow soil column studies in order to simultaneously analyze the three main underlying phenomena (adsorption/desorption, degradation and transport). The continuous-flow soil column experiments generated the breakthrough curves for each LAS homologue, C10, C11, C12 and C13, and by adding them up, for total LAS, from which the relevant retention, degradation and transport parameters could be estimated, after proposing adequate models. Several transport equations were considered, including the degradation of the sorbate in solution and its retention by soil, under equilibrium and non-equilibrium conditions between the sorbent and the sorbate. In general, the results obtained for the estimates of those parameters that were common to the various models studied (such as the isotherm slope, first order degradation rate coefficient and the hydrodynamic dispersion coefficient) were rather consistent, meaning that mass transfer limitations are not playing a major role in the experiments. These three parameters increase with the length of the LAS homologue chain. The study will provide the underlying conceptual framework and fundamental parameters to understand, simulate and predict the environmental behaviour of LAS compounds in agricultural soils. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Spontaneous modification of graphite anode by anthraquinone-2-sulfonic acid for microbial fuel cells. (United States)

    Tang, Xinhua; Li, Haoran; Du, Zhuwei; Ng, How Yong


    In this study, anthraquinone-2-sulfonic acid (AQS), an electron transfer mediator, was immobilized onto graphite felt surface via spontaneous reduction of the in situ generated AQS diazonium cations. Cyclic voltammetry (CV) and energy dispersive spectrometry (EDS) characterizations of AQS modified graphite demonstrated that AQS was covalently grafted onto the graphite surface. The modified graphite, with a surface AQS concentration of 5.37 ± 1.15 × 10(-9)mol/cm(2), exhibited good electrochemical activity and high stability. The midpoint potential of the modified graphite was about -0.248 V (vs. normal hydrogen electrode, NHE), indicating that electrons could be easily transferred from NADH in bacteria to the electrode. AQS modified anode in MFCs increased the maximum power density from 967 ± 33 mW/m(2) to 1872 ± 42 mW/m(2). These results demonstrated that covalently modified AQS functioned as an electron transfer mediator to facilitate extracellular electron transfer from bacteria to electrode and significantly enhanced the power production in MFCs. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Adsorption of perfluorooctane sulfonate on soils: Effects of soil characteristics and phosphate competition. (United States)

    Qian, Jin; Shen, Mengmeng; Wang, Peifang; Wang, Chao; Hou, Jun; Ao, Yanhui; Liu, Jingjing; Li, Kun


    Perfluorooctane sulfonate (PFOS) is an emerging contaminant, whose presence has been detected in different compartments of the environment in many countries. In this study, the effects of soil characteristics and phosphate competition on the adsorption of PFOS on soils were investigated. Results from batch sorption experiments showed that all the adsorption isotherms of PFOS on three tested soils were nonlinear. In experiments without the addition of phosphate (P) to the soil solution, the Freundlich sorption affinity (Kf) of PFOS on S (original soil), S1 (soil from which soil organic matter (SOM) had been removed), and S2 (soil from which both SOM and ferric oxides had been removed) were 23.13, 10.37 and 15.95, respectively. The results suggested that a high amount of SOM in soil can increase the sorption affinity of PFOS on soils and that a greater amount of ferric oxides can reduce it. The addition of P in the soil solution reduced the Kf of PFOS on S, S1, and S2 by approximately 25%, 50%, and 15%, respectively. For the binary system of PFOS and P, soil with higher ferric oxide content showed greater Kf reduction after P addition; whereas soil with higher SOM content showed less Kf reduction. Our results suggest that for soils dominated by ferric oxides, P is a more effective competitor than PFOS for the adsorption sites in the binary system; whereas in soils containing more SOM, P is a weak competitor. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Decolorization and detoxification of sulfonated azo dye methyl orange by Kocuria rosea MTCC 1532. (United States)

    Parshetti, G K; Telke, A A; Kalyani, D C; Govindwar, S P


    Kocuria rosea (MTCC 1532) showed 100% decolorization of methyl orange (50 mg l(-1)) under static condition. The optimum pH and temperature for dye decolorization was 6.8 and 30 degrees C, respectively. The K. rosea (MTCC 1532) showed maximum decolorization of methyl orange when growth medium containing yeast extract as compared to other substrates. The culture exhibited significant ability to decolorize repeated additions of dye, with reduction in time up to 12 h at eighth dye aliquot addition. Significant induction of reductases (NADH-DCIP reductase and azoreductase) suggests its involvement in decolorization of methyl orange. The metabolites formed after decolorization of methyl orange, such as 4-amino sulfonic acid and N,N'-dimethyl p-phenyldiamine were characterized using FTIR and MS. Phytotoxicity and microbial toxicity study showed the methyl orange was toxic and metabolites obtained after its decolorization was nontoxic for experimental plants (Triticum aestivum and Phaseolus mungo) and bacteria (K. rosea, Pseudomonas aurugenosa and Azatobacter vinelandii). 2009 Elsevier B.V. All rights reserved.

  18. Metallic nanomesh

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Zhifeng; Sun, Tianyi; Guo, Chuanfei


    A transparent flexible nanomesh having at least one conductive element and sheet resistance less than 300.OMEGA./.quadrature. when stretched to a strain of 200% in at least one direction. The nanomesh is formed by depositing a sacrificial film, depositing, etching, and oxidizing a first metal layer on the film, etching the sacrificial film, depositing a second metal layer, and removing the first metal layer to form a nanomesh on the substrate.

  19. Poly(vinylidene fluoride) modification induced by gamma irradiation for application as ionic polymer-metal composite; Modificacao de poli(fluoreto de vinilideno) induzida por radiacao gama para aplicacao como composito ionomerico de metal-polimero

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Henrique Perez


    Gamma-radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses from 1 to 100 kGy in the presence of a styrene/N,N- dimethylformamide (DMF) solution (1:1, v/v) and styrene/toluene (1:1, v/v) at dose rate of 5 kGy h-1 was carried out by simultaneous method under nitrogen atmosphere at room temperature, using gamma rays from a Co-60. After grafting reactions, the polymer was then sulfonated in chlorosulfonic acid/1,2-dichloroethane (2 and 10%) for 3 hours. The films were characterized before and after modification by calculating the degree of grafting (DOG), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). DOG results show that grafting increases with dose, and varies enormously depending on the solvent used, with DOGs about 20 times greater in DMF than in toluene. It was possible to confirm the grafting of styrene by FT-IR due to the appearance of the new characteristic peaks and by the TG and DSC which exhibited changes in the thermal behavior of the grafted/sulfonated material. Sulfonated material was also characterized by ion exchange capacity (IEC) showed that both DOG and sulfonic acid concentration increase IEC values. Results showed that it is possible to obtain materials with ion exchange capacity of possible application as ionic polymer-metal composites. (author)

  20. VLSI metallization

    CERN Document Server

    Einspruch, Norman G; Gildenblat, Gennady Sh


    VLSI Electronics Microstructure Science, Volume 15: VLSI Metallization discusses the various issues and problems related to VLSI metallization. It details the available solutions and presents emerging trends.This volume is comprised of 10 chapters. The two introductory chapters, Chapter 1 and 2 serve as general references for the electrical and metallurgical properties of thin conducting films. Subsequent chapters review the various aspects of VLSI metallization. The order of presentation has been chosen to follow the common processing sequence. In Chapter 3, some relevant metal deposition tec

  1. Effects of sulfonated polyether-etherketone (SPEEK) and composite membranes on the proton exchange membrane fuel cell (PEMFC) performance

    Energy Technology Data Exchange (ETDEWEB)

    Erce Senguel; Erdener, Huelya; Akay, R. Gueltekin; Yuecel, Hayrettin; Eroglu, inci [Chemical Engineering Department, Middle East Technical University, 06531 Ankara (Turkey); Bac, Nurcan [Chemical Engineering Department, Yeditepe University, 34755 Istanbul (Turkey)


    Sulfonated polyether-etherketone (SPEEK) has a potential for proton exchange fuel cell applications. However, its conductivity and thermohydrolytic stability should be improved. In this study the proton conductivity was improved by addition of an aluminosilicate, zeolite beta. Moreover, thermohydrolytic stability was improved by blending poly-ether-sulfone (PES). Sulfonated polymers were characterized by H-NMR. Composite membranes prepared were characterized by Electrochemical Impedance Spectroscopy (EIS) for their proton conductivity. Degree of sulfonation (DS) values calculated from H-NMR results, and both proton conductivity and thermohydrolytic stability was found to strongly depend on DS. Therefore, DS values were controlled time in the range of 55-75% by controlling the reaction time. Zeolite beta fillers at different SiO{sub 2}/Al{sub 2}O{sub 3} ratios (20, 30, 40, 50) were synthesized and characterized by XRD, EDX, TGA, and SEM. The proton conductivity of plain SPEEK membrane (DS = 68%) was 0.06 S/cm at 60 C and the conductivity of the composite membrane containing of zeolite beta filled SPEEK was found to increase to 0.13 S/cm. Among the zeolite Beta/SPEEK composite membranes the best conductivity results were achieved with zeolite beta having a SiO{sub 2}/Al{sub 2}O{sub 3} ratio of 50 at 10 wt% loading. Single fuel cell tests performed at different operating temperatures indicated that SPES/SPEEK membrane is more stable hydrodynamically and also performed better than pristine SPEEK membranes which swell excessively. Membrane electrode assemblies (MEAs) were prepared by gas diffusion layer (GDL) spraying method. The highest performance of 400 mA/cm{sup 2} was obtained for SPEEK membrane (DS 56%) at 0.6 V for a H{sub 2}-O{sub 2}/PEMFC working at 1 atm and 70 C. At the same conditions Nafion {sup registered} 112 gave 660 mA/cm{sup 2}. It was observed that the operating temperature can be increased up to 90 C with polymer blends containing poly-ether-sulfone

  2. Sulfonation of 17{beta}-estradiol and inhibition of sulfotransferase activity by polychlorobiphenylols and celecoxib in channel catfish, Ictalurus punctatus

    Energy Technology Data Exchange (ETDEWEB)

    Wang Liquan [Department of Medicinal Chemistry, College of Pharmacy, University of Florida, Gainesville, FL 32610 (United States); James, Margaret O. [Department of Medicinal Chemistry, College of Pharmacy, University of Florida, Gainesville, FL 32610 (United States)]. E-mail:


    The sulfonation of 17{beta}-estradiol (E2) by human liver and recombinant sulfotransferases is influenced by environmental contaminants such as hydroxylated metabolites of polychlorinated biphenyls (OH-PCBs), which are potent inhibitors, and the therapeutic drug, celecoxib, which affects positional sulfonation of E2. In some locations, the aquatic environment is contaminated by PCBs, OH-PCBs and widely used therapeutic drugs. The objectives of this study were to investigate the sulfonation kinetics of E2 in liver cytosol from channel catfish (Ictalurus punctatus); to examine the effect of OH-PCBs on E2 sulfonation; and to determine if celecoxib altered the position of E2 sulfonation, as it does with human liver cytosol. E2 was converted to both 3- and 17-sulfates by catfish liver cytosol. At E2 concentrations below 1{mu}M, formation of E2-3-sulfate (E2-3-S) predominated, but substrate inhibition was observed at higher concentrations. Rates of E2-3-S formation at different E2 concentrations were fit to a substrate inhibition model, with K{sup '}{sub m} and V{sup '}{sub max} values of 0.40+/-0.10{mu}M and 91.0+/-4.7pmol/min/mg protein, respectively and K{sub i} of 1.08+/-0.09{mu}M. The formation of E2-17-S fit Michaelis-Menten kinetics over the concentration range 25nM to 2.5{mu}M, with K{sub m} and V{sub max} values of 1.07+/-0.23{mu}M and 25.7+/-4.43pmol/min/mg protein, respectively. The efficiency (V{sub max}/K{sub m}) of formation of E2-3-S was 9.8-fold higher than that of E2-17-S. Several OH-PCBs inhibited E2 3-sulfonation, measured at an E2 concentration of 1nM. Of those tested, the most potent inhibitor was 4'-OH-CB79, with two chlorine atoms flanking the OH group (IC{sub 50}: 94nM). The inhibition of estrogen sulfonation by OH-PCBs may disrupt the endocrine system and thus contribute to the known toxic effects of these compounds. Celecoxib did not stimulate E2-17-S formation, as is the case with human liver cytosol, but did inhibit the

  3. Raman spectroscopic characterization of isomers of metal N-phenyl protoporphyrin IX dimethylesters

    Energy Technology Data Exchange (ETDEWEB)

    Shelnutt, J.A.; Sparks, L.D.; Chamberlain, J.R.; Hsu, P.; Ondrias, M.R. (Sandia National Lab., Albuquerque, NM (United States) Univ. of New Mexico, Albuquerque (United States)); Swanson, B.; Montellano, P.O. de (Univ. of California, San Francisco (United States))


    The reaction of heme proteins with phenylhydrazine results in N-phenylprotoporphyrin formation. The authors are using resonance Raman and UV-visible adsorption spectroscopies to investigate the structure of N-phenylprotoporphyrin dimethylesters (N[Phi]PPDME) metal derivatives. Distortion from planarity of the protoporphyrin macrocycle results from addition of the phenyl group. Porphyrin planarity is thought to influence chemical and electron-transfer properties of tetrapyrroles contained in proteins such as methylreductase and the photosynthetic reaction center. Specifically, the authors investigated the conformation of regioisomers obtained by substitution at the A, B, C, and D pyrrole rings on the distal side. Isomers A and B of Cu- and ZnN[Phi]PPDME show spectroscopic similarities and isomers C and D are similar; A and B are different from isomers C and D. This difference is due mainly to the location of the vinyl substituents at the periphery of the porphyrin. In the Raman spectra, the differences show up primarily in the vinyl vibrational modes and vinyl-sensitive porphyrin modes. Molecular mechanics calculations also are used to interpret the spectroscopic results. The calculations were carried out for various isomers and conformers of Fe(III) N-phenylprotoporphyrin chloride and Cu(II) N-phenylprotoporphyrin. Predicted structures are similar to reported N-substituted tetraphenylporphyrins, with the major distortion from planarity occurring for the N-substituted pyrrole ring. The energies are found to be affected by orientations of the vinyl substituent groups.

  4. Heavy metal

    African Journals Online (AJOL)

    niloticus after exposure to sublethal concentrations of heavy metals such as copper, lead and zinc for a 12-week period, using static renewable toxicity tests. The concentrations of the metals accumulated in the tissue of exposed fish were about 3-5 times higher than the concentrations detected in control fish.

  5. An Ethylmethane Sulfonate Mutant Resource in Pre-Green Revolution Hexaploid Wheat. (United States)

    Dhaliwal, Amandeep K; Mohan, Amita; Sidhu, Gaganjot; Maqbool, Rizwana; Gill, Kulvinder S


    Mutagenesis is a powerful tool used for studying gene function as well as for crop improvement. It is regaining popularity because of the development of effective and cost efficient methods for high-throughput mutation detection. Selection for semi-dwarf phenotype during green revolution has reduced genetic diversity including that for agronomically desirable traits. Most of the available mutant populations in wheat (Triticum aestivum L.) were developed in post-green revolution cultivars. Besides the identification and isolation of agronomically important alleles in the mutant population of pre-green revolution cultivar, this population can be a vital resource for expanding the genetic diversity for wheat breeding. Here we report an Ethylmethane Sulfonate (EMS) generated mutant population consisting of 4,180 unique mutant plants in a pre-green revolution spring wheat cultivar 'Indian'. Released in early 1900s, 'Indian' is devoid of any known height-reducing mutations. Unique mutations were captured by proceeding with single M2 seed from each of the 4,180 M1 plants. Mutants for various phenotypic traits were identified by detailed phenotyping for altered morphological and agronomic traits on M2 plants in the greenhouse and M3 plants in the field. Of the 86 identified mutants, 75 (87%) were phenotypically stable at the M4 generation. Among the observed phenotypes, variation in plant height was the most frequent followed by the leaf morphology. Several mutant phenotypes including looped peduncle, crooked plant morphology, 'gritty' coleoptiles, looped lower internodes, and burnt leaf tips are not reported in other plant species. Considering the extent and diversity of the observed mutant phenotypes, this population appears to be a useful resource for the forward and reverse genetic studies. This resource is available to the scientific community.

  6. Environmental monitoring study of linear alkylbenzene sulfonates and insoluble soap in Spanish sewage sludge samples. (United States)

    Cantarero, Samuel; Zafra-Gómez, Alberto; Ballesteros, Oscar; Navalón, Alberto; Reis, Marco S; Saraiva, Pedro M; Vílchez, José L


    In this work we present a monitoring study of linear alkylbenzene sulfonates (LAS) and insoluble soap performed on Spanish sewage sludge samples. This work focuses on finding statistical relations between LAS concentrations and insoluble soap in sewage sludge samples and variables related to wastewater treatment plants such as water hardness, population and treatment type. It is worth to mention that 38 samples, collected from different Spanish regions, were studied. The statistical tool we used was Principal Component Analysis (PC), in order to reduce the number of response variables. The analysis of variance (ANOVA) test and a non-parametric test such as the Kruskal-Wallis test were also studied through the estimation of the p-value (probability of obtaining a test statistic at least as extreme as the one that was actually observed, assuming that the null hypothesis is true) in order to study possible relations between the concentration of both analytes and the rest of variables. We also compared LAS and insoluble soap behaviors. In addition, the results obtained for LAS (mean value) were compared with the limit value proposed by the future Directive entitled "Working Document on Sludge". According to the results, the mean obtained for soap and LAS was 26.49 g kg(-1) and 6.15 g kg(-1) respectively. It is worth noting that LAS mean was significantly higher than the limit value (2.6 g kg(-1)). In addition, LAS and soap concentrations depend largely on water hardness. However, only LAS concentration depends on treatment type.

  7. Applying moving bed biofilm reactor for removing linear alkylbenzene sulfonate using synthetic media

    Directory of Open Access Journals (Sweden)

    Jalaleddin Mollaei


    Full Text Available Detergents and problems of their attendance into water and wastewater cause varied difficulties such as producing foam, abnormality in the growth of algae, accumulation and dispersion in aqueous environments. One of the reactors was designated with 30% of the media with the similar conditions exactly same as the other which had filling rate about 10 %, in order to compare both of them together. A standard method methylene blue active substance was used to measure anionic surfactant. The concentrations of linear alkylbenzene sulfonate which examined were 50, 100, 200, 300 and 400 mg/l in HRT 72, 24 and 8 hrs. The removal percentage for both of reactors at the beginning of operating at50 mg/l concentration of pollutant had a bit difference and with gradually increasing the pollutant concentration and decreasing Hydraulic retention time, the variation between the removal percentage of both reactors became significant as the reactor that had the filling rate about 30 %, showed better condition than the other reactor with 10 % filling rate. Ideal condition in this experiment was caught at hydraulic retention time about 72 hrs and 200 mg/l pollutants concentration with 99.2% removal by the reactor with 30% filling rate. While the ideal condition for the reactor with 10% filling rate with the same hydraulic retention time and 100 mg/l pollutants concentrations was obtained about 99.4% removal. Regarding anionic surfactant standard in Iran which is 1.5 mg/l for surface water discharge, using this process is suitable for treating municipal wastewater and industrial wastewater which has a range of the pollutant between 100-200 mg/l. but for the industries that produce detergents products which make wastewater containing more than 200 mg/l surfactants, using secondary treatment process for achieving discharge standard is required.

  8. An Ethylmethane Sulfonate Mutant Resource in Pre-Green Revolution Hexaploid Wheat.

    Directory of Open Access Journals (Sweden)

    Amandeep K Dhaliwal

    Full Text Available Mutagenesis is a powerful tool used for studying gene function as well as for crop improvement. It is regaining popularity because of the development of effective and cost efficient methods for high-throughput mutation detection. Selection for semi-dwarf phenotype during green revolution has reduced genetic diversity including that for agronomically desirable traits. Most of the available mutant populations in wheat (Triticum aestivum L. were developed in post-green revolution cultivars. Besides the identification and isolation of agronomically important alleles in the mutant population of pre-green revolution cultivar, this population can be a vital resource for expanding the genetic diversity for wheat breeding. Here we report an Ethylmethane Sulfonate (EMS generated mutant population consisting of 4,180 unique mutant plants in a pre-green revolution spring wheat cultivar 'Indian'. Released in early 1900s, 'Indian' is devoid of any known height-reducing mutations. Unique mutations were captured by proceeding with single M2 seed from each of the 4,180 M1 plants. Mutants for various phenotypic traits were identified by detailed phenotyping for altered morphological and agronomic traits on M2 plants in the greenhouse and M3 plants in the field. Of the 86 identified mutants, 75 (87% were phenotypically stable at the M4 generation. Among the observed phenotypes, variation in plant height was the most frequent followed by the leaf morphology. Several mutant phenotypes including looped peduncle, crooked plant morphology, 'gritty' coleoptiles, looped lower internodes, and burnt leaf tips are not reported in other plant species. Considering the extent and diversity of the observed mutant phenotypes, this population appears to be a useful resource for the forward and reverse genetic studies. This resource is available to the scientific community.

  9. Fuel cell performance of pendent methylphenyl sulfonated poly(ether ether ketone ketone)s (United States)

    Zhang, Hanyu; Stanis, Ronald J.; Song, Yang; Hu, Wei; Cornelius, Chris J.; Shi, Qiang; Liu, Baijun; Guiver, Michael D.


    Meta- and para-linked homopolymers bearing 3-methylphenyl (Me) pendent groups were postsulfonated to create sulfonated poly(ether ether ketone ketone) (SPEEKK) backbone isomers, which are referred to as Me-p-SPEEKK and Me-m-SPEEKK. Their thermal and oxidative stability, mechanical properties, dimensional stability, methanol permeability, and proton conductivity are characterized. Me-p-SPEEKK and Me-m-SPEEKK proton conductivities at 100 °C are 116 and 173 mS cm-1, respectively. Their methanol permeabilities are 3.3-3.9 × 10-7 cm2 s-1, and dimensional swelling at 100 °C is 16.4-17.5%. Me-p-SPEEKK and Me-m-SPEEKK were fabricated into membrane electrode assemblies (MEAs), and electrochemical properties were evaluated within a direct methanol fuel cell (DMFC) and proton-exchange membrane fuel cell (PEMFC). When O2 is used as the oxidant at 80 °C and 100% RH, the maximum power density of Me-m-SPEEKK reaches 657 mW cm-2, which is higher than those of Nafion 115 (552 mW cm-2). DMFC performance is 85 mW cm-2 at 80 °C with 2.0 M methanol using Me-p-SPEEKK due to its low MeOH crossover. In general, these electrochemical results are comparable to Nafion. These ionomer properties, combined with a potentially less expensive and scalable polymer manufacturing process, may broaden their potential for many practical applications.

  10. Adsorption Mechanisms of Dodecylbenzene Sulfonic Acid by Corn Straw and Poplar Leaf Biochars

    Directory of Open Access Journals (Sweden)

    Nan Zhao


    Full Text Available Biochar is an eco-friendly, renewable, and cost-effective material that can be used as an adsorbent for the remediation of contaminated environments. In this paper, two types of biochar were prepared through corn straw and poplar leaf pyrolysis at 300 °C and 700 °C (C300, C700, P300, P700. Brunaer–Emmett–Teller N2 surface area, scanning electron microscope, elemental analysis, and infrared spectra were used to characterize their structures. These biochars were then used as adsorbents for the adsorption of dodecylbenzene sulfonic acid (DBSA. The microscopic adsorption mechanisms were studied by using infrared spectra, 13C-nuclear magnetic resonance spectra, and electron spin resonance spectra. The surface area and pore volume of C700 (375.89 m2/g and 0.2302 cm3/g were the highest among all samples. Elemental analysis results showed that corn straw biochars had a higher aromaticity and carbon to nitrogen (C/N ratio than the poplar leaf biochars. High temperature caused the increase of carbon content and the decrease of oxygen content, which also gave the biochars a higher adsorption rate. Pseudo-second order kinetic provided a better fit with the experimental data. Adsorption isotherm experiments showed that the adsorption isotherm of C300 fit the linear model. For other biochars, the adsorption isotherms fitted Langmuir model. Biochars with high temperatures exhibited enhanced adsorption capacity compared with ones at low temperatures. The qmax values of biochars to DBSA followed the order of P700 > C700 > P300. The adsorption mechanisms were complex, including partition, anion exchange, the formation of H bonds, covalent bonds, and charge transfer. The adsorption by covalent bonding might be the key mechanism determining the adsorption capacity of P700.

  11. Pistacia lentiscus resin regulates intestinal damage and inflammation in trinitrobenzene sulfonic acid-induced colitis. (United States)

    Gioxari, Aristea; Kaliora, Andriana C; Papalois, Apostolos; Agrogiannis, George; Triantafillidis, John K; Andrikopoulos, Nikolaos K


    Mastic (Pistacia lentiscus) of the Anacardiaceae family has exhibited anti-inflammatory and antioxidant properties in patients with Crohn's disease. This study was based on the hypothesis that mastic inhibits intestinal damage in inflammatory bowel disease, regulating inflammation and oxidative stress in intestinal epithelium. Four different dosages of P. lentiscus powder in the form of powder were administered orally to trinitrobenzene sulfonic acid-induced colitic rats. Eighty-four male Wistar rats were randomly assigned to seven groups: A, control; B, colitic; C-F, colitic rats daily supplemented with P. lentiscus powder at (C) 50 mg/kg, (D) 100 mg/kg, (E) 200 mg/kg, and (F) 300 mg/kg of body weight; and G, colitic rats treated daily with cortisone (25 μg/kg of body weight). Colonic damage was assessed microscopically. The cytokines tumor necrosis factor-α, intercellular adhesion molecule-1 (ICAM-1), interleukin (IL)-6, IL-8, and IL-10 and malonaldehyde were measured in colonic specimens. Results were expressed as mean ± SE values. Histological amelioration of colitis (P≤.001) and significant differences in colonic indices occurred after 3 days of treatment. Daily administration of 100 mg of P. lentiscus powder/kg of body weight decreased all inflammatory cytokines (P≤.05), whereas 50 mg of P. lentiscus powder/kg of body weight and cortisone treatment reduced only ICAM-1 (P≤.05 and P≤.01, respectively). Malonaldehyde was significantly suppressed in all treated groups (P≤.01). IL-10 remained unchanged. Cytokines and malonaldehyde remained unaltered after 6 days of treatment. Thus P. lentiscus powder could possibly have a therapeutic role in Crohn's disease, regulating oxidant/antioxidant balance and modulating inflammation.

  12. Uptake of gas phase sulfur species methanesulfonic acid, dimethylsulfoxide, and dimethyl sulfone by aqueous surfaces

    Energy Technology Data Exchange (ETDEWEB)

    De Bruyn, W.J.; Shorter, J.A.; Davidovits, P. [Boston College, Chestnut Hill, MA (United States); Worsnop, D.R.; Zahniser, M.S.; Kolb, C.E. [Aerodyne Research, Inc., Billerica, MA (United States)


    Biogenic reduced sulfur species are emitted from the oceans and then oxidized in the marine boundary layer. The gas/liquid interactions of these oxidized species must be understood in order to evaluate the relative contributions to marine boundary layer aerosol levels from anthropogenic and biogenic sources and to assess the overall impact of these aerosols on global climate. A key parameter in understanding these interactions is the mass accommodation coefficient, which is simply the probability that a gas phase molecule enters into a liquid on striking the liquid surface. The mass accommodation coefficients for dimethylsulfoxide, dimethyl sulfone, and methanesulfonic acid into water have been measured as a function of temperature (260-280 K), pH (1-14), and NaCl concentration (0-3.5 M). The experimental method employs a monodispersed train of fast droplets in a low-pressure flow reactor. The mass accommodation coefficients show a negative temperature dependence varying from {approximately} 0.1 to {approximately} 0.2 over the range of temperatures studied. The measured uptake is independent of pH and NaCl concentration in the ranges studied. The mass accommodation coefficients are well expressed in terms of an observed Gibbs free energy {Delta}G{sub obs}{sup No.} - T{Delta}S{sub obs}{sup No.} as {alpha}/(1 - {alpha}) = exp (-{Delta}G{sub obs}{sup No.}/RT). The results are discussed in terms of a previously described uptake model. In the marine boundary layer, mass transfer of these species into aerosols will be limited by mass accommodation for aerosols with diameters of less than 2 {mu}m. 28 refs., 5 figs., 2 tabs.

  13. Effects of perfluorooctane sulfonate (PFOS) on swimming behavior and membrane potential of paramecium caudatum. (United States)

    Kawamoto, Kosuke; Nishikawa, Yasuo; Oami, Kazunori; Jin, Yihe; Sato, Itaru; Saito, Norimitsu; Tsuda, Shuji


    Persistent perfluorinated organic compounds such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were distributed widely in the global. PFOS (15 microM or higher) caused backward swimming of paramecia. The Triton-extracted paramecia, where the membrane was disrupted and the externally applied chemicals are freely accessible to the ciliary apparatus, showed forward swimming up to 0.1 microM Ca2+ in the medium and backward swimming at about 0.2 microM and higher. PFOS (0.1 mM) did not change the relationship between the swimming directions and free Ca2+ concentrations. Effects of various surfactants including PFOS and PFOA on the swimming direction of paramecia were compared with the hemolysis of mouse erythrocytes as an indicator of surfactant activities. The hemolysis did not correlate with their swimming behavior. PFOS caused triphasic membrane potential changes both in the wild-type paramecia and caudatum non-reversal (CNR) mutants, the latter is defective in voltage-gated Ca2+ channels. An action potential of the wild-type specimen was induced at lower current intensity when PFOS was present in the medium. Voltage-clamp study indicated that PFOS had no effect on the depolarization-induced Ca2+ influx responsible for the action potential. The membrane potential responses obtained were similar to those obtained by the application of some bitter substances such as quinine that activate chemoreceptors of paramecia. Since the CNR specimens did not exhibit PFOS-induced backward swimming at concentrations examined, the backward swimming is attributable to the influx of Ca2+ into the cilia through voltage-gated Ca2+ channels. The Ca2+ channels are most probably activated by the depolarizing receptor potentials resulted from the PFOS-induced activation of chemoreceptors.

  14. Effect of adding Nanoclay (Cloisite-30B on the Proton Conductivity of Sulfonated Polybenzimidazole

    Directory of Open Access Journals (Sweden)

    Hashem Ahmadizadegan


    Full Text Available A novel sulfonated polybenzimidazole/organoclay (Cloisite-30B (SPBI/clay nanocomposite membranes was successfully synthesized based on aromatic diacide (1 and diaminobenzidine. Nanocomposite membranes were fabricated using 1, 4-bis (hydroxymethyl benzene (BHMB as cross-linker, and Cloisite-30B organoclay as the pseudo cross-linker. The cross-linked SPBI/clay nanocomposite membranes were prepared via solution intercalation method. Participation of reactive organoclay in the cross-linking process was established from ion exchange capacity (IEC measurements and FTIR studies. Wide angle X-ray diffraction (WAXD, field emission-scanning electron microscopy (FE-SEM, and transmission electron microscopy (TEM techniques confirmed the presence of a combination of the intercalated and partially exfoliated clay confirmed mixed clay dispersion morphology of intercalation and partial exfoliation of the clay platelets in the cross-linked SPBI/clay nanocomposite membrane. The cross-linked SPBI/clay nanocomposite membranes showed higher tensile strength, modulus and lower elongation at break compared to neat cross-linked SPBI. Water and methanol uptake studies revealed superior barrier properties of cross-linked SPBI/clay nanocomposite membranes compared to cross-linked SPBI. Furthermore, thermal stability, residual solvent in the membrane film, and structural ruination of membranes were analyzed by thermal gravimetric analysis (TGA. TGA data indicated an increase in thermal stability of the SPBI/clay nanocomposite membranes in compared to the pure polymer. The oxidative stability of SPBI improved remarkably with cross-linking and subsequent clay addition. These improvements in the thermo-mechanical, barrier and oxidative stability of the membranes could be achieved without significantly affecting the protonic conductivity.

  15. Ultrasound-assisted adsorption of 4-dodecylbenzene sulfonate from aqueous solutions by corn cob activated carbon. (United States)

    Milenković, D D; Bojić, A Lj; Veljković, V B


    This study was aimed at removal of 4-dodecylbenzene sulfonate (DBS) ions from aqueous solutions by ultrasound-assisted adsorption onto the carbonized corn cob (AC). The main attention was focused on modeling the equilibrium and kinetics of adsorption of DBS onto the AC. The AC was prepared from ground dried corn cob by carbonization and activation by carbon dioxide at 880°C for 2h in a rotary furnace. The adsorption isotherm data were fitted by the Langmuir model in both the absence and the presence of ultrasound (US). The maximum adsorption capacities of the adsorbent for DBS, calculated from the Langmuir isotherms, were 29.41mg/g and 27.78mg/g in the presence of US and its absence, respectively. The adsorption process in the absence and the presence of US obeyed the pseudo second-order kinetics. The intraparticular diffusion model indicated that the adsorption of DBS ions on the AC was diffusion controlled as well as that US promoted intraparticular diffusion. The ΔG° values, -24.03kJ/mol, -25.78kJ/mol and -27.78kJ/mol, were negative at all operating temperatures, verifying that the adsorption of DBS ions was spontaneous and thermodynamically favorable. The positive value of ΔS°=187J/molK indicated the increased randomness at the adsorbent-adsorbate interface during the adsorption of DBS ions by the AC. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Occurrence of Perfluorooctanoic Acid and Perfluorooctane Sulfonate in Milk and Yogurt and Their Risk Assessment. (United States)

    Xing, Zhenni; Lu, Jianjiang; Liu, Zilong; Li, Shanman; Wang, Gehui; Wang, Xiaolong


    Although perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been identified in milk and dairy products in many regions, knowledge on their occurrence in Xinjiang (China) is rare. This study was conducted to measure the levels of PFOA and PFOS in milk and yogurt from Xinjiang and to investigate the average daily intake (ADI) of these two compounds. PFOA and PFOS levels were analyzed using ultrasonic extraction with methanol and solid-phase extraction followed by liquid chromatography-mass spectrometry. Retail milk and yogurt samples present higher detection rates (39.6% and 48.1%) and mean concentrations (24.5 and 31.8 ng/L) of PFOS than those of PFOA (33.0% and 37.0%; 16.2 and 22.6 ng/L, respectively). For raw milk samples, only PFOS was detected. The differences in the levels of the two compounds between samples from the north and south regions were observed, and northern regions showed higher pollution levels than southern regions. On the basis of the retail milk measurements and consumption data, the ADIs of PFOA and PFOS for Xinjiang adults were calculated to be 0.0211 and 0.0318 ng/kg/day, respectively. Furthermore, the estimated intakes of PFOA and PFOS varied among different groupings (age, area, gender, and race) and increased with increasing age. Relevant hazard ratios were found to be far less than 1.0, and this finding suggested that no imminent health damages were produced by PFOA and PFOS intake via milk and yogurt consumption in the Xinjiang population.

  17. Occurrence of Perfluorooctanoic Acid and Perfluorooctane Sulfonate in Milk and Yogurt and Their Risk Assessment

    Directory of Open Access Journals (Sweden)

    Zhenni Xing


    Full Text Available Although perfluorooctanoic acid (PFOA and perfluorooctane sulfonate (PFOS have been identified in milk and dairy products in many regions, knowledge on their occurrence in Xinjiang (China is rare. This study was conducted to measure the levels of PFOA and PFOS in milk and yogurt from Xinjiang and to investigate the average daily intake (ADI of these two compounds. PFOA and PFOS levels were analyzed using ultrasonic extraction with methanol and solid-phase extraction followed by liquid chromatography–mass spectrometry. Retail milk and yogurt samples present higher detection rates (39.6% and 48.1% and mean concentrations (24.5 and 31.8 ng/L of PFOS than those of PFOA (33.0% and 37.0%; 16.2 and 22.6 ng/L, respectively. For raw milk samples, only PFOS was detected. The differences in the levels of the two compounds between samples from the north and south regions were observed, and northern regions showed higher pollution levels than southern regions. On the basis of the retail milk measurements and consumption data, the ADIs of PFOA and PFOS for Xinjiang adults were calculated to be 0.0211 and 0.0318 ng/kg/day, respectively. Furthermore, the estimated intakes of PFOA and PFOS varied among different groupings (age, area, gender, and race and increased with increasing age. Relevant hazard ratios were found to be far less than 1.0, and this finding suggested that no imminent health damages were produced by PFOA and PFOS intake via milk and yogurt consumption in the Xinjiang population.

  18. Removal of perfluorooctanoic acid and perfluorooctane sulfonate via ozonation under alkaline condition

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Angela Yu-Chen, E-mail: [Graduate Institute of Environmental Engineering, National Taiwan University, 71, Chou-Shan Rd., Taipei 106, Taiwan (China); Panchangam, Sri Chandana; Chang, Cheng-Yi [Graduate Institute of Environmental Engineering, National Taiwan University, 71, Chou-Shan Rd., Taipei 106, Taiwan (China); Hong, P.K. Andy [Department of Civil and Environmental Engineering, University of Utah, Salt Lake City, Utah 84112 (United States); Hsueh, Han-Fang [Graduate Institute of Environmental Engineering, National Taiwan University, 71, Chou-Shan Rd., Taipei 106, Taiwan (China)


    Highlights: Black-Right-Pointing-Pointer PFOA and PFOS are degraded by O{sub 3} or O{sub 3}/H{sub 2}O{sub 2} treatment at pH 11. Black-Right-Pointing-Pointer Degradation of PFOA and PFOS by O{sub 3} or O{sub 3}/H{sub 2}O{sub 2} under alkaline condition is enhanced when the compounds are pretreated by 15 min of ozonation at ambient pH (4-5). Black-Right-Pointing-Pointer PFOA and PFOS removal by O{sub 3} or O{sub 3}/H{sub 2}O{sub 2} at pH 11 was efficient relative to existing methods in terms of energy and contact time. - Abstract: The elimination of recalcitrant, ubiquitous perfluoroalkyl acids (PFAAs) such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) is desirable for reducing potential human health and environmental risks. We here report the degradation of PFOA and PFOS by 85-100% via ozonation under alkaline condition being studied at environmentally relevant contaminant concentrations of 50 {mu}g L{sup -1} to 5 mg L{sup -1}, with enhanced removal rates by addition of hydrogen peroxide. Enhanced removal is achieved by ozonation pretreatment for 15 min at the ambient pH (i.e. 4-5), followed by elevation of pH to 11 and continued ozonation treatment for 4 h. The ozonation pretreatment resulted in increased degradation of PFOA by 56% and PFOS by 42%. The results indicated hydroxyl radical-driven degradation of PFOA and PFOS in both treatments by ozone and peroxone under alkaline conditions. Wastewaters from electronics and semiconductor fabrication plants in the Science Park of Hsinchu city, Taiwan containing PFOA and PFOS have been readily treated by ozonation under alkaline condition. Treatment of PFAAs by ozone or peroxone proves to be efficient in terms of energy requirement, contact time, and removal rate.

  19. Perfluorinated carboxylates and sulfonates in open ocean waters of the Pacific and Atlantic oceans

    Energy Technology Data Exchange (ETDEWEB)

    Taniyasu, Sachi; Yamashita, Nobuyoshi; Horii, Yuichi [National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan); Kannan, K.; Sinclair, E. [Wadsworth Center, New York State Department of Health, Albany, CA (United States); Petrick, G. [Kiel Univ. (Germany). Inst. for Marine Research; Gamo, Toshitaka [Tokyo Univ. (Japan). Ocean Research Institute


    Environmentally stable perfluorinated compounds (PFCs) have appeared as a new class of global pollutants within the last four years. These compounds in general, and perfluorooctane sulfonate (PFOS) in particular, can elicit toxic effects in wildlife and humans. PFCs have unique physicochemical properties due to the highly persistent C-F bond of the non-polar moiety and exhibit a wide variety of volatility/ water solubility depending on the nature of the substituted polar moiety. Environmental kinetics of PFCs is very complex because of the unique characteristics and their wide applications in various products. It is clear that PFCs pollution is a global problem involving several international organizations such as OECD. We have reported the initial survey of open ocean pollution by PFCs in 2003. Our studies have shown that part per quadrillion (ppq) level analysis of PFCs is necessary to obtain reliable information of open ocean pollution. We have developed reliable analytical and sampling method for ultra-trace level analysis of PFCs that is applicable to global survey of open ocean pollution. Analysis of PFCs in open ocean waters is challenging because of the need for ppq level analysis and no earlier studies have reported such a sensitive method. There were two approaches to enable trace level analysis of PFCs, namely, to decrease the blank and to solve co-elution problem. We have tested low blank solid phase extraction method and improvements in the analytical procedures and instrumentation, the blank/background levels of target perfluorinated acids were reduced significantly. Field blanks containing 800 mL of HPLC-grade water taken in a polypropylene bottle were transported to sampling locations. Two hundred microliter of sodium thiosulfate solution has been added to the field blanks. Although the concentrations of target fluorochemicals in field blanks were similar to those in procedural blanks in most cases, any sample sets that were found to have notable

  20. Hydrated electron based decomposition of perfluorooctane sulfonate (PFOS) in the VUV/sulfite system. (United States)

    Gu, Yurong; Liu, Tongzhou; Wang, Hongjie; Han, Huili; Dong, Wenyi


    As one of the most reactive species, hydrated electron (eaq(-)) is promising for reductive decomposition of recalcitrant organic pollutants, such as perfluorooctane sulfonate (PFOS). In this study, PFOS decomposition using a vacuum ultraviolet (VUV)/sulfite system was systematically investigated in comparison with sole VUV and ultraviolet (UV)/sulfite systems. A fast and nearly complete (97.3%) PFOS decomposition was observed within 4h from its initial concentration of 37.2μM in the VUV/sulfite system. The observed rate constant (kobs) for PFOS decomposition in the studied system was 0.87±0.0060h(-1), which was nearly 7.5 and 2 folds faster than that in sole VUV and UV/sulfite systems, respectively. Compared to previously studied UV/sulfite system, VUV/sulfite system enhanced PFOS decomposition in both weak acidic and alkaline pH conditions. In weak acidic condition (pH6.0), PFOS predominantly decomposed via direct VUV photolysis, whereas in alkaline condition (pH>9.0), PFOS decomposition was mainly induced by eaq(-) generated from both sulfite and VUV photolytic reactions. At a fixed initial solution pH (pH10.0), PFOS decomposition kinetics showed a positive linear dependence with sulfite dosage. The co-presence of humic acid (HA) and NO3(-) obviously suppressed PFOS decomposition, whereas HCO3(-) showed marginal inhibition. A few amount of short chain perfluorocarboxylic acids (PFCAs) were detected in PFOS decomposition process, and a high defluorination efficiency (75.4%) was achieved. These results suggested most fluorine atoms in PFOS molecule ultimately mineralized into fluoride ions, and the mechanisms for PFOS decomposition in the VUV/sulfite system were proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Effect of sulfonated lignin on enzymatic activity of the ligninolytic enzymes Cα-dehydrogenase LigD and β-etherase LigF. (United States)

    Wang, Chao; Ouyang, Xianhong; Su, Sisi; Liang, Xiao; Zhang, Chao; Wang, Wenya; Yuan, Qipeng; Li, Qiang


    NAD(+)-dependent Cα-dehydrogenase LigD and glutathione-dependent β-etherase LigF which selectively cleave the β-O-4 aryl ether linkage present in lignin, are key-enzymes for the biocatalytic depolymerization of lignin. However, the catalytic efficiency of the two enzymes is low when they are used to break down the β-aryl ether linkage in natural lignin. When sulfonated lignin was added to LigF hydrolysis reactions, the conversion rate of MPHPV decreased significantly from 99.5% to 32.6%. On the contrary, sulfonated lignin has little affection on LigD, which the conversion rate of GGE only decreased from 41.7% to 41%. The strong nonspecific interactions of enzymes onto sulfonated lignin detected by surface plasmon resonance (SPR) and isothermal titration calorimetric (ITC) was obvious and universal, which can reduce enzyme activity of many enzymes, including ligninolytic enzyme β-etherase LigF. To elucidate the exact mechanisms by which β-etherase LigF interact with lignin, molecular modeling was applied. Finally, analysis on catalytic efficiency of LigD and LigF in different concentrations and molecular weights of sulfonated lignin, solution ionic strength, pH, temperature and concentration of Tween 80 revealed that electrostatic interactions and hydrophobic interactions play important roles in absorption between LigF and sulfonated lignin. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. State of the water in crosslinked sulfonated poly(ether ether ketone). Two-dimensional differential scanning calorimetry correlation mapping

    Energy Technology Data Exchange (ETDEWEB)

    Al Lafi, Abdul G. [Department of Chemistry, Atomic Energy Commission, Damascus, P.O. Box 6091 (Syrian Arab Republic); Hay, James N., E-mail: [The School of Metallurgy and Materials, College of Physical Sciences and Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)


    Highlights: • 2D-DSC mapping was applied to analyze the heat flow responses of hydrated crosslinked sPEEK. • Two types of loosely bond water were observed. • The first was bond to the sulfonic acid groups and increased with ion exchange capacity. • The second was attributed to the polar groups introduced by ions irradiation and increased with crosslinking degree. • DSC combined with 2D mapping provides a powerful tool for polymer structural determination. - Abstract: This paper reports the first application of two-dimensional differential scanning calorimetry correlation mapping, 2D-DSC-CM to analyze the heat flow responses of sulphonated poly(ether ether ketone), sPEEK, films having different ion exchange capacity and degrees of crosslinks. With the help of high resolution and high sensitivity of 2D-DSC-CM, it was possible to locate two types of loosely bound water within the structure of crosslinked sPEEK. The first was bound to the sulfonic acid groups and dependent on the ion exchange capacity of the sPEEK. The second was bound to other polar groups, either introduced by irradiation with ions and dependent on the crosslinking degree or present in the polymer such as the carbonyl groups or terminal units. The results suggest that the ability of the sulfonic acid groups in the crosslinked sPEEK membranes to adsorb water molecules is increased by crosslinking, probably due to the better close packing efficiency of the crosslinked samples. DSC combined with 2D correlation mapping provides a fast and powerful tool for polymer structural determination.

  3. Phase segregation of sulfonate groups in Nafion interface lamellae, quantified via neutron reflectometry fitting techniques for multi-layered structures. (United States)

    DeCaluwe, Steven C; Kienzle, Paul A; Bhargava, Pavan; Baker, Andrew M; Dura, Joseph A


    Neutron reflectometry analysis methods for under-determined, multi-layered structures are developed and used to determine the composition depth profile in cases where the structure is not known a priori. These methods, including statistical methods, sophisticated fitting routines, and coupling multiple data sets, are applied to hydrated and dehydrated Nafion nano-scaled films with thicknesses comparable to those found coating electrode particles in fuel cell catalyst layers. These results confirm the lamellar structure previously observed on hydrophilic substrates, and demonstrate that for hydrated films they can accurately be described as layers rich in both water and sulfonate groups alternating with water-poor layers containing an excess of fluorocarbon groups. The thickness of these layers increases slightly and the amplitude of the water volume fraction oscillation exponentially decreases away from the hydrophilic interface. For dehydrated films, the composition oscillations die out more rapidly. The Nafion-SiO2 substrate interface contains a partial monolayer of sulfonate groups bonded to the substrate and a large excess of water compared to that expected by the water-to-sulfonate ratio, λ, observed throughout the rest of the film. Films that were made thin enough to truncate this lamellar region showed a depth profile nearly identical to thicker films, indicating that there are no confinement or surface effects altering the structure. Comparing the SLD profile measured for films dried at 60 °C to modeled composition profiles derived by removing water from the hydrated lamellae suggests incomplete re-mixing of the polymer groups upon dehydration, indicated limited polymer mobility in these Nafion thin films.

  4. Controlled Modulation of Serum Protein Binding and Biodistribution of Asymmetric Cyanine Dyes by Variation of the Number of Sulfonate Groups

    Directory of Open Access Journals (Sweden)

    Franziska M. Hamann


    Full Text Available To assess the suitability of asymmetric cyanine dyes for in vivo fluoro-optical molecular imaging, a comprehensive study on the influence of the number of negatively charged sulfonate groups governing the hydrophilicity of the DY-67x family of asymmetric cyanines was performed. Special attention was devoted to the plasma protein binding capacity and related pharmacokinetic properties. Four members of the DY-67x cyanine family composed of the same main chromophore, but substituted with a sequentially increasing number of sulfonate groups (n = 1−4; DY-675, DY-676, DY-677, DY-678, respectively, were incubated with plasma proteins dissolved in phosphate-buffered saline. Protein binding was assessed by absorption spectroscopy, gel electrophoresis, ultrafiltration, and dialysis. Distribution of dye in organs was studied by intraveneous injection of 62 nmol dye/kg body weight into mice (n = 12; up to 180 minutes postinjection using whole-body near-infrared fluorescence imaging. Spectroscopic studies, gel electrophoresis, and dialysis demonstrated reduced protein binding with increasing number of sulfonate groups. The bovine serum albumin binding constant of the most hydrophobic dye, DY-675, is 18 times higher than that of the most hydrophilic fluorophore, DY-678. In vivo biodistribution analysis underlined a considerable influence of dye hydrophilicity on biodistribution and excretion pathways, with the more hydrophobic dyes, DY-675 and DY-676, accumulating in the liver, followed by strong fluorescence signals in bile and gut owing to accumulation in feces and comparatively hydrophilic DY-678-COOH accumulating in the bladder. Our results demonstrate the possibility of selectively controlling dye-protein interactions and, thus, biodistribution and excretion pathways via proper choice of the fluorophore's substitution pattern. This underlines the importance of structure-property relationships for fluorescent labels. Moreover, our data could provide the

  5. Differently substituted sulfonated polyanilines: the role of polymer compositions in electron transfer with pyrroloquinoline quinone-dependent glucose dehydrogenase. (United States)

    Sarauli, David; Xu, Chenggang; Dietzel, Birgit; Schulz, Burkhard; Lisdat, Fred


    Sulfonated polyanilines have become promising building blocks in the construction of biosensors, and therefore we use here differently substituted polymer forms to investigate the role of their structural composition and properties in achieving a direct electron transfer with the redox enzyme pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH). To this end, new copolymers containing different ratios of 2-methoxyaniline-5-sulfonic acid (MAS), 3-aminobenzenesulfonic acid (ABS) and 3-aminobenzoic acid (AB) units have been chemically synthesized. All polymers have been studied with respect to their ability to react directly with PQQ-GDH. This interaction has been monitored initially in solution, and subsequently on electrode surfaces. The results show that only copolymers with MAS and aniline units can directly react with PQQ-GDH in solution; the background can be mainly ascribed to the emeraldine salt redox state of the polymer, allowing rather easy reduction. However, when polymers and the enzyme are immobilized on the surface of carbon nanotube-containing electrodes, direct bioelectrocatalysis is also feasible in the case of copolymers composed of ABS/AB and MAS/AB units, existing initially in pernigraniline base form. This verifies that a productive interaction of the enzyme with differently substituted polymers is feasible when the electrode potential can be used to drive the reaction towards the oxidation of the substrate-reduced enzyme. These results clearly demonstrate that enzyme electrodes based on sulfonated polyanilines and direct bioelectrocatalysis can be successfully constructed. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  6. Metals 2000

    Energy Technology Data Exchange (ETDEWEB)

    Allison, S.W.; Rogers, L.C.; Slaughter, G. [Oak Ridge National Lab., TN (United States); Boensch, F.D. [6025 Oak Hill Lane, Centerville, OH (United States); Claus, R.O.; de Vries, M. [Virginia Polytechnic Inst. and State Univ., Blacksburg, VA (United States)


    This strategic planning exercise identified and characterized new and emerging advanced metallic technologies in the context of the drastic changes in global politics and decreasing fiscal resources. In consideration of a hierarchy of technology thrusts stated by various Department of Defense (DOD) spokesmen, and the need to find new and creative ways to acquire and organize programs within an evolving Wright Laboratory, five major candidate programs identified are: C-17 Flap, Transport Fuselage, Mach 5 Aircraft, 4.Fighter Structures, and 5. Missile Structures. These results were formed by extensive discussion with selected major contractors and other experts, and a survey of advanced metallic structure materials. Candidate structural applications with detailed metal structure descriptions bracket a wide variety of uses which warrant consideration for the suggested programs. An analysis on implementing smart skins and structures concepts is given from a metal structures perspective.

  7. Development and characterization of acid-doped polybenzimidazole/sulfonated polysulfone blend polymer electrolytes for fuel cells

    DEFF Research Database (Denmark)

    Hasiotis, C.; Li, Qingfeng; Deimede, V.


    Polymeric membranes from blends of sulfonated polysulfones (SPSF) and polybenzimidazole (PBI) doped with phosphoric acid were developed as potential high-temperature polymer electrolytes for fuel cells and other electrochemical applications. The water uptake and acid doping of these polymeric...... it was found to be higher than 10/sup -2/ S cm/sup -1/. Much improvement in the mechanical strength is observed for the blend polymer membranes, especially at higher temperatures. Preliminary work has demonstrated the feasibility of these polymeric membranes for fuel-cell applications...

  8. 2-Methyl-3-(2-methylphenyl-4-oxo-3,4-dihydroquinazolin-8-yl 4-bromobenzene-1-sulfonate

    Directory of Open Access Journals (Sweden)

    Edward R. T. Tiekink


    Full Text Available The title molecule, C22H17BrN2O4S, has a twisted U shape, the dihedral angle between the quinazolin-4-one and bromobenzene ring systems being 46.25 (8°. In order to avoid steric clashes with adjacent substituents on the quinazolin-4-one ring, the N-bound tolyl group occupies an orthogonal position [dihedral angle = 89.59 (8°]. In the crystal, molecules are connected into a three-dimensional architecture by C—H...O interactions, with the ketone O atom accepting two such bonds and a sulfonate O atom one.

  9. Study of adjuvant effect of model surfactants from the groups of alkyl sulfates, alkylbenzene sulfonates, alcohol ethoxylates and soaps

    DEFF Research Database (Denmark)

    Clausen, S K; Sobhani, S; Poulsen, O M


    The sodium salts of representatives of anionic surfactants, dodecylbenzene sulfonate (SDBS), dodecyl sulfate (SDS) and coconut oil fatty acids, and a nonionic surfactant, dodecyl alcohol ethoxylate, were studied for adjuvant effect on the production of specific IgE antibodies in mice...... showed a statistically significant increase in OVA specific IgE levels. After two boosters, a statistically significant suppression in OVA-specific IgE production occurred with SDS (1000 mg/l), SDBS (1000 and 100 mg/l), coconut soap (1000 mg/l) and the alcohol ethoxylate (10 mg/l). This study suggests...

  10. Plasma metallization

    CERN Document Server

    Crowther, J M


    Many methods are currently used for the production of thin metal films. However, all of these have drawbacks associated with them, for example the need for UHV conditions, high temperatures, exotic metal precursors, or the inability to coat complex shaped objects. Reduction of supported metal salts by non-isothermal plasma treatment does not suffer from these drawbacks. In order to produce and analyse metal films before they become contaminated, a plasma chamber which could be attached directly to a UHV chamber with XPS capability was designed and built. This allowed plasma treatment of supported metal salts and surface analysis by XPS to be performed without exposure of the metal film to the atmosphere. Non-equilibrium plasma treatment of Nylon 66 supported gold(lll) chloride using hydrogen as the feed gas resulted in a 95% pure gold film, the remaining 5% of the film being carbon. If argon or helium were used as the feed gases during plasma treatment the resultant gold films were 100% pure. Some degree of s...

  11. Analysis of trace metals and perfluorinated compounds in 43 representative tea products from South China. (United States)

    Zheng, Hai; Li, Jian-Long; Li, Hai-Hang; Hu, Guo-Cheng; Li, Hua-Shou


    Six trace metals (Cd, Pb, Cr, Cu, Zn, and Mn) and 2 perfluorinated compounds (PFCs), perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), were analyzed in 43 representative tea products (including 18 green, 12 Oolong, and 13 black teas) from 7 main tea production provinces in China, using the atomic absorption spectrophotometer for trace metals analysis and HPLC-MS/MS for PFOS and PFOA analysis. The average contents of the 3 essential metals Mn, Cu, and Zn ions in the tea samples were 629.74, 17.75, and 37.38 mg/kg, whereas 3 toxic metals Cd, Cr, and Pb were 0.65, 1.02, and 1.92 mg/kg, respectively. The contents of heavy metals in the 3 types of tea were in the order of black tea > Oolong tea > green tea. Both PFOS and PFOA contents were low and PFOA content was higher than PFOS in the tea samples. The highest concentration of PFOA was 0.25 ng/g dry weight found in a Hunan green tea. The Principal component analysis was performed with the trace metals and PFCs to analyze the relationships of these indices. The results showed that black teas had higher trace metals and PFCs than green and Oolong teas, and the teas from Hunan and Zhejiang provinces had higher Pb and Cr than others. This paper reports trace metals, and perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in wide range of tea products produced in the south China area. This paper also warns the low PFOS and PFOA pollution in tea. © 2014 Institute of Food Technologists®

  12. Evaluation of the toxicological effects of perfluorooctane sulfonic acid in the common carp (Cyprinus carpio)

    Energy Technology Data Exchange (ETDEWEB)

    Hoff, P.T.; Dongen, W. van; Esmans, E.L.; Blust, R.; Coen, W.M. de


    In the present study we evaluated the toxicological effects of a scarcely documented environmental pollutant, perfluorooctane sulfonic acid (PFOS), on selected biochemical endpoints in the common carp, Cyprinus carpio. Juvenile organisms were exposed to PFOS through a single intraperitoneal injection (liver concentrations ranging from 16 to 864 ng/g after 5 days of exposure) and after 1 and 5 days effects were assessed in liver and serum of the exposed organisms. The investigation of the hepatotoxicity of PFOS included the determination of the peroxisome proliferating potential (peroxisomal palmitoyl CoA oxidase and catalase activity) and the compounds influence on the average DNA basepair length (ABPL) by agarose gel electrophoresis. Total antioxidant activity (TAA), cholesterol and triglyceride levels were monitored in the serum. After 1 day of exposure the ABPL was significantly increased in the 270 and 864 ng/g treatment groups. After 5 days of exposure significant increases relative to the control were observed for the 16, 270 and 864 ng/g treatment groups. Enzyme leakage from the liver was investigated by measurement of alanine aminotransferase (ALT) and aspartate aminotransferase (AST) activities in the serum. At 561, 670 and 864 ng/g PFOS a significant increase in serum ALT activity became apparent after 5 days of exposure with values ranging from 159 to 407% relative to the control. For serum AST activity a significant increase for the 864 ng/g treatment group was observed with a value of 112% relative to the control. Determination of the polymorphonuclear leukocyte migration into liver tissue as assessed through myeloperoxidase (MPO) activity in liver, was used as an indicator for inflammation. It appeared that inflammation was not involved in the observed membranous enzyme leakage for the 561, 670 and 864 ng/g PFOS treatment groups. The results of this study suggest that PFOS induces inflammation-independent enzyme leakage through liver cell membranes

  13. Effects of linear alkylbenzene sulfonate (LAS) on the interspecific competition between Microcystis and Scenedesmus. (United States)

    Zhu, Wei; Chen, Huaimin; Guo, Lili; Li, Ming


    The widespread use of detergents increases the concentration of surfactant in lakes and reservoirs. High surfactant loads produces toxicity to algae; however, the influence of the increasing surfactant on the competition between algae is not clear. In this paper, different amounts of linear alkylbenzene sulfonate (LAS) were added to test the effects of LAS on the competition between Microcystis aeruginosa and Scenedesmus obliquus under eutrophic condition. In single culture, the growth of S. obliquus was promoted under lower LAS concentrations (1 and 20 mg L(-1)), but cell density of S. obliquus reduced when treated with higher LAS concentration (100 mg L(-1)). The growth of M. aeruginosa was inhibited markedly with 20 and 100 mg L(-1) LAS. Compared with single culture, the result was opposite in co-cultures and the cell density of S. obliquus increased significantly when treated with LAS of 1, 20, and 100 mg L(-1). The specific growth rates of S. obliquus and M. aeruginosa in both cultures were 0.4-0.5 day(-1) and 0.6-0.7 day(-1), respectively, except that the specific growth rate of M. aeruginosa in both cultures treated with 100 mg L(-1) LAS was about 0.2 day(-1). M. aeruginosa dominated over S. obliquus in the co-culture without LAS, while the competition was completely opposite with the addition of 20 mg L(-1) LAS. The growth of S. obliquus treated with 20 mg L(-1) LAS was not affected significantly in single culture but was promoted by 75 % in co-culture. Moreover, the growth of S. obliquus in co-culture treated with 100 mg L(-1) LAS was promoted by more than 97 %. These results suggested that the increasing LAS would overturn the competition of algae in freshwater ecosystems.

  14. Synthesis of 3-O-sulfonated heparan sulfate octasaccharides that inhibit the herpes simplex virus type 1 host-cell interaction (United States)

    Hu, Yu-Peng; Lin, Shu-Yi; Huang, Cheng-Yen; Zulueta, Medel Manuel L.; Liu, Jing-Yuan; Chang, Wen; Hung, Shang-Cheng


    Cell surface carbohydrates play significant roles in a number of biologically important processes. Heparan sulfate, for instance, is a ubiquitously distributed polysulfated polysaccharide that is involved, among other things, in the initial step of herpes simplex virus type 1 (HSV-1) infection. The virus interacts with cell-surface heparan sulfate to facilitate host-cell attachment and entry. 3-O-Sulfonated heparan sulfate has been found to function as an HSV-1 entry receptor. Achieving a complete understanding of these interactions requires the chemical synthesis of such oligosaccharides, but this remains challenging. Here, we present a convenient approach for the synthesis of two irregular 3-O-sulfonated heparan sulfate octasaccharides, making use of a key disaccharide intermediate to acquire different building blocks for the oligosaccharide chain assembly. Despite substantial structural differences, the prepared 3-O-sulfonated sugars blocked viral infection in a dosage-dependent manner with remarkable similarity to one another.

  15. Gas chromatography/mass spectrometric analysis of methyl esters of N,N-dialkylaminoethane-2-sulfonic acids for verification of the Chemical Weapons Convention. (United States)

    Pardasani, Deepak; Gupta, Arvinda K; Palit, Meehir; Shakya, Purushottam; Kanaujia, Pankaj K; Sekhar, K; Dubey, Devendra K


    This paper describes the synthesis and gas chromatography/electron ionization mass spectrometric (GC/EI-MS) analysis of methyl esters of N,N-dialkylaminoethane-2-sulfonic acids (DAESAs). These sulfonic acids are important environmental signatures of nerve agent VX and its toxic analogues, hence GC/EI-MS analysis of their methyl esters is of paramount importance for verification of the Chemical Weapons Convention. DAESAs were prepared by condensation of 2-bromoethane sulfonic acid with dialkylamines, and by condensation of dialkylaminoethyl chloride with sodium bisulfite. GC/EI-MS analysis of methyl esters of DAESAs yielded mass spectra; based on these spectra, generalized fragmentation routes are proposed that rationalize most of the characteristic ions. (c) 2005 John Wiley & Sons, Ltd.

  16. Liquid-liquid phase separation in dilute solutions of poly(styrene sulfonate) with multivalent cations: Phase diagrams, chain morphology, and impact of temperature. (United States)

    Hansch, Markus; Hämisch, Benjamin; Schweins, Ralf; Prévost, Sylvain; Huber, Klaus


    The dilute solution behavior of sodium poly(styrene sulfonate) is studied in the presence of trivalent Al3+ and bivalent Ba2+ cations at various levels of excess NaCl. The study evaluates the phase behavior and the morphology of the polyelectrolyte chains with increasing extent of decoration with the Al3+ and Ba2+ cations and analyses the effect of temperature on these decorated chains. The phase behavior is presented in the form of the cation concentration versus the respective poly(styrene sulfonate) concentration, recorded at the onset of precipitation. Whereas poly(styrene sulfonate) with Al3+ exhibits a linear phase boundary, denoted as the "threshold line," which increases with increasing poly(styrene sulfonate) concentration, Ba2+ cations show a threshold line which is independent of the poly(styrene sulfonate) concentration. An additional re-entrant phase, at considerably higher cation content than those of the threshold lines, is observed with Al3+ cations but not with Ba2+ cations. The threshold line and the re-entrant phase boundary form parts of the liquid-liquid phase boundary observed at the limit of low polymer concentration. The dimensions of the polyelectrolyte chains shrink considerably while approaching the respective threshold lines on increase of the Al3+ and Ba2+ cation content. However, subtle differences occur between the morphological transformation induced by Al3+ and Ba2+. Most strikingly, coils decorated with Al3+ respond very differently to temperature variations than coils decorated with Ba2+ do. As the temperature increases, the poly(styrene sulfonate) chains decrease their size in the presence of Al3+ cations but increase in size in the presence of Ba2+ cations.

  17. Methyl sulfone induces loss of metastatic properties and reemergence of normal phenotypes in a metastatic cloudman S-91 (M3 murine melanoma cell line.

    Directory of Open Access Journals (Sweden)

    Joan McIntyre Caron

    Full Text Available BACKGROUND: The most deadly form of cancer is not lung or colon, breast or prostate; it is any cancer that has become metastatic. Mortality due to metastatic melanoma, one of the most aggressive and deadly cancers, has increased steadily over the last several decades. Unfortunately, the arsenal of chemotherapeutic agents available today is most often unsuccessful at extending and improving the life expectancy of afflicted individuals. We sought to identify an effective and nontoxic agent against metastatic melanoma. METHODOLOGY/PRINCIPAL FINDINGS: We chose to study Cloudman S-91 mouse melanoma cells (sub-clone M3, CCL53.1 because these cells are highly aggressive and metastatic, representing one of the deadliest types of cancer. Melanoma cells also had an experimental advantage because their morphology, which is easily monitored, relates to the physiology of metastatic cells and normal melanocytes. We chose to test methyl sulfone as a chemotherapeutic agent for two reasons. Because of its chemical structure, we speculated a potential anti-cancer activity by targeting microtubules. Equally important, methyl sulfone has a well-established safety profile in humans. Surprisingly, we found that malignant melanoma cells exposed to methyl sulfone demonstrated the loss of phenotypes characteristic of malignant cells, and the reemergence of phenotypes characteristic of healthy melanocytes. Briefly, over time methyl sulfone induced contact inhibition, loss of ability to migrate through an extracellular matrix, loss of anchorage-independent growth, proper wound healing followed by contact inhibition, irreversible senescence followed by arborization with melanosomes in arbors as seen in normal melanocytes. CONCLUSIONS/SIGNIFICANCE: Methyl sulfone may have clinical potential as a non-toxic agent effective against metastatic melanoma. Additionally, methyl sulfone has promise as a tool to explore molecular mechanisms of metastatic transformation as well as

  18. In vitro hemocompatibility of sulfonated polypropylene non-woven fabric prepared via a facile γ-ray pre-irradiation grafting method

    Energy Technology Data Exchange (ETDEWEB)

    Li, Rong [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Wu, Guozhong [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); School of Physical Science and Technology, ShanghaiTech University, Shanghai 200031 (China); Ye, Yin, E-mail: [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China)


    Graphical abstract: - Highlights: • Sulfonated PP{sub NWF} was successfully fabricated via γ-ray pre-irradiation-induced graft polymerization of SSS method with the aid of AAm. • Compared with the pristine PP{sub NWF}, the sulfonated PP{sub NWF} material presented outstanding hydrophilicity. • The sulfonated PP{sub NWF} exhibited good hemocompatibility. - Abstract: Sulfonated polypropylene non-woven fabric (PP{sub NWF}) was successfully prepared via γ-ray pre-irradiation-induced graft polymerization of sodium styrenesulfonate (SSS) and acrylamide (AAm). The effect of pre-irradiation dose, reaction temperature, reaction time and concentration of binary monomer on the degree of grafting (DG) was studied. The chemical structure of the original and modified PP{sub NWF} materials were investigated by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the successful introduction of sulfonated (−SO{sub 3}{sup −}) group. The wettability was examined via measurement of de-ionized water adsorption percentage, which demonstrated that the hydrophilicity of PP{sub NWF} was greatly enhanced after graft modification. A little amount of bovine serum albumin (BSA) adsorption and nearly no platelet adhesion on the surface of modified PP{sub NWF} and low hemolytic ratio of the modified PP{sub NWF} revealed that the sulfonated PP{sub NWF} exhibited good hemocompatibility. Besides, blood clotting time measurement indicated that the anticoagulant property of PP{sub NWF} was effectively enhanced via SSS modification. Consequently, the hydrophilicity, in vitro hemocompatibility and anticoagulant effect of PP{sub NWF} were significantly improved by γ-ray pre-irradiation-induced graft polymerization of SSS.

  19. Enhanced response of microbial fuel cell using sulfonated poly ether ether ketone membrane as a biochemical oxygen demand sensor

    Energy Technology Data Exchange (ETDEWEB)

    Ayyaru, Sivasankaran; Dharmalingam, Sangeetha, E-mail:


    Graphical abstract: - Highlights: • Sulfonated poly ether ether ketone (SPEEK) membrane in SCMFC used to determine the BOD. • The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm. • This sensing range was 62.5% higher than that of Nafion{sup ®}. • SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}. • Nafion{sup ®} shows high anodic internal resistance (67 Ω) than the SPEEK (39 Ω). - Abstract: The present study is focused on the development of single chamber microbial fuel cell (SCMFC) using sulfonated poly ether ether ketone (SPEEK) membrane to determine the biochemical oxygen demand (BOD) matter present in artificial wastewater (AW). The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm when using artificial wastewater. This sensing range was 62.5% higher than that of Nafion{sup ®}. The most serious problem in using MFC as a BOD sensor is the oxygen diffusion into the anode compartment, which consumes electrons in the anode compartment, thereby reducing the coulomb yield and reducing the electrical signal from the MFC. SPEEK exhibited one order lesser oxygen permeability than Nafion{sup ®}, resulting in low internal resistance and substrate loss, thus improving the sensing range of BOD. The system was further improved by making a double membrane electrode assembly (MEA) with an increased electrode surface area which provide high surface area for electrically active bacteria.

  20. Preparation of Nafion-sulfonated clay nanocomposite membrane for direct menthol fuel cells via a film coating process (United States)

    Kim, Tae Kyoung; Kang, Myeongsoon; Choi, Yeong Suk; Kim, Hae Kyung; Lee, Wonmok; Chang, Hyuk; Seung, Doyoung

    Nafion sulfonated clay nanocomposite membranes were successfully produced via a film coating process using a pilot coating machine. For producing the composite membranes, we optimized the solvent ratio of N-methyl-2-pyrrolidinone (NMP) to N, N‧-dimethylacetamide (DMAc), the amount of sulfonated montmorillonite (S-MMT) in composite membranes and the overall concentration of composite dispersions. Based on the optimized viscosity and composition, the composite dispersions were coated on a poly(ethylene terephthalate) (PET) substrate film. The distance between a metering roll and a PET film and the ratio of metering roll speed versus coating roll speed of the pilot coating machine were varied to control membrane thickness. The film coated composite membrane exhibited enhanced properties in the swelling behavior against MeOH solution, ion conductivity and MeOH permeability, compared to the cast Nafion composite membrane due to the higher dispersion state of S-MMT in Nafion matrix and the uniform distribution of small-size ion clusters. These properties influenced a cell performance test of a direct methanol fuel cell (DMFC), showing the film coated composite membrane had a higher power density than that of Nafion 115. The power density was also related with the higher selectivity of the composite membrane than Nafion 115.

  1. Experimental determination and prediction of phase behavior for 1-butyl-3-methylimidazolium nonafluorobutyl sulfonate and carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Soon Kang; Park, YoonKook [Hongik University, Sejong (Korea, Republic of); Pore, Dattaprasad Marutrao [Shivaji University, Kolhapur (India)


    The vapor-liquid equilibrium of the binary system CO{sub 2}+1-butyl-3-methylimidazolium nonafluorobutyl sulfonate ([BMIM][NfO]) was measured over a temperature range of 298.2-323.2 K at intervals of 5.0 K for CO{sub 2} mole fraction ranging from 0.137 to 0.900 using a high-pressure variable-volume view cell. The Peng-Robinson equation of state was then applied with two-parameter mixing rules over the same range and the results compared with the experimentally obtained data. Increasing the alkyl chain length in perfluorinated sulfonate from methyl to butyl markedly increased the CO{sub 2} solubility. To investigate the effect of the number of fluorine atoms in the anion on the phase behavior of imidazolium based ionic liquid, these experimental results were then compared with those reported in previous experimental studies of 1-alkyl-3-methylimidazolium cations and with modeling data. It looks likely that both the number of fluorine atoms in the anion and the presence of S=O groups play an important role in designing CO{sub 2}-philic molecules.

  2. Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells (United States)

    Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui


    A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

  3. Spectrophotometric determination of aminomethylbenzoic acid using sodium 1,2-naphthoquinone-4-sulfonate as the chemical derivative chromogenic reagent (United States)

    Li, Quan-Min; Yang, Zhan-Jun


    A new method has been established for the determination of aminomethylbenzoic acid using sodium 1,2-naphthoquinone-4-sulfonate as the chemical derivative chromogenic reagent. This method is based on the formation of a pink compound from the reaction of aminomethylbenzoic acid and sodium 1,2-naphthoquinone-4-sulfonate. The nucleophilic substitution reaction proceeds quantitatively in pH 12.0 buffer solution. The stoichiometric ratio of the reaction, maximum absorption wavelength and the value of ɛ430 were 1:1, 430 nm, and 2.87 × 10 3 L mol -1 cm -1, respectively. Beer's law was obeyed in the range of 0.80-80 mg/L of aminomethylbenzoic acid. The data have been filled to a linear regression equation A = 0.03183 + 0.01658 C (mg/L), with a correlation coefficient of 0.9996. The detection limit is 0.11 mg/L, R.S.D. is 0.54%, and average recovery is over 99.6%. This paper further improves the determination of aminomethylbenzoic acid compared to the previous methods. The kinetic property and reaction mechanism have also been discussed. This proposed method has been successfully applied to the determination of aminomethylbenzoic acid in injection of aminomethylbenzoic acid with satisfactory results.

  4. Nanocomposite Based on Functionalized Gold Nanoparticles and Sulfonated Poly(ether ether ketone Membranes: Synthesis and Characterization

    Directory of Open Access Journals (Sweden)

    Iole Venditti


    Full Text Available Gold nanoparticles, capped by 3-mercapto propane sulfonate (Au-3MPS, were synthesized inside a swollen sulfonated poly(ether ether ketone membrane (sPEEK. The formation of the Au-3MPS nanoparticles in the swollen sPEEK membrane was observed by spectroscopic and microscopic techniques. The nanocomposite containing the gold nanoparticles grown in the sPEEK membrane, showed the plasmon resonance λmax at about 520 nm, which remained stable over a testing period of three months. The size distribution of the nanoparticles was assessed, and the sPEEK membrane roughness, both before and after the synthesis of nanoparticles, was studied by AFM. The XPS measurements confirm Au-3MPS formation in the sPEEK membrane. Moreover, AFM experiments recorded in fluid allowed the production of images of the Au-3MPS@sPEEK composite in water at different pH levels, achieving a better understanding of the membrane behavior in a water environment; the dynamic hydration process of the Au-3MPS@sPEEK membrane was investigated. These preliminary results suggest that the newly developed nanocomposite membranes could be promising materials for fuel cell applications.

  5. Synthesis and properties of reprocessable sulfonated polyimides cross-linked via acid stimulation for use as proton exchange membranes (United States)

    Zhang, Boping; Ni, Jiangpeng; Xiang, Xiongzhi; Wang, Lei; Chen, Yongming


    Cross-linked sulfonated polyimides are one of the most promising materials for proton exchange membrane (PEM) applications. However, these cross-linked membranes are difficult to reprocess because they are insoluble. In this study, a series of cross-linkable sulfonated polyimides with flexible pendant alkyl side chains containing trimethoxysilyl groups is successfully synthesized. The cross-linkable polymers are highly soluble in common solvents and can be used to prepare tough and smooth films. Before the cross-linking reaction is complete, the membranes can be reprocessed, and the recovery rate of the prepared films falls within an acceptable range. The cross-linked membranes are obtained rapidly when the cross-linkable membranes are immersed in an acid solution, yielding a cross-linking density of the gel fraction of greater than 90%. The cross-linked membranes exhibit high proton conductivities and tensile strengths under hydrous conditions. Compared with those of pristine membranes, the oxidative and hydrolytic stabilities of the cross-linked membranes are significantly higher. The CSPI-70 membrane shows considerable power density in a direct methanol fuel cell (DMFC) test. All of these results suggest that the prepared cross-linked membranes have great potential for applications in proton exchange membrane fuel cells.

  6. Study of the factors determining the mobility of ions in the polypyrrole films doped with aromatic sulfonate anions

    Energy Technology Data Exchange (ETDEWEB)

    Raudsepp, Terje; Marandi, Margus [Institute of Chemistry, University of Tartu, Jakobi 2, 51014 Tartu (Estonia); Tamm, Tarmo [Institute of Technology, University of Tartu, Jakobi 2, 51014 Tartu (Estonia); Sammelselg, Vaeino [Institute of Chemistry, University of Tartu, Jakobi 2, 51014 Tartu (Estonia); Tamm, Jueri [Institute of Chemistry, University of Tartu, Jakobi 2, 51014 Tartu (Estonia)], E-mail:


    The electrochemical redox behavior of the polypyrrole (PPy) films doped with benzenesulfonate (BS), p-toluenesulfonate (pTS) and naphtalene-1,5-disulfonate (NDS) was investigated by cyclic voltammetry, the chemical composition of the films was determined by XDS, the surface morphology was characterized by AFM, and the interactions between pyrrole oligomers and the anions were modeled with quantum chemical methods. It is the first detailed comparative study of the properties of these interesting systems with two complementing interactions (electrostatic and aromatic stacking). It was shown than these relatively similar aromatic sulfonate anions have rather different behavior in PPy films. The results showed that the redoxactivity of polypyrrole films doped with sulfonate ions increases in the sequence pTS < BS < NDS. The comparison of voltammograms measured in the presence of different anions with PPy films synthesized in the same solution show that the PPy/pTS films have the most densely packed and the PPy/NDS films the least densely packed structure of the three. The mobility of ions in these films is mainly determined by the packing of the films, which in turn partly depends on the interactions between the dopant-anion and polymer chains.

  7. Preparation of Pt/polypyrrole-para toluene sulfonate hydrogen peroxide sensitive electrode for the utilizing as a biosensor. (United States)

    Çete, Servet; Bal, Özgür


    A film electrode with electropolymerization of pyrrole (Py) and para-toluene sulfonate (pTS) as a anionic dopant is prepared and its sensitivity to hydrogen peroxide is investigated. The polypyrrole is deposited on a 0.5 cm(2) Pt plate an electrochemically prepared pTS ion-doped polypyrrole film by scanning the electrode potential between - 0.8 and + 0.8 V at a scan rate of 20 mV/s. The electrode's sensitivity to hydrogen peroxide is investigated at room temperature using 0.1 M phosphate buffer at pH 7.5. The working potential is found as a 0.3 V. The concentrations of pyrrole and pTS are 50mM M and 25 mM. Polypyrrole was coated on the electrode surface within 10 cycles. İmmobilization of glucose oxidase carried out on Pt/polypyrrole-para toluene sulfonate (Pt/PPy-pTS) film by cross-linking with glutaraldehyde. The morphology of electrodes was characterized by SEM and AFM. Moreover, contact angle measurements were made with 1 μL water of polymer film and enzyme electrode. It has shown that enzyme electrode is very sensitive against to glucose.

  8. Simultaneous determination of ofloxacin and gatifloxacin on cysteic acid modified electrode in the presence of sodium dodecyl benzene sulfonate. (United States)

    Zhang, Fenfen; Gu, Shuqing; Ding, Yaping; Li, Li; Liu, Xiao


    A novel cysteic acid modified carbon paste electrode (cysteic acid/CPE) based on electrochemical oxidation of L-cysteine was developed to simultaneously determine ofloxacin and gatifloxacin in the presence of sodium dodecyl benzene sulfonate (SDBS). Fourier transform infrared spectra (FTIR) indicated that L-cysteine was oxidated to cysteic acid. Electrochemical impedance spectroscopy (EIS) and cyclic voltammograms (CV) indicated that cysteic acid was successfully modified on electrode. The large peak separation (116 mV) between ofloxacin and gatifloxacin was obtained on cysteic acid/CPE while only one oxidation peak was found on bare electrode. And the peak currents increased 5 times compared to bare electrode. Moreover, the current could be further enhanced in the presence of an anionic surfactant, sodium dodecyl benzene sulfonate. The differential pulse voltammograms (DPV) exhibited that the oxidation peak currents were linearly proportional to their concentrations in the range of 0.06-10 μM for ofloxacin and 0.02-200 μM for gatifloxacin, and the detection limits of ofloxacin and gatifloxacin were 0.02 μM and 0.01 μM (S/N=3), respectively. This proposed method was successfully applied to determine ofloxacin and gatifloxacin in pharmaceutical formulations and human serum samples. Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.

  9. Positional isomers of linear sodium dodecyl benzene sulfonate: solubility, self-assembly, and air/water interfacial activity. (United States)

    Ma, Jian-Guo; Boyd, Ben J; Drummond, Calum J


    Commercial linear alkyl benzene sulfonates (ABS) are a very important class of anionic surfactants that are employed in a wide variety of applications, especially those involving wetting and detergency. Linear ABS surfactants generally consist of a complex mixture of different chain lengths and positional isomers. This diversity and level of complexity makes it difficult to develop fundamental structure-property correlations for the commercial surfactants. In this work, six monodisperse headgroup positional isomers of sodium para-dodecyl benzene sulfonate (Na-x-DBS, x = 1-6) have been studied. The influence of headgroup position and added electrolyte (NaCl) on the solubility and self-assembly (micellar and vesicular aggregation and lyotropic liquid crystalline phase behavior) in the temperature range from 10 to 90 degrees C have been investigated. Additionally, the air-aqueous solution interfacial adsorption at 25 (no added NaCl) and 50 degrees C (from 0 to 1.0 M added NaCl) has been examined. The observed physicochemical behavior is interpreted in terms of local molecular packing constraints, and in the case of the lyotropic liquid crystalline behavior global aggregate packing constraints as well.

  10. Preparation of Nafion-sulfonated clay nanocomposite membrane for direct methanol fuel cells via a film coating process

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Tae Kyoung; Kang, Myeongsoon [Research Institute of Chemical and Electronic Materials, Cheil Industries Inc., Uiwang-si 437-711 (Korea); Choi, Yeong Suk; Kim, Hae Kyung; Lee, Wonmok; Chang, Hyuk; Seung, Doyoung [Energy and Materials Research Lab, Samsung Advanced Institute of Technology (SAIT) P.O. Box 111, Suwon 449-600 (Korea)


    Nafion sulfonated clay nanocomposite membranes were successfully produced via a film coating process using a pilot coating machine. For producing the composite membranes, we optimized the solvent ratio of N-methyl-2-pyrrolidinone (NMP) to N,N'-dimethylacetamide (DMAc), the amount of sulfonated montmorillonite (S-MMT) in composite membranes and the overall concentration of composite dispersions. Based on the optimized viscosity and composition, the composite dispersions were coated on a poly(ethylene terephthalate) (PET) substrate film. The distance between a metering roll and a PET film and the ratio of metering roll speed versus coating roll speed of the pilot coating machine were varied to control membrane thickness. The film coated composite membrane exhibited enhanced properties in the swelling behavior against MeOH solution, ion conductivity and MeOH permeability, compared to the cast Nafion composite membrane due to the higher dispersion state of S-MMT in Nafion matrix and the uniform distribution of small-size ion clusters. These properties influenced a cell performance test of a direct methanol fuel cell (DMFC), showing the film coated composite membrane had a higher power density than that of Nafion 115. The power density was also related with the higher selectivity of the composite membrane than Nafion 115. (author)

  11. Degradation of poly(ether sulfone)/polyvinylpyrrolidone membranes by sodium hypochlorite: insight from advanced electrokinetic characterizations. (United States)

    Hanafi, Yamina; Szymczyk, Anthony; Rabiller-Baudry, Murielle; Baddari, Kamel


    Poly(ether sulfone) (PES)/polyvinylpyrrolidone (PVP) membranes are widely used in various industrial fields such as drinking water production and in the dairy industry. However, the use of oxidants to sanitize the processing equipment is known to impair the integrity and lifespan of polymer membranes. In this work we showed how thorough electrokinetic measurements can provide essential information regarding the mechanism of degradation of PES/PVP membranes by sodium hypochlorite. Tangential streaming current measurements were performed with ultrafiltration and nanofiltration PES/PVP membranes for various aging times. The electrokinetic characterization of membranes was complemented by FTIR-ATR spectroscopy. Results confirmed that sodium hypochlorite induces the degradation of both PES and PVP. This latter is easily oxidized by sodium hypochlorite, which leads to an increase in the negative charge density of the membrane due to the formation of carboxylic acid groups. The PVP was also found to be partly released from the membrane with aging time. Thanks to the advanced electrokinetic characterization implemented in this work it was possible for the first time to demonstrate that two different mechanisms are involved in the degradation of PES. Phenol groups were first formed as a result of the oxidation of PES aromatic rings by substitution of hydrogen by hydroxyl radicals. For more severe aging conditions, this membrane degradation mechanism was followed by the formation of sulfonic acid functions, thus indicating a second degradation process through scission of PES chains.

  12. Liquid Chromatography-Tandem Mass Spectrometry Analysis of Perfluorooctane Sulfonate and Perfluorooctanoic Acid in Fish Fillet Samples

    Directory of Open Access Journals (Sweden)

    Viviana Paiano


    Full Text Available Perfluorooctane sulfonate (PFOS and perfluorooctanoic (PFOA acid are persistent contaminants which can be found in environmental and biological samples. A new and fast analytical method is described here for the analysis of these compounds in the edible part of fish samples. The method uses a simple liquid extraction by sonication, followed by a direct determination using liquid chromatography-tandem mass spectrometry (LC-MS/MS. The linearity of the instrumental response was good, with average regression coefficients of 0.9971 and 0.9979 for PFOS and PFOA, respectively, and the coefficients of variation (CV of the method ranged from 8% to 20%. Limits of detection (LOD were 0.04 ng/g for both the analytes and recoveries were 90% for PFOS and 76% for PFOA. The method was applied to samples of homogenized fillets of wild and farmed fish from the Mediterranean Sea. Most of the samples showed little or no contamination by perfluorooctane sulfonate and perfluorooctanoic acid, and the highest concentrations detected among the fish species analyzed were, respectively, 5.96 ng/g and 1.89 ng/g. The developed analytical methodology can be used as a tool to monitor and to assess human exposure to perfluorinated compounds through sea food consumption.

  13. Water and proton transport properties of hexafluorinated sulfonated poly(arylenethioethersulfone) copolymers for applications to proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Khalfan, Amish N.; Sanchez, Luz M.; Kodiweera, Chandana; Greenbaum, Steve G. [Hunter College of the City University of New York, Physics Department, 695 Park Avenue, New York, NY 10021 (United States); Bai, Zongwu [University of Dayton Research Institute, University of Dayton, 300 College Park Drive, Dayton, OH 45469 (United States); Dang, Thuy D. [Air Force Research Laboratory/MLBP, Material and Manufacturing Directorate, Wright-Patterson Air Force Base, OH 45433 (United States)


    In the present study, we examine the water and proton transport properties of hexafluorinated sulfonated poly(arylenethioethersulfone) (6F-SPTES) copolymer membranes for applications to proton exchange membrane fuel cells (PEMFCs). The 6F-SPTES copolymer membranes build upon the structures of previously studied sulfonated poly(arylenethioethersulfone) (SPTES) copolymer membranes to include CF{sub 3} functional groups in efforts to strengthen water retention and extend membrane performance at elevated temperatures (above 120 C). The 6F-SPTES copolymer membranes sustain higher water self-diffusion and greater proton conductivities than the commercial Nafion {sup registered} membrane. Water diffusion studies of the 6F-SPTES copolymer membranes using the pulsed-field gradient spin-echo NMR technique reveal, however, the fluorinated membranes to be somewhat unfavorable over their non-fluorinated counterparts as high temperature membranes. In addition, proton conductivity measurements of the fluorinated membranes up to 85 C show comparable results with the non-fluorinated SPTES membranes. (author)

  14. Sulfonate groups grafted on Ti6Al4V favor MC3T3-E1 cell performance in serum free medium conditions. (United States)

    Felgueiras, Helena; Migonney, Véronique


    Ten years ago, we synthesized "bioactive model polymers" bearing sulfonate groups and proposed a mechanism of their modulation effect at different steps of the cell response. Then, we set up the grafting of polymers bearing sulfonate on Ti6Al4V surfaces by a grafting "from" technique making sure of the creation of covalent bonds between the grafted polymer and the Ti6Al4V surface. We have checked and confirmed the positive effect of grafted sulfonate groups on the osteoblastic cell response in vivo and in vitro but we did not elucidate the mechanism. The aim of this basic work consists first in investigating the role of sulfonate groups in the presence and in the absence of proteins at early stages of the osteointegration process on poly(sodium styrene sulfonate) poly(NaSS) grafted and ungrafted Ti6Al4V surfaces, in vitro. To understand the role of poly(NaSS) grafted chains on osteoblast-like cell response and to confirm/elucidate the importance of fetal bovine serum (FBS) proteins in the culture medium, MC3T3-E1 cells were seeded onto poly(NaSS) grafted and non-grafted Ti6Al4V surfaces. Cultures were carried out in a complete (10% FBS) and in a non-complete medium (without FBS). Cell viability assay, cell attachment number and cell adhesion strength were followed up to 3days of culture. The presence of proteins enhanced cell growth and development whatever the surface and the presence of sulfonate groups enhanced the cell attachment even in the absence of proteins, which suggests and confirms that the sulfonate groups can modify the activity of cells such as the secretion of binding proteins. Statistical differences were found in the attachment strength tests on poly(NaSS) grafted and ungrafted surfaces and showed that the sulfonate groups play an important role in the cell resistance to shear stress. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Brain region-specific perfluoroalkylated sulfonate (PFSA) and carboxylic acid (PFCA) accumulation and neurochemical biomarker responses in east Greenland polar bears (Ursus maritimus)

    DEFF Research Database (Denmark)

    Pedersen, Kathrine Eggers; Basu, Niladri; Letcher, Robert J.


    Perfluoroalkyl substances (PFASs) is a growing class of contaminants in the Arctic environment, and include the established perfluorinated sulfonates (PFSAs; especially perfluorooctane sulfonate (PFOS)) and carboxylic acids (PFCAs). PFSAs and PFCAs of varying chain length have been reported...... to bioaccumulate in lipid rich tissues of the brain among other tissues such as liver, and can reach high concentrations in top predators including the polar bear. PFCA and PFSA bioaccummulation in the brain has the potential to pose neurotoxic effects and therefore we conducted a study to investigate...

  16. Proton Conductivity of Nafion/Ex-Situ Sulfonic Acid-Modified Stöber Silica Nanocomposite Membranes As a Function of Temperature, Silica Particles Size and Surface Modification (United States)

    Muriithi, Beatrice; Loy, Douglas A.


    The introduction of sulfonic acid modified silica in Nafion nanocomposite membranes is a good method of improving the Nafion performance at high temperature and low relative humidity. Sulfonic acid-modified silica is bifunctional, with silica phase expected to offer an improvement in membranes hydration while sulfonic groups enhance proton conductivity. However, as discussed in this paper, this may not always be the case. Proton conductivity enhancement of Nafion nanocomposite membranes is very dependent on silica particle size, sometimes depending on experimental conditions, and by surface modification. In this study, Sulfonated Preconcentrated Nafion Stober Silica composites (SPNSS) were prepared by modification of Stober silica particles with mercaptopropyltriethoxysilane, dispersing the particles into a preconcentrated solution of Nafion, then casting the membranes. The mercapto groups were oxidized to sulfonic acids by heating the membranes in 10 wt % hydrogen peroxide for 1 h. At 80 °C and 100% relative humidity, a 20%–30% enhancement of proton conductivity was only observed when sulfonic acid modified particle less than 50 nm in diameter were used. At 120 °C, and 100% humidity, proton conductivity increased by 22%–42% with sulfonated particles with small particles showing the greatest enhancement. At 120 °C and 50% humidity, the sulfonated particles are less efficient at keeping the membranes hydrated, and the composites underperform Nafion and silica-Nafion nanocomposite membranes. PMID:26828525

  17. Metallic glasses

    NARCIS (Netherlands)

    Schaafsma, Arjen Sybren


    It is shown in section 7.1. that the influence of topological disorder on the range of magnetic interactions in ferromagnetic transition metal-metalloid (TM-M) glasses, is much less than often assumed. This is demonstrated via a study of the temperature dependence of the average iron hyperfine field

  18. Tetrapyrroles and associated compounds in Dead Sea asphalts

    Energy Technology Data Exchange (ETDEWEB)

    Aizenshtat, Z. (Hebrew Univ. of Jerusalem, Israel); Dinur, D.; Nissenbaum, A.


    Metallo- and free porphyrins (1000 to 1500 ppM) isolated from asphalts occurring as huge blocks floating in the northern part of the Dead Sea, have been analyzed by visible-uv (v-uv) spectrophotometry and by mass spectrometry. The concentration of vanadyl porphyrins in the asphalts exceeds by far that of the Ni-porphyrins, despite the l:3 V/Ni ratio found in the total asphalt sample. The free porphyrins resemble those from the Uinta Basin (USA) gilsonite and contain a mixture of homologous Aetio- and deoxyphyllo-erythroaetioporphyrins (DPEP). The non-porphyrin fraction of the asphalt showed an identical aliphatic, hydrocarbon distribution with that of heavy crude oil from the same area. The more polar fraction associated with the porphyrins was compared with the polar fraction of the previously described ozokerite from the Dead Sea area. From high-resolution MS, IR, v-uv and NMR spectra, combined with hydrolysis and GLC analysis, it is suggested that even-numbered (C/sub 12/, C/sub 16/, C/sub 18/, C/sub 18/ /sub 1/, C/sub 22/) fatty acids are associated with the asphaltic porphyrins, probably in the triglyceride form.

  19. Complexation of uranyl ion with sulfonates. One- to three-dimensional assemblies with 1,5- and 2,7-naphthalenedisulfonates

    Energy Technology Data Exchange (ETDEWEB)

    Thuery, Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France); Harrowfield, Jack [ISIS, Universite de Strasbourg (France)


    Uranyl nitrate was treated with the sodium salt of either 1,5- or 2,7-naphthalenedisulfonate (1,5-ndsNa{sub 2} or 2,7-ndsNa{sub 2}, respectively) under (solvo)-hydrothermal conditions, in the presence of additional coligands and/or metal cations, to give six new complexes, which were characterized by determination of their crystal structures. Complex [UO{sub 2}(1,5-nds)(H{sub 2}O)] (1) crystallizes as a three-dimensional (3D) framework, with both sulfonate groups coordinated in the O,O{sup '}-bridging mode. In the presence of the N-chelating species 2,2{sup '}-bipyridine (bipy) or 1,10-phenanthroline (phen), the three complexes [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(bipy){sub 2}].H{sub 2}O (2), [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(bipy){sub 2}].bipy (3) and [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(phen){sub 2}] (4) were obtained, in which doubly hydroxide-bridged uranyl dimers are assembled into one-dimensional (1D) chains by bis(unidentate) disulfonate ligands. Complex [Cu(bipy){sub 2}Cl][UO{sub 2}(2,7-nds)(OH)].H{sub 2}O (5) displays anionic, two-dimensional (2D) sheets in which unidentate/O,O{sup '}-bridging disulfonate ligands link hydroxide-bridged uranyl dimers. In the additional presence of cucurbit[6]uril (CB6), complex [(UO{sub 2}){sub 4}Na{sub 4}(2,7-nds){sub 2}(CB6)Cl{sub 4}O{sub 2}(H{sub 2}O){sub 10}].5H{sub 2}O (6) crystallizes as a 3D framework of intricate architecture, with bis(μ{sub 3}-oxo)-bridged uranyl tetranuclear moieties connected to CB6-bound sodium cations by doubly O,O{sup '}-bridging disulfonates. Complexes 2 and 4 display intense and well-resolved uranyl emission in the solid state, while nearly complete quenching is observed in 3 and 5. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Electrocatalytic oxidation of ethylene glycol at palladium-bimetallic nanocatalysts (PdSn and PdNi) supported on sulfonate-functionalised multi-walled carbon nanotubes

    CSIR Research Space (South Africa)

    Ramulifho, T


    Full Text Available Electrocatalytic oxidation of ethylene glycol (EG) in alkaline medium using nano-scaled palladium-based bimetallic catalysts (PdM, where M = Ni and Sn) supported on sulfonated multi-walled carbon nanotubes (SF-MWCNTs) is compared. The bimetallic...