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Sample records for nafion membranes modified

  1. A modified Nafion membrane with in situ polymerized polypyrrole for the direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Smit, M. A.; Ocampo, A. L.; Espinosa-Medina, M. A.; Sebastián, P. J.

    Nafion membranes were modified by the in situ electrodeposition of polypyrrole inside the membrane pores and on the anode side only, in order to prevent the cross-over of methanol in the direct methanol fuel cell (DMFC). Pretreated Nafion membranes were first immersed in 0.1 M sulphuric acid containing the pyrrole monomer and subsequently removed from this solution and placed in a two-electrode solid-state electrochemical cell, where the polypyrrole was formed galvanostatically. The modified membranes were studied in terms of morphology, electrochemical characteristics and methanol permeability. FTIR and SEM confirmed the presence of the polypyrrole on the anode side of the Nafion membrane. SEM shows the polymer to be present both on the membrane surface and inside the membrane pores. It was found to be deposited as small grains, with two distinct sizes, the smallest particles have a diameter of around 100 nm, while the larger particles have diameters of around 700 nm. Methanol permeability was determined electrochemically and was shown to be effectively reduced. Cyclic voltammetry was performed in sulphuric acid, in pure methanol and in 50 vol.% methanol. The untreated Nafion membrane showed CV curves which were similar in all electrolytes with electroactivity only at the extreme ends of the curve. The Nafion/Ppy membrane showed typical polypyrrole curves, with current densities lowest in sulphuric acid, and highest in the 50 vol.% methanol, respectively. For the methanol containing electrolytes, an additional oxidative peak appears in the CV, which may be related to electrocatalytic activity of the polypyrrole for methanol oxidation.

  2. Amino-silica modified Nafion membrane for vanadium redox flow battery

    NASA Astrophysics Data System (ADS)

    Lin, Chien-Hong; Yang, Ming-Chien; Wei, Hwa-Jou

    2015-05-01

    A hybrid membrane of Nafion/amino-silica (amino-SiO2) for vanadium redox flow battery (VRB) systems is prepared via the sol-gel method to improve the selectivity of the Nafion membrane, to reduce the crossover of vanadium ions, and to decrease water transfer across the membranes. The sulfonated pores of the pristine Nafion membrane are filled with amino-SiO2 nanoparticles localized by electrostatic interaction. The permeability of vanadium ions through the Nafion/amino-SiO2 hybrid membrane is determined by electrometric titration. The results indicate the crossover of vanadium ions through the hybrid membrane is 26.8% of the pristine Nafion membrane. The presence of amino-SiO2 in the hybrid membrane is verified by X-ray photoelectron spectroscopy (XPS). Nafion/amino-SiO2 hybrid membrane exhibits through plane conductivity about the same as the pristine Nafion membrane. The ion exchange capacity (IEC) of the hybrid membrane is 9.4% higher than that of the pristine Nafion membrane. In addition, Nafion/amino-SiO2 hybrid membrane exhibits a higher coulombic efficiency (CE), voltage efficiency (VE), and energy efficiency (EE) over a range of current densities from 20 to 80 mA cm-2. The performance of VRB with Nafion/amino-SiO2 hybrid membrane varies little around a charge-discharge current density of 80 mA cm-2 for 150 cycles. Thus, the Nafion/amino-SiO2 hybrid membrane can suppress the vanadium ions crossover in VRB.

  3. Proton Conductivity of Nafion/Ex-Situ Sulfonic Acid-Modified Stöber Silica Nanocomposite Membranes As a Function of Temperature, Silica Particles Size and Surface Modification

    PubMed Central

    Muriithi, Beatrice; Loy, Douglas A.

    2016-01-01

    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

  4. Proton Conductivity of Nafion/Ex-Situ Sulfonic Acid-Modified Stöber Silica Nanocomposite Membranes As a Function of Temperature, Silica Particles Size and Surface Modification.

    PubMed

    Muriithi, Beatrice; Loy, Douglas A

    2016-01-28

    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.

  5. Correlation of Structural Differences between Nafion/Polyaniline and Nafion/Polypyrrole Composite Membranes and Observed Transport Properties

    SciTech Connect

    Schwenzer, Birgit; Kim, Soowhan; Vijayakumar, M.; Yang, Zhenguo; Liu, Jun

    2011-04-15

    Polyaniline/Nafion and polypyrrole/Nafion composite membranes, prepared by chemical polymerization, are studied by infrared and nuclear magnetic resonance spectroscopy, and scanning electron microscopy. Differences in vanadium ion diffusion through the membranes and in the membranes’ area specific resistance are linked to analytical observations that polyaniline and polypyrrole interact differently with Nafion. Polypyrrole, a weakly basic polymer, binds less strongly to the sulfonic acid groups of the Nafion membrane, and thus the hydrophobic polymer aggregates in the center of the Nafion channel rather than on the hydrophilic side chains of Nafion that contain sulfonic acid groups. This results in a drastically elevated membrane resistance and an only slightly decreased vanadium ion permeation compared to a Nafion membrane. Polyaniline on the other hand is a strongly basic polymer, which forms along the sidewalls of the Nafion pores and on the membrane surface, binding tightly to the sulfonic acid groups of Nafion. This leads to a more effective reduction in vanadium ion transport across the polyaniline/Nafion membranes and the increase in membrane resistance is less severe. The performance of selected polypyrrole/Nafion composite membranes is tested in a static vanadium redox cell. Increased coulombic efficiency, compared to a cell employing Nafion, further confirms the reduced vanadium ion transport through the composite membranes.

  6. An in-situ nano-scale swelling-filling strategy to improve overall performance of Nafion membrane for direct methanol fuel cell application

    NASA Astrophysics Data System (ADS)

    Li, Jing; Fan, Kun; Cai, Weiwei; Ma, Liying; Xu, Guoxiao; Xu, Sen; Ma, Liang; Cheng, Hansong

    2016-11-01

    A novel in-situ nano-scale swelling-filling (SF) strategy is proposed to modify commercial Nafion membranes for performance enhancement of direct methanol fuel cells (DMFCs). A Nafion membrane was filled in-situ with proton conductive macromolecules (PCMs) in the swelling process of a Nafion membrane in a PCM solution. As a result, both proton conductivity and methanol-permeation resistivity of the SF-treated Naifion membrane was substantially improved with the selectivity nearly doubled compared to the original Nafion membrane. The mechanical strength of the optimal SF treated Nafion membrane was also enforced due to the strong interaction between the PCM fillers and the Nafion molecular chains. As a result, a DMFC equipped with the SF-treated membrane yielded a 33% higher maximum power density than that offered by the DMFC with the original Nafion membrane.

  7. Aqua-vanadyl ion interaction with Nafion® membranes

    SciTech Connect

    Vijayakumar, Murugesan; Govind, Niranjan; Li, Bin; Wei, Xiaoliang; Nie, Zimin; Thevuthasan, Suntharampillai; Sprenkle, Vince L.; Wang, Wei

    2015-03-23

    Lack of comprehensive understanding about the interactions between Nafion membrane and battery electrolytes prevents the straightforward tailoring of optimal materials for redox flow battery applications. In this work, we analyzed the interaction between aqua-vanadyl cation and sulfonic sites within the pores of Nafion membranes using combined theoretical and experimental X-ray spectroscopic methods. Molecular level interactions, namely, solvent share and contact pair mechanisms are discussed based on Vanadium and Sulfur K-edge spectroscopic analysis.

  8. Organically functionalized titanium oxide/Nafion composite proton exchange membranes for fuel cells applications

    NASA Astrophysics Data System (ADS)

    Cozzi, Dafne; de Bonis, Catia; D'Epifanio, Alessandra; Mecheri, Barbara; Tavares, Ana C.; Licoccia, Silvia

    2014-02-01

    An organically-modified ceramic material (TiO2-RSO3H) to be used as filler in Nafion-based composite membranes was synthesized by covalently grafting propylsulfonic acid groups on the surface of TiO2 nanoparticles. Higher ion exchange capacity (IEC) and proton conductivity of the hybrid material (one order of magnitude higher for the functionalized filler) reflected in superior performance of Nafion/TiO2-RSO3H composite membranes compared to Nafion. The highest conductivity value was obtained for the composite membrane containing 10 wt. % TiO2-RSO3H (σ = 0.08 S cm-1 at 140 °C). The membranes were tested in a DMFC single cell. The presence of the filler resulted in a general enhancement in the cell response, in terms of both higher power density (PD) delivered and lower methanol crossover with respect to unfilled Nafion membrane. The DMFC containing N_10TiO2-RSO3H membrane showed the best performance at 110 °C with a PD of 64 mW cm-2, corresponding to a PD improvement of about 40% with respect to that of Nafion membrane.

  9. Structure and Water Transport in Nafion Nanocomposite Membranes

    NASA Astrophysics Data System (ADS)

    Davis, Eric; Page, Kirt

    2014-03-01

    Perfluorinated ionomers, specifically Nafion, are the most widely used ion exchange membranes for vanadium redox flow battery applications, where an understanding of the relationship between membrane structure and transport of water/ions is critical to battery performance. In this study, the structure of Nafion/SiO2 nanocomposite membranes, synthesized using sol-gel chemistry, as well as cast directly from Nafion/SiO2 nanoparticle dispersions, was measured using both small-angle neutron scattering (SANS) and ultra-small-angle neutron scattering (USANS). Through contrast match studies of the SiO2 nanoparticles, direct information on the change in the structure of the Nafion membranes and the ion-transport channels within was obtained, where differences in membrane structure was observed between the solution-cast membranes and the membranes synthesized using sol-gel chemistry. Additionally, water sorption and diffusion in these Nafion/SiO2 nanocomposite membranes were measured using in situ time-resolved Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy and dynamic vapor sorption (DVS).

  10. Spray deposition of Nafion membranes: Electrode-supported fuel cells

    NASA Astrophysics Data System (ADS)

    Bayer, Thomas; Pham, Hung Cuong; Sasaki, Kazunari; Lyth, Stephen Matthew

    2016-09-01

    Fuel cells are a key technology for the successful transition towards a hydrogen society. In order to accelerate fuel cell commercialization, improvements in performance are required. Generally, polymer electrolyte membrane fuel cells (PEFCs) are membrane-supported; the electrocatalyst layer is sprayed onto both sides of the membrane, and sandwiched between carbon-based gas diffusion layers (GDLs). In this work we redesign the membrane electrode assembly (MEA) and fabricate an electrode-supported PEFC. First the electrocatalyst layer is sprayed onto the GDL, and then Nafion dispersion is sprayed over the top of this to form a thin membrane. This method has the advantage of simplifying the fabrication process, allowing the fabrication of extremely thin electrolyte layers (down to ∼10 μm in this case), and reducing the amount of ionomer required in the cell. Electrode-supported PEFCs operate at significantly increased power density compared to conventional membrane-supported PEFCs, with a maximum of 581 mW/cm2 at 80 °C (atmospheric pressure, air at the cathode). Impedance spectroscopy confirmed that the origin of the improved performance was an 80% reduction in the membrane resistance due the thinner Nafion layer. This novel fabrication method is a step towards cheaper, thinner, fully printable PEFCs with high power density and efficiency.

  11. Structure and acoustic properties of hydrated nafion membranes.

    PubMed

    Plazanet, M; Bartolini, P; Torre, R; Petrillo, C; Sacchetti, F

    2009-07-30

    The propagation of acoustic waves in water-hydrated Nafion membrane has been monitored using heterodyne-detected transient grating spectroscopy. At room temperature, upon increasing the water content, the speed of sound drops to a value lower than the respective velocities of sound in pure Nafion and pure water. This counterintuitive effect can be explained by a simple calculation of the sound velocity in an effective medium made of water and Nafion polymer. Upon cooling, a phase separation occurs in the sample, and the formation of ice is observed (M. Pineri et al. J. Power Sources 2007, 172, 587-596). This phase transition is characterized via a second acoustic wave observed in the signal. Sound propagation and X-ray diffraction confirm the formation of crystalline ice on the membrane surface, that reversibly melts upon heating. The amount of ice that forms in the sample is monitored as a function of temperature and represents an order parameter for the transition. This parameter follows a power law with an exponent of 0.5, indicating the critical nature of the observed process. PMID:19719280

  12. Sulfated Titania-Silica Reinforced Nafion Nanocomposite Membranes for Proton Exchange Membrane Fuel Cells.

    PubMed

    Abu Sayeed, M D; Kim, Hee Jin; Gopalan, A I; Kim, Young Ho; Lee, Kwang-Pill; Choi, Sang-June

    2015-09-01

    Sulfated titania-silica (SO4(2-)-/TiO2-SiO2) composites were prepared by a sol-gel method with sulfate reaction and characterized by X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). The nanometric diameter and geometry of the sulfated titania-silica (STS) was investigated by transmission electron microscopy (TEM). A small amount of the STS composite in the range of 0.5-3 wt% was then added as reinforcing into the Nafion membrane by water-assisted solution casting method to prepare STS reinforced Nafion nanocomposite membranes (STS-Nafion nanocomposite membranes). The additional functional groups, sulfate groups, of the nanocomposite membrane having more surface oxygenated groups enhanced the fuel cell membrane properties. The STS-Nafion nanocomposite membranes exhibited improved water uptake compared to that of neat Nafion membranes, whereas methanol uptake values were decreased dramatically improved thermal property of the prepared nanocomposite membranes were measured by thermogravimetric analysis (TGA). Furthermore, increased ion exchange capacity values were obtained by thermoacidic pretreatment of the nanocomposite membranes.

  13. Nafion/PTFE composite membranes for direct methanol fuel cell applications

    NASA Astrophysics Data System (ADS)

    Lin, Hsiu-Li; Yu, T. Leon; Huang, Li-Ning; Chen, Li-Chung; Shen, Kun-Sheng; Jung, Guo-Bin

    Using dynamic light scattering and scanning electron microscope (SEM), it is shown that a high-carbon-number alcohol/water, i.e., 2-propanol/water, mixed solvent is more effective than low-carbon-number alcohol/water, i.e., ethanol/water and methanol/water, mixed solvents in dispersing Nafion molecules. Thus, it is a better solvent for the preparation of Nafion/PTFE (poly(tetrafluoroethylene)) composite membranes. The performance of direct methanol fuel cells (DMFCs) with a Nafion/PTFE composite membrane, which was prepared in-house, a commercial Nafion-117 membrane, or a commercial Nafion-112 membrane were investigated by feeding various concentrations, i.e., 2-5 M, of methanol to the anode. The Nafion/PTFE composite membrane gave a better DMFC performance than that obtained with Nafion-117 or Nafion-112 membranes. Using a DMFC model and varying the methanol concentration at the anode, cell voltage data were analyzed with respect to methanol concentration and cell current. The results indicate that inserting porous PTFE into Nafion polymer causes a reduction not only in methanol diffusion cross-over but also in the electro-osmosis of methanol cross-over in the membrane.

  14. Sulfonated graphene oxide/nafion composite membrane for vanadium redox flow battery.

    PubMed

    Kim, Byung Guk; Han, Tae Hee; Cho, Chang Gi

    2014-12-01

    Nafion is the most frequently used as the membrane material due to its good proton conductivity, and excellent chemical and mechanical stabilities. But it is known to have poor barrier property due to its well-developed water channels. In order to overcome this drawback, graphene oxide (GO) derivatives were introduced for Nafion composite membranes. Sulfonated graphene oxide (sGO) was prepared from GO. Both sGO and GO were treated each with phenyl isocyanate and transformed into corresponding isGO and iGO in order to promote miscibility with Nafion. Then composite membranes were obtained, and the adaptability as a membrane for vanadium redox flow battery (VRFB) was investigated in terms of proton conductivity and vanadium permeability. Compared to a pristine Nafion, proton conductivities of both isGO/Nafion and iGO/Nafion membranes showed less temperature sensitivity. Both membranes also showed quite lower vanadium permeability at room temperature. Selectivity of the membrane was the highest for isGO/Nafion and the lowest for the pristine Nafion.

  15. Nafion-Initiated ATRP of 1-Vinylimidazole for Preparation of Proton Exchange Membranes.

    PubMed

    Feng, Kai; Liu, Lei; Tang, Beibei; Li, Nanwen; Wu, Peiyi

    2016-05-11

    Nafion is one of the most widely investigated materials applied in proton exchange membranes. Interestingly, it was found that Nafion could serve as a macroinitiator to induce atom transfer radical polymerization (ATRP) on its C-F sites. In this study, poly(1-vinylimidazole) was selectively bonded on the side chains of Nafion via the Nafion-initiated ATRP process, which was confirmed by the measurements of (1)H/(19)F nuclear magnetic resonance spectra, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, differential scanning calorimeter and matrix-assisted laser desorption ionization-time-of-flight/time-of-flight mass spectrometry. The as-prepared Nafion-co-poly(1-vinylimidazole) (Nafion-PVIm) membranes, with tunable loading amount of imidazole rings, presented greatly enhanced proton conductivity and methanol resistivity due to their well-controlled chemical structures. Especially, chemically bonding PVIm with Nafion chains endowed the Nafion-PVIm membranes with high stability in proton conductivity. For the first time, we revealed the great potentials of the Nafion-initiated ATRP process in developing high-performance proton exchange membranes. PMID:27077232

  16. Functionalized carbon nanotube via distillation precipitation polymerization and its application in nafion-based composite membranes.

    PubMed

    He, Guangwei; Zhao, Jing; Hu, Shen; Li, Lingqiao; Li, Zongyu; Li, Yifan; Li, Zhen; Wu, Hong; Yang, Xinlin; Jiang, Zhongyi

    2014-09-10

    The objective of this study is to develop a novel approach to in situ functionalizing multiwalled carbon nanotubes (MWCNTs) and exploring their application in Nafion-based composite membranes for efficient proton conduction. Covalent grafting of acrylate-modified MWCNTs with poly(methacrylic acid-co-ethylene glycol dimethacrylate), poly(vinylphosphonic acid-co-ethylene glycol dimethacrylate), and sulfonated poly(styrene-co-divinylbenzene) was achieved via surface-initiated distillation precipitation polymerization. The formation of core-shell structure was verified by TEM images, and polymer layers with thickness around 30 nm were uniformly covered on the MWCNTs. The graft yield reached up to 93.3 wt % after 80 min of polymerization. The functionalized CNTs (FCNTs) were incorporated into the Nafion matrix to prepare composite membranes. The influence of various functional groups (-COOH, -PO3H2, and -SO3H) in FCNTs on proton transport of the composite membranes was studied. The incorporation of FCNTs afforded the composite membranes significantly enhanced proton conductivities under reduced relative humidity. The composite membrane containing 5 wt % phosphorylated MWCNTs (PCNTs) showed the highest proton conductivity, which was attributed to the construction of lower-energy-barrier proton transport pathways by PCNTs, and excellent water-retention and proton-conduction properties of the cross-linked polymer in PCNTs. Moreover, the composite membranes exhibited an enhanced mechanical stability. PMID:25109828

  17. Enhanced ionic polymer metal composite actuator with porous nafion membrane using zinc oxide particulate leaching method

    NASA Astrophysics Data System (ADS)

    Jung, Sun Yong; Ko, Seong Young; Park, Jong-Oh; Park, Sukho

    2015-03-01

    In this study, to improve the performance of an ionic polymer metal composite (IPMC), we suggest a porous nafion membrane fabricated with the particulate leaching method with zinc oxide and propose an IPMC that uses the porous nafion membrane. To fabricate this membrane, the proper ratio of nafion and zinc oxide powder is dispersed in a solvent. Then the zinc oxide embedded in the nafion membrane is fabricated with a casting method. With the particulate leaching method, the embedded zinc oxide particles are dissolved by an acid solution, and the spaces of the zinc oxide particles changed to pores. Finally, through electroless plating and ion exchange procedures, an IPMC with the porous nafion membrane is fabricated. The proposed IPMC has higher water uptake (WUP) and ion exchange capacity (IEC) and can show better actuation performance compared to the conventional nafion-based IPMC. We also measure the actuation displacement and blocking forces of the proposed IPMC. Compared with the conventional nafion-based IPMC, the proposed IPMC with the porous nafion membrane has increased displacements: about 80% at ac input and about 250% at dc input, and increased blocking force about 130% at dc input.

  18. Spectroscopic Investigations of the Fouling Process on Nafion Membranes in Vanadium Redox Flow Batteries

    SciTech Connect

    Vijayakumar, M.; Sivakumar, Bhuvaneswari M.; Nachimuthu, Ponnusamy; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Liu, Jun; Graff, Gordon L.; Thevuthasan, Suntharampillai; Hu, Jian Z.

    2011-01-01

    The Nafion-117 membrane used in vanadium redox flow battery (VRFB) is analyzed by X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface due to their low diffusivity. On the other hand, the 17O NMR spectrum explores the diffused vanadium cation from the bulk part of Nafion and shows the chemical bonding of cation and the host membrane. The 19F NMR shows the basic Nafion structure is not altered due to the presence of diffused vanadium cation. Based on these spectroscopic studies, the chemical environment of diffused vanadium cation in the Nafion membrane is discussed. This study also shed light into the possible cause for the high diffusivity of certain vanadium cations inside the Nafion membranes.

  19. Insights into the Impact of the Nafion Membrane Pretreatment Process on Vanadium Flow Battery Performance.

    PubMed

    Jiang, Bo; Yu, Lihong; Wu, Lantao; Mu, Di; Liu, Le; Xi, Jingyu; Qiu, Xinping

    2016-05-18

    Nafion membranes are now the most widely used membranes for long-life vanadium flow batteries (VFBs) because of their extremely high chemical stability. Today, the type of Nafion membrane that should be selected and how to pretreat these Nafion membranes have become critical issues, which directly affects the performance and cost of VFBs. In this work, we chose the Nafion 115 membrane to investigate the effect of the pretreatment process (as received, wet, boiled, and boiled and dried) on the performance of VFBs. The relationship between the nanostructure and transport properties of Nafion 115 membranes is elucidated by wide-angle X-ray diffraction and small-angle X-ray scattering techniques. The self-discharge process, battery efficiencies, electrolyte utilization, and long-term cycling stability of VFBs with differently pretreated Nafion membranes are presented comprehensively. An online monitoring system is used to monitor the electrolyte volume that varies during the long-term charge-discharge test of VFBs. The capacity fading mechanism and electrolyte imbalance of VFBs with these Nafion 115 membranes are also discussed in detail. The optimal pretreatment processes for the benchmark membrane and practical application are synthetically selected. PMID:27123693

  20. RADIATION STABILITY OF NAFION MEMBRANES USED FOR ISOTOPE SEPARATION BY PROTON EXCHANGE MEMBRANE ELECTROLYSIS

    SciTech Connect

    Fox, E

    2009-05-15

    Proton Exchange Membrane Electrolyzers have potential interest for use for hydrogen isotope separation from water. In order for PEME to be fully utilized, more information is needed on the stability of Nafion when exposed to radiation. This work examines Nafion 117 under varying exposure conditions, including dose rate, total dosage and atmospheric condition. Analytical tools, such as FT-IR, ion exchange capacity, DMA and TIC-TOC were used to characterize the exposed membranes. Analysis of the water from saturated membranes can provide important data on the stability of the membranes during radiation exposure. It was found that the dose rate of exposure plays an important role in membrane degradation. Potential mechanisms for membrane degradation include peroxide formation by free radicals.

  1. Design and characterization of Nafion/ex-situ silica nanocomposite membranes: Effects of particle size and surface modification

    NASA Astrophysics Data System (ADS)

    Muriithi, Beatrice Wanjku

    This dissertation focuses on the preparation of new Nafion RTM/ex-situ silica nanocomposite membranes and the impact of particle size of spherical silica particles on the nanocomposites' properties. To achieve acceptable power production, fuel cell polymer membranes are required with good proton conductivity, water retention, thermal and mechanical stability. However, to avoid poisoning of fuel cell electrocatalysts with CO or other fuel contaminants, they must be operated at temperatures (>100°C). At these temperatures, fuel cell membranes dehydrate resulting in dramatic decreases in proton conductivity or complete failure as membranes crack due to volumetric stress from water loss. Even if fuel cell is kept in a humidified chamber, increasing temperature will eventually shut the cell down as Nafion RTM's bicontinuous structure "dissolves" into a single poorly conducting phase at temperatures above the polymer's Tg. This research provides systematic studies of effects of silica particle size on properties of silica-NafionRTM nanocomposites. Results of this study include new insights into requirements for reproducible particle syntheses, practical methods for avoiding silica particle floatation during NafionRTM nanocomposite membranes preparation, and a summary of the influence of particle size and functionalization on NafionRTM membrane properties. Stober particle syntheses showed high sensitive to ammonia concentration and we discovered that literature procedures' variability is likely due to researchers' failure to accurately measure ammonia concentration in their aqueous base (which can be 50% or more off). Homogeneous nanocomposite membranes, as determined by AFM and SEM, were successfully prepared using more viscous dispersions. It was observed that nanocomposite membranes with small particles (<50 nm) showed significant increases in proton conductivity at temperatures above 80°C. Surface modification of the silica particles improved the proton conductivity

  2. Performance of composite Nafion/PVA membranes for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Mollá, Sergio; Compañ, Vicente

    2011-03-01

    This work has been focused on the characterization of the methanol permeability and fuel cell performance of composite Nafion/PVA membranes in function of their thickness, which ranged from 19 to 97 μm. The composite membranes were made up of Nafion® polymer deposited between polyvinyl alcohol (PVA) nanofibers. The resistance to methanol permeation of the Nafion/PVA membranes shows a linear variation with the thickness. The separation between apparent and true permeability permits to give an estimated value of 4.0 × 10-7 cm2 s-1 for the intrinsic or true permeability of the bulk phase at the composite membranes. The incorporation of PVA nanofibers causes a remarkable reduction of one order of magnitude in the methanol permeability as compared with pristine Nafion® membranes. The DMFC performances of membrane-electrode assemblies prepared from Nafion/PVA and pristine Nafion® membranes were tested at 45, 70 and 95 °C under various methanol concentrations, i.e., 1, 2 and 3 M. The nanocomposite membranes with thicknesses of 19 μm and 47 μm reached power densities of 211 mW cm-2 and 184 mW cm-2 at 95 °C and 2 M methanol concentration. These results are comparable to those found for Nafion® membranes with similar thickness at the same conditions, which were 210 mW cm-2 and 204 mW cm-2 respectively. Due to the lower amount of Nafion® polymer present within the composite membranes, it is suggested a high degree of utilization of Nafion® as proton conductive material within the Nafion/PVA membranes, and therefore, significant savings in the consumed amount of Nafion® are potentially able to be achieved. In addition, the reinforcement effect caused by the PVA nanofibers offers the possibility of preparing membranes with very low thickness and good mechanical properties, while on the other hand, pristine Nafion® membranes are unpractical below a thickness of 50 μm.

  3. Energy Conversion from Salinity Gradient Using Microchip with Nafion Membrane

    NASA Astrophysics Data System (ADS)

    Chang, Che-Rong; Yeh, Ching-Hua; Yeh, Hung-Chun; Yang, Ruey-Jen

    2016-06-01

    When a concentrated salt solution and a diluted salt solution are separated by an ion-selective membrane, cations and anions would diffuse at different rates depending on the ion selectivity of the membrane. The difference of positive and negative charges at both ends of the membrane would produce a potential, called the diffusion potential. Thus, electrical energy can be converted from the diffusion potential through reverse electrodialysis. This study demonstrated the fabrication of an energy conversion microchip using the standard micro-electromechanical technique, and utilizing Nafion junction as connecting membrane, which was fabricated by a surface patterned process. Through different salinity gradient of potassium chloride solutions, we experimentally investigated the diffusion potential and power generation from the microchip, and the highest value measured was 135 mV and 339 pW, respectively. Furthermore, when the electrolyte was in pH value of 3.8, 5.6, 10.3, the system exhibited best performance at pH value of 10.3; whereas, pH value of 3.8 yielded the worst.

  4. Prism-patterned Nafion membrane for enhanced water transport in polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Kim, Sang Moon; Kang, Yun Sik; Ahn, Chiyeong; Jang, Segeun; Kim, Minhyoung; Sung, Yung-Eun; Yoo, Sung Jong; Choi, Mansoo

    2016-06-01

    Here, we report a simple and effective strategy to enhance the performance of the polymer electrolyte membrane fuel cell by imprinting prism-patterned arrays onto the Nafion membrane, which provides three combined effects directly related to the device performance. First, a locally thinned membrane via imprinted micro prism-structures lead to reduced membrane resistance, which is confirmed by electrochemical impedance spectroscopy. Second, increments of the geometrical surface area of the prism-patterned Nafion membrane compared to a flat membrane result in the increase in the electrochemical active surface area. Third, the vertically asymmetric geometry of prism structures in the cathode catalyst layer lead to enhanced water transport, which is confirmed by oxygen gain calculation. To explain the enhanced water transport, we propose a simple theoretical model on removal of water droplets existing in the asymmetric catalyst layer. These three combined effects achieved via incorporating prism patterned arrays into the Nafion membrane effectively enhance the performance of the polymer electrolyte membrane fuel cell.

  5. Electrospun Nafion®/Polyphenylsulfone composite membranes for regenerative Hydrogen bromine fuel cells

    DOE PAGES

    Park, Jun; Wycisk, Ryszard; Pintauro, Peter N.; Yarlagadda, Venkata; Van Nguyen, Trung

    2016-02-29

    Here, the regenerative H2/Br2-HBr fuel cell, utilizing an oxidant solution of Br2 in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA) ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU), for mechanical reinforcement, and swelling control.more » After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H2-Br2 fuel cell power output with a 65 m thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 m Nafion® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H2/Br2-HBr systems.« less

  6. Nafion-porous cerium oxide nanotubes composite membrane for polymer electrolyte fuel cells operated under dry conditions

    NASA Astrophysics Data System (ADS)

    Ketpang, Kriangsak; Oh, Kwangjin; Lim, Sung-Chul; Shanmugam, Sangaraju

    2016-10-01

    A composite membrane operated in polymer electrolyte fuel cells (PEFCs) under low relative humidity (RH) is developed by incorporating cerium oxide nanotubes (CeNT) into a perfluorosulfonic acid (Nafion®) membrane. Porous CeNT is synthesized by direct heating a precursor impregnated polymer fibers at 500 °C under an air atmosphere. Compared to recast Nafion and commercial Nafion (NRE-212) membranes, the Nafion-CeNT composite membrane generates 1.1 times higher power density at 0.6 V, operated at 80 °C under 100% RH. Compared to Nafion-cerium oxide nanoparticles (Nafion-CeNP) membrane, the Nafion-CeNT provides 1.2 and 1.7 times higher PEFC performance at 0.6 V when operated at 80 °C under 100% and 18% RH, respectively. Additionally, the Nafion-CeNT composite membrane exhibits a good fuel cell operation under 18% RH at 80 °C. Specifically, the fluoride emission rate of Nafion-CeNT composite membrane is 20 times lower than that of the commercial NRE-212 membrane when operated under 18% RH at 80 °C for 96 h. The outstanding PEFC performance and durability operated under dry conditions is mainly attributed to the facile water diffusion capability as well as the effective hydroxyl radical scavenging property of the CeNT filler, resulting in significantly mitigating both the ohmic resistance and Nafion membrane degradation.

  7. Simple electrochemical sensor for caffeine based on carbon and Nafion-modified carbon electrodes.

    PubMed

    Torres, A Carolina; Barsan, Madalina M; Brett, Christopher M A

    2014-04-15

    A simple, economic, highly sensitive and highly selective method for the detection of caffeine has been developed at bare and Nafion-modified glassy carbon electrodes (GCE). The electrochemical behaviour of caffeine was examined in electrolyte solutions of phosphate buffer saline, sodium perchlorate, and in choline chloride plus oxalic acid, using analytical determinations by fixed potential amperometry, phosphate buffer saline being the best. Modifications of the GCE surface with poly(3,4-ethylenedioxythiophene) (PEDOT), Nafion, and multi-walled carbon nanotubes were tested in order to evaluate possible sensor performance enhancements, Nafion giving the most satisfactory results. The effect of interfering compounds usually found in samples containing caffeine was examined at GCE without and with Nafion coating, to exclude interferences, and the sensors were successfully applied to determine the caffeine content in commercial beverages and drugs.

  8. Simple electrochemical sensor for caffeine based on carbon and Nafion-modified carbon electrodes.

    PubMed

    Torres, A Carolina; Barsan, Madalina M; Brett, Christopher M A

    2014-04-15

    A simple, economic, highly sensitive and highly selective method for the detection of caffeine has been developed at bare and Nafion-modified glassy carbon electrodes (GCE). The electrochemical behaviour of caffeine was examined in electrolyte solutions of phosphate buffer saline, sodium perchlorate, and in choline chloride plus oxalic acid, using analytical determinations by fixed potential amperometry, phosphate buffer saline being the best. Modifications of the GCE surface with poly(3,4-ethylenedioxythiophene) (PEDOT), Nafion, and multi-walled carbon nanotubes were tested in order to evaluate possible sensor performance enhancements, Nafion giving the most satisfactory results. The effect of interfering compounds usually found in samples containing caffeine was examined at GCE without and with Nafion coating, to exclude interferences, and the sensors were successfully applied to determine the caffeine content in commercial beverages and drugs. PMID:24295698

  9. Metallic plate corrosion and uptake of corrosion products by nafion in polymer electrolyte membrane fuel cells.

    PubMed

    Bozzini, Benedetto; Gianoncelli, Alessandra; Kaulich, Burkhard; Kiskinova, Maya; Prasciolu, Mauro; Sgura, Ivonne

    2010-07-19

    Nafion contamination by ferrous-alloy corrosion products, resulting in dramatic drops of the Ohmic potential, is a suspected major failure mode of polymer electrolyte membrane fuel cells that make use of metallic bipolar plates. This study demonstrates the potential of scanning transmission X-ray microscopy combined with X-ray absorption and fluorescence microspectroscopy for exploring corrosion processes of Ni and Fe electrodes in contact with a hydrated Nafion film in a thin-layer cell. The imaged morphology changes of the Ni and Fe electrodes and surrounding Nafion film that result from relevant electrochemical processes are correlated to the spatial distribution, local concentration, and chemical state of Fe and Ni species. The X-ray fluorescence maps and absorption spectra, sampled at different locations, show diffusion of corrosion products within the Nafion film only in the case of the Fe electrodes, whereas the Ni electrodes appear corrosion resistant. PMID:20564283

  10. Nafion/PTFE/silicate composite membranes for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Huang, Li-Ning; Chen, Li-Chun; Yu, T. Leon; Lin, Hsiu-Li

    Poly(tetrafluoro ethylene) (PTFE)/Nafion composite membranes (PN composite membranes) were prepared by impregnating micro-porous PTFE membranes in Nafion/2-propanol/water solutions. The PN composite membranes were then further impregnated with tetraethoxysilane (TEOS) solutions to prepare PTFE/Nafion/silicate (PNS) composite membranes. The influence of hybridizing silicate into the PN membranes on their direct methanol fuel cell (DMFC) performance and methanol crossover was investigated. Silicate in PN membranes causes reduction both in proton conductivity and methanol crossover of membranes. Thus PNS had a higher voltage than PN at low current densities due to the lower methanol crossover of PNS. However, at high current densities, PNS had a lower voltage than PN due to the higher resistance to proton transference of PNS. The range of lower current densities where PNS had a higher voltage than PN was i = 0-120 mA cm -2 when the methanol feed concentration was 2 M. This lower current density range became broader as the methanol feed concentration was increased, and it was broadened to i = 0-190 mA cm -2 as the methanol feed concentration was increased to 5 M. A comparison of the methanol crossover on the DMFC performance of PN and PNS with Nafion-112 was also studied. We showed that Nafion-112 exhibits higher methanol electro-osmosis than PN and PNS. Thus at a high current density, the higher methanol crossover via electro-osmosis caused Nafion-112 to have a lower voltage than PN and PNS.

  11. Composite Nafion 117-TMSP membrane for Fe-Cr redox flow battery applications

    NASA Astrophysics Data System (ADS)

    Haryadi, Gunawan, Y. B.; Mursid, S. P.; Harjogi, D.

    2016-04-01

    The modification of Nafion 117 - TMSP (trimethoxysylilprophanthiol) composite membrane has been conducted by in-situ sol-gel method followed by characterization of structural and properties of material using spectroscopic techniques. The performance of composite membrane has then been examined in the single stack module of Fe-Cr Redox Flow Battery. It was found that the introduction of silica from TMSP through sol-gel process within the Nafion 117 membrane produced composite membrane that has slightly higher proton conductivity values as compared to the pristine of Nafion 117 membrane observed by electrochemical impedance spectroscopy. The degree of swelling of water in the composite membrane demonstrated greatly reduced than a pristine Nafion 117 signifying low water cross over. The SEM-EDX measurements indicated that there was no phase separation occurred suggesting that silica nanoparticles are distributed homogeneously within the composite membrane. The composite membrane used as separator in the system of Fe-Cr Redox Flow Battery revealed no cross mixing (crossover) occurred between anolyte and catholyte in the system as observed from the total voltage measurements that closed to the theoretical value. The battery efficiency generally increased as the volume of the electrolytes enlarged.

  12. Atomistic Simulations of Perfluoro Phosphonic and Phosphinic Acid Membranes and Comparisons to Nafion

    SciTech Connect

    Idupulapati, Nagesh B.; Devanathan, Ramaswami; Dupuis, Michel

    2011-03-31

    We used classical molecular dynamics (MD) simulations to investigate the nanoscale morphology and proton transport properties of perfluoro phosphonic (FPA) and phosphinic acid (FPA-I) membranes as they are being considered for use in low temperature fuel cells. We systematically investigated these properties as a function of the hydration level. The changes in nanostructure, in transport dynamics of water and hydronium ions, and in water network percolation were extracted from MD simulations and compared with Nafion. Phosphonic and phosphinic acid moieties in FPA and FPA-I, have lower acidity than sulfonic acid in Nafion, yet the diffusion of water was observed to be faster in FPA and FPA-I than in Nafion, particularly at low hydration levels. However this did not give rise to notable differences in hydronium ion diffusion and water network percolation for these membranes over Nafion. Similar observations were also reported by our group recently in a study of perfluoro-sulfonyl imide membranes carrying stronger super-acids than sulfonic acid of Nafion. These findings together suggest no strong apparent correlation between the acidity strength of the functional acid groups and the dynamics of water and hydronium ions in hydrated polymer electrolyte membranes (PEMs) with similar fluorocarbon backbones and acidic group-carrying side chains. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  13. In-situ measurement of electroosmotic drag coefficient in Nafion membrane for the PEMFC.

    PubMed

    Peng, Zhe; Morin, Arnaud; Huguet, Patrice; Schott, Pascal; Pauchet, Joël

    2011-11-10

    A new method based on hydrogen pump has been developed to measure the electroosmotic drag coefficient in representative PEMFC operating conditions. It allows eliminating the back-flow of water which leads to some errors in the calculation of this coefficient with previously reported electrochemical methods. Measurements have been performed on 50 μm thick Nafion membranes both extruded and recast. Contrary to what has been described in most of previous published works, the electroosmotic drag coefficient decreases as the membrane water content increases. The same trend is observed for temperatures between 25 and 80 °C. For the same membrane water content, the electroosmotic drag coefficient increases with temperature. In the same condition, there is no difference in drag coefficient for extruded Nafion N112 and recast Nafion NRE212. These results are discussed on the basis of the two commonly accepted proton transport mechanisms, namely, Grotthus and vehicular.

  14. Nanoscale Distribution of Sulfonic Acid Groups Determines Structure and Binding of Water in Nafion Membranes

    PubMed Central

    Ling, Xiao; Bonn, Mischa

    2016-01-01

    Abstract The connection between the nanoscale structure of two chemically equivalent, yet morphologically distinct Nafion fuel‐cell membranes and their macroscopic chemical properties is demonstrated. Quantification of the chemical interactions between water and Nafion reveals that extruded membranes have smaller water channels with a reduced sulfonic acid head group density compared to dispersion‐cast membranes. As a result, a disproportionally large amount of non‐bulk water molecules exists in extruded membranes, which also exhibit larger proton conductivity and larger water mobility compared to cast membranes. The differences in the physicochemical properties of the membranes, that is, the chemical constitution of the water channels and the local water structure, and the accompanying differences in macroscopic water and proton transport suggest that the chemistry of nanoscale channels is an important, yet largely overlooked parameter that influences the functionality of fuel‐cell membranes. PMID:26895211

  15. Nanoscale Distribution of Sulfonic Acid Groups Determines Structure and Binding of Water in Nafion Membranes.

    PubMed

    Ling, Xiao; Bonn, Mischa; Parekh, Sapun H; Domke, Katrin F

    2016-03-14

    The connection between the nanoscale structure of two chemically equivalent, yet morphologically distinct Nafion fuel-cell membranes and their macroscopic chemical properties is demonstrated. Quantification of the chemical interactions between water and Nafion reveals that extruded membranes have smaller water channels with a reduced sulfonic acid head group density compared to dispersion-cast membranes. As a result, a disproportionally large amount of non-bulk water molecules exists in extruded membranes, which also exhibit larger proton conductivity and larger water mobility compared to cast membranes. The differences in the physicochemical properties of the membranes, that is, the chemical constitution of the water channels and the local water structure, and the accompanying differences in macroscopic water and proton transport suggest that the chemistry of nanoscale channels is an important, yet largely overlooked parameter that influences the functionality of fuel-cell membranes.

  16. Exfoliated Pt-clay/Nafion nanocomposite membrane for self-humidifying polymer electrolyte fuel cells.

    PubMed

    Zhang, Wenjing; Li, Martin Ka Shing; Yue, Po-Lock; Gao, Ping

    2008-03-18

    Monolayers of Pt nanoparticles of diameters of 2-3 nm with a high crystallinity were successfully anchored onto exfoliated nanoclay surfaces using a novel chemical vapor deposition process. Chemical bonding of Pt to the oxygen on the clay surface ensured the stability of the Pt nanoparticles, and hence, no leaching of Pt particles was observed after a prolonged ultrasonication and a rigorous mechanical agitation of Pt-clay in the Nafion solution during the membrane casting process. Systematic analysis using WAXD and TEM showed that the recasting process produced a new self-humidifying exfoliated Pt-clay/Nafion nanocomposite membrane with a high crystallinity and proton conductivity. In situ water production for humidification of the dry membranes without any external humidification was characterized by a combined water uptake and FTIR analysis of the as-prepared membrane after a single cell testing without using electrodes. The power density at 0.5 V of a single cell made of a Pt-clay/Nafion nanocomposite membrane was 723 mW/cm2, which is 170% higher than that made of a commercial Nafion 112 membrane of similar thickness. No compromise in mechanical properties was observed.

  17. Electro-osmotic drag effect on the methanol permeation for sulfonated poly(ether ether ketone) and nafion 117 membranes.

    PubMed

    Chi, Nguyen Thi Que; Bae, Byungchan; Kim, Dukjoon

    2013-11-01

    Electro-osmotic drag effect on the methanol permeation was investigated for sulfonated poly(ether ether ketone) (sPEEK) membrane, and its result was compared with that of Nafion 117 membrane. The electro-osmotic drag coefficient was determined from the limiting current density measured at different temperature. The methanol permeability of sPEEK membrane increased with temperature but its temperature dependence was not as strong as that of Nafion 117 membrane. The methanol permeability or the total methanol flux of Nafion 117 membrane was at least twice higher than that of sPEEK70 membrane (sPEEK membrane with 70% sulfonation degree), as the methanol permeation was highly contributed by the electro-osmotic drag effect. This higher electro-osmotic drag of Nafion 117 membrane is attributed to the bigger ion cluster and waster channel in nanophase and thus more free water absorption than sPEEK membrane.

  18. Characterization of direct methanol fuel cell (DMFC) applications with H 2SO 4 modified chitosan membrane

    NASA Astrophysics Data System (ADS)

    Osifo, Peter O.; Masala, Aluwani

    Chitosan (Chs) flakes were prepared from chitin materials that were extracted from the exoskeleton of Cape rock lobsters in South Africa. The Chs flakes were prepared into membranes and the Chs membranes were modified by cross-linking with H 2SO 4. The cross-linked Chs membranes were characterized for the application in direct methanol fuel cells. The Chs membrane characteristics such as water uptake, thermal stability, proton resistance and methanol permeability were compared to that of high performance conventional Nafion 117 membranes. Under the temperature range studied 20-60 °C, the membrane water uptake for Chs was found to be higher than that of Nafion. Thermal analysis revealed that Chs membranes could withstand temperature as high as 230 °C whereas Nafion 117 membranes were stable to 320 °C under nitrogen. Nafion 117 membranes were found to exhibit high proton resistance of 284 s cm -1 than Chs membranes of 204 s cm -1. The proton fluxes across the membranes were 2.73 mol cm -2 s -1 for Chs- and 1.12 mol cm -2 s -1 Nafion membranes. Methanol (MeOH) permeability through Chs membrane was less, 1.4 × 10 -6 cm 2 s -1 for Chs membranes and 3.9 × 10 -6 cm 2 s -1 for Nafion 117 membranes at 20 °C. Chs and Nafion membranes were fabricated into membrane electrode assemblies (MAE) and their performances measure in a free-breathing commercial single cell DMFC. The Nafion membranes showed a better performance as the power density determined for Nafion membranes of 0.0075 W cm -2 was 2.7 times higher than in the case of Chs MEA.

  19. PEDOT:PSS self-assembled films to methanol crossover reduction in Nafion® membranes

    NASA Astrophysics Data System (ADS)

    Almeida, Tiago P.; Miyazaki, Celina M.; Paganin, Valdecir A.; Ferreira, Marystela; Saeki, Margarida J.; Perez, Joelma; Riul, Antonio

    2014-12-01

    Alternative energy sources are on a global demand, with fuel cells as promising devices from mobile to stationary applications. Nafion® is at the heart of many of these appliances, being mostly used due to its high proton conduction and good chemical stability at ambient temperature in proton exchange membranes (PEM). Therefore, methanol permeation throughout Nafion® films reduces drastically the performance of direct methanol fuel cells (DMFC). We present here the deposition of layer-by-layer (LbL) nanostructured thin films of poly(allylamine hydrochloride) (PAH) and poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) onto commercial Nafion® 212 membranes. It was observed a good adherence of the LbL films onto Nafion® 212, with UV-vis results displaying a linear characteristic growth, indicative that the same amount of material was deposited at each deposition step during the layer-by-layer assembly. In addition, the LbL films also act as a good barrier to avoid methanol crossover, with an observed reduction in the methanol permeation from 5.5 × 10-6 cm2 s-1 to 3.2 × 10-6 cm2 s-1, respectively to pristine Nafion® 212 and a 5-bilayer PAH/PEDOT:PSS LbL film deposited on Nafion®212. The measured power density in a DMFC set-up was not significantly changed (∼12 mW cm-2) due to the LbL films, since the PAH/PEDOT:PSS nanostructure is impeding water and ion transport, consequently affecting the proton conduction throughout the membrane.

  20. Investigation of local environments in Nafion-SiO(2) composite membranes used in vanadium redox flow batteries.

    PubMed

    Vijayakumar, M; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Thevuthasan, S; Liu, Jun; Graff, Gordon L; Hu, Jianzhi

    2012-04-01

    Proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, polymer composite membranes, such as SiO(2) incorporated Nafion membranes, are recently reported as highly promising for the use in redox flow batteries. However, there is conflicting reports regarding the performance of this type of Nafion-SiO(2) composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO(2) composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transform Infra Red (FTIR) spectroscopy, and ultraviolet-visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the (19)F and (29)Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The (29)Si NMR shows that the silica particles interact via hydrogen bonds with the sulfonic groups of Nafion and the diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO(2) composite membrane materials in vanadium redox flow batteries.

  1. Investigation of Local Environments in Nafion-SiO2 Composite Membranes used in Vanadium Redox Flow Batteries

    SciTech Connect

    Vijayakumar, M.; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Thevuthasan, Suntharampillai; Liu, Jun; Graff, Gordon L.; Hu, Jian Z.

    2012-04-01

    The proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, the polymer composite membranes such as SiO2 incorporated Nafion membranes are recently reported as highly promising for the redox flow batteries. However, there is conflicting reports regarding the performance of this Nafion-SiO2 composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO2 composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transformed Infra Red (FTIR) spectroscopy, and ultraviolet visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the 19F and 29Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The 29Si NMR shows that the silica particles interaction via hydrogen bonds to the sulfonic groups of Nafion and diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO2 composite membrane materials in vanadium redox flow batteries.

  2. Composite Nafion/sulfonated zirconia membranes: effect of the filler surface properties on proton transport characteristics

    PubMed Central

    D’Epifanio, Alessandra; Navarra, Maria Assunta; Weise, F. Christoph; Mecheri, Barbara; Farrington, Jaime; Licoccia, Silvia; Greenbaum, Steve

    2009-01-01

    Due to their strong acidity and water affinity, sulfated zirconia nanoparticles were evaluated as inorganic additives in the formation of composite Nafion-based membranes. Two types of sulfated zirconia were obtained according to the preparation experimental conditions. Sulfated zirconia-doped Nafion membranes were prepared by a casting procedure. The properties of the composite membranes were compared with those of an unfilled Nafion membrane obtained by the same preparation method. The water uptake, measured at room temperature in a wide relative humidity range, was higher for the composite membranes, this confirming the hydrophilic nature of the selected additives. The membrane doped by zirconia particles having the highest sulphate group concentration showed the highest water diffusion coefficient in the whole range of temperature and relative humidity investigated due to the presence of SO42− providing extra acid sites for water diffusion. The proton diffusivity calculated from impedance spectroscopy measurements was compared with water self diffusion coefficients measured by NMR Spectroscopy. The difference between proton and water diffusivity became significant only at high humidification levels, highlighting the role of water in the intermolecular proton transfer mechanism. Finally, great improvements were found when using the composite membrane as electrolyte in a fuel cell working at very low relative humidity. PMID:20209115

  3. Investigation of water structure in nafion membranes by infrared spectroscopy and molecular dynamics simulation.

    PubMed

    Hofmann, Detlef W M; Kuleshova, Liudmila; D'Aguanno, Bruno; Di Noto, Vito; Negro, Enrico; Conti, Fosca; Vittadello, Michele

    2009-01-22

    The structure and interactions of water species in hydrated Nafion membranes as a function of water content were investigated on the basis of medium-infrared spectral analysis and molecular dynamics (MD) simulations. The spectral decomposition of the FT-IR data in the stretching OH region was performed on different levels of hydration of the sulfate functional groups (lambdaH2O/RSO3- = 2-22). Quantum mechanical calculations of two model systems [perfluoroethanesulfonic acid/(H2O)6 cluster] and a [perfluorobutanesulfonic acid/(H2O)6 crystal] were carried out in order to account for the band assignments of Nafion in the stretching OH region (2500-4000 cm-1). Our findings indicated that the secondary structure of water species in Nafion can be accurately explained in terms of our reactive force field for water. The distinction between "surface" and "bulk" water contributions in Nafion membrane pores is proposed along with a quantitative estimate of the different types of OH groups present in the system. The average pore size was calculated and supported by the spectral results. PMID:19113878

  4. Pervaporation of Water from Aqueous Sulfuric Acid at Elevated Temperatures Using Nafion® Membranes

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart

    2009-01-01

    The concentration of sulfuric acid by pervaporation has been studied using Nafion-112® and Nafion-117® membranes, which have been characterized in terms of flux, permeability, and selectivity at 100 ºC and 120 ºC. Feed concentrations investigated ranged from 40 to over 80 weight percent. In general, water fluxes ranged from 100-8000 g/m2h, depending on feed acid concentration and separations factors as high as 104 were observed. Membrane stability was probed using Dynamic Mechanical Analysis that revealed some embrittlement of the membranes during use. Further studies showed that the embrittlement was due to an interaction with the acid and was not induced by the operating temperature.

  5. Ultra-thin polytetrafluoroethene/Nafion/silica composite membrane with high performance for vanadium redox flow battery

    NASA Astrophysics Data System (ADS)

    Teng, Xiangguo; Dai, Jicui; Bi, Fangyuan; Yin, Geping

    2014-12-01

    Ultra-thin and high performance polytetrafluoroethene (PTFE)/Nafion/silica composite membrane has been successfully prepared by solution casting and sol-gel method for all vanadium redox flow battery (VRB). Thickness of ∼25 μm polytetrafluoroethene/Nafion (P/N) membrane is first prepared by impregnating porous PTFE membrane with Nafion solution, and then the P/N membrane is immersed in tetraethoxysilane (TEOS) solution to prepare PTFE/Nafion/silica (P/N/S) composite membranes. The chemical structures of membranes are investigated by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR), which prove that the Nafion resin and silica are well impregnated in PTFE membrane. The water uptake, proton conductivity, vanadium permeability and VRB single cell tests of the composite membrane are also investigated in detail. At 80 mA cm-2, coulombic efficiency, voltage efficiency and energy efficiency of the VRB with P/N/S-7 (7 wt.% SiO2 in P/N/S) membrane are 93.9%, 87.2% and 81.9%, respectively. Furthermore, the self-discharge rate of the VRB with P/N/S membrane is much slower than that of the VRB with P/N membrane, which indicates that the membrane has good vanadium block ability. Fifty cycles charge-discharge test proves that the P/N/S membrane is very stable and possesses high chemical stability under the strong acid solutions.

  6. Passive approach for the improved dispersion of polyvinyl alcohol-based functionalized multi-walled carbon nanotubes/Nafion membranes for polymer electrolyte membrane fuel cells.

    PubMed

    Abu Sayeed, M D; Talukdar, Krishan; Kim, Hee Jin; Park, Younjin; Gopalan, A I; Kim, Young Ho; Lee, Kwang-Pill; Choi, Sang-June

    2014-12-01

    Multi-walled carbon nanotubes (MWCNTs) are regarded as ideal fillers for Nafion polymer electrolyte membranes (PEMs) for fuel cell applications. The highly aggregated properties of MWCNTs can be overcome by the successful cross-linking with polyvinyl alcohol (PVA) into the MWCNTs/Nafion membrane. In this study, a series of nanocomposite membranes were fabricated with the PVA-influenced functionalized MWCNTs reinforced into the Nafion polymer matrix by a solution casting method. Several different PVA contents were blended to f-MWCNTs/Nafion nanocomposite membranes followed by successful cross-linking by annealing. The surface morphologies and the inner structures of the resulting PVA-MWCNTs/Nafion nanocomposite membranes were then observed by optical microscopy and scanning electron microscopy (SEM) to investigate the dispersion of MWCNTs into the PVA/Nafion composite membranes. After that, the nanocomposite membranes were characterized by thermo-gravimetric analysis (TGA) to observe the thermal enhancement caused by effective cross-linking between the f-MWCNTs with the composite polymer matrixes. Improved water uptake with reduced methanol uptake revealed the successful fabrication of PVA-blended f-MWCNTs/Nafion membranes. In addition, the ion exchange capacity (IEC) was evaluated for PEM fuel cell (PEMFC) applications.

  7. Glucose oxidase as a biocatalytic enzyme-based bio-fuel cell using Nafion membrane limiting crossover

    NASA Astrophysics Data System (ADS)

    Naidoo, S.; Naidoo, Q.; Blottnitz, H.; Vaivars, G.

    2013-12-01

    A novel combination for an Enzyme-based Biofuel cell included a Nafion membrane as an ion transporter that maintained a working cell charge and inhibited membrane degradation. The prototype cell chamber used oxygen (O2) in the cathode cell and glucose in the anode. The Nafion membrane stability studied here was evidently in the region of 0% loss of conductivity as the charge was constant and increased after the addition of glucose. The prototype cell chamber used NaCl in the cathode cell and glucose oxidase (GOx) in the anodic chamber was successfully studied for membrane stability showed in this study no evidence of poisoning from membrane leakage in a controlled pH environment. There was no crossover at the anaerobic operating ambient temperatures and under physiological pH 5 - 7 conditions. In this research we have successfully used a Nafion membrane together with GOx and under controlled conditions produced respectable power densities.

  8. Bacterial nanocellulose/Nafion composite membranes for low temperature polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Jiang, Gao-peng; Zhang, Jing; Qiao, Jin-li; Jiang, Yong-ming; Zarrin, Hadis; Chen, Zhongwei; Hong, Feng

    2015-01-01

    Novel nanocomposite membranes aimed for both proton-exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC) are presented in this work. The membranes are based on blending bacterial nanocellulose pulp and Nafion (abbreviated as BxNy, where x and y indicates the mass ratio of bacterial cellulose to Nafion). The structure and properties of BxNy membranes are characterized by FTIR, SEM, TG, DMA and EIS, along with water uptake, swelling behavior and methanol permeability tests. It is found that the BxNy composite membranes with reinforced concrete-like structure show excellent mechanical and thermal stability regardless of annealing. The water uptake plus area and volume swelling ratios are all decreased compared to Nafion membranes. The proton conductivities of pristine and annealed B1N9 are 0.071 and 0.056 S cm-1, respectively, at 30 °C and 100% humidity. Specifically, annealed B1N1 exhibited the lowest methanol permeability of 7.21 × 10-7 cm2 s-1. Through the selectivity analysis, pristine and annealed B1N7 are selected to assemble the MEAs. The performances of annealed B1N7 in PEMFC and DMFC show the maximum power densities of 106 and 3.2 mW cm-2, respectively, which are much higher than those of pristine B1N7 at 25 °C. The performances of the pristine and annealed B1N7 reach a level as high as 21.1 and 20.4 mW cm-2 at 80 °C in DMFC, respectively.

  9. Spatial and temporal mapping of water content across Nafion membranes under wetting and drying conditions.

    PubMed

    Zhang, Ziheng; Marble, Andrew E; MacMillan, Bryce; Promislow, Keith; Martin, Jonathan; Wang, Haijiang; Balcom, Bruce J

    2008-10-01

    Water transport and water management are fundamental to polymer electrolyte membrane fuel cell operation. Accurate measurements of water content within and across the Nafion layer are required to elucidate water transport behavior and validate existing numerical models. We report here a direct measurement of water content profiles across a Nafion layer under wetting and drying conditions, using a novel magnetic resonance imaging methodology developed for this purpose. This method, multi-echo double half k-space spin echo single point imaging, based on a pure phase encode spin echo, is designed for high resolution 1D depth imaging of thin film samples. The method generates high resolution (<8 microm) depth images with an SNR greater than 20, in an image acquisition time of less than 2 min. The high temporal resolution permits water content measurements in the transient states of wetting and drying, in addition to the steady state.

  10. Nafion ® nanocomposite membranes: Effect of fluorosurfactants on hydrophobic silica nanoparticle dispersion and direct methanol fuel cell performance

    NASA Astrophysics Data System (ADS)

    Park, Chi Hoon; Kim, Hong Keon; Lee, Chang Hyun; Park, Ho Bum; Lee, Young Moo

    Nafion ®-silica nanocomposite membranes are successfully prepared by adding hydrophobic silica nanoparticles to a Nafion ® solution. To distribute these nanoparticles evenly in the Nafion ® matrix, various fluorosurfactants of different ionic character are employed. Fluorosurfactants with acid groups such as phosphonic acid and sulfonic acid play an important role in simultaneously increasing the homogeneous dispersion of silica nanoparticles, enhancing proton conductivity, and reducing the methanol permeability of the nanocomposite membranes. Therefore, the dispersion properties of inorganic fillers such as silica can significantly affect nanocomposite performance in direct methanol fuel cell (DMFC) applications, whereas surfactants, if used properly, can improve the nanocomposite membrane properties. In particular, a commercial fluorosurfactant containing a sulfonic acid group (Zonyl ® TBS) at the end of the surfactant chain exhibits better miscibility with the Nafion ® ionomer. This feature results in a reduction in the dimensional change of the nanocomposite membrane due to relatively lower water swelling and significantly reduced methanol permeability through the membrane. A membrane-electrode assembly (MEA) prepared from a Nafion ®-silica nanocomposite membrane with TBS shows the highest DMFC performance in terms of voltage vs. current density (V- I) and power density vs. current density (P- I). The current densities at 0.4 V and 90 °C are 342, 508, and 538 mA cm -2 with 1, 3 and 5 M methanol being fed at the anode side, respectively.

  11. Comparison of electrochemical and microbiological characterization of microbial fuel cells equipped with SPEEK and Nafion membrane electrode assemblies.

    PubMed

    Suzuki, Kei; Owen, Rubaba; Mok, Joann; Mochihara, Hiroki; Hosokawa, Takuya; Kubota, Hiroko; Sakamoto, Hisatoshi; Matsuda, Atsunori; Tashiro, Yosuke; Futamata, Hiroyuki

    2016-09-01

    Microbial fuel cells equipped with SPEEK-MEA (SPEEK-MFC) and Nafion-MEA (Nafion-MFC) were constructed with organic waste as electron donor and lake sediment as inoculum and were then evaluated comprehensively by electrochemical and microbial analyses. The proton conductivity of SPEEK was several hundreds-fold lower than that of Nafion 117, whereas the oxygen mass and diffusion transfer coefficients of SPEEK were 10-fold lower than those of Nafion 117. It was difficult to predict which was better membrane for MFC based on the feature of membrane. Analyses of polarization curves indicated that the potential of electricity production was similar in both MFCs, as the SPEEK-MFC produced 50-80% of the practical current density generated by the Nafion-MFC. Chronopotentiometry analyses indicated that the Nafion-MEA kept the performance longer than the SPEEK-MEA for long period, whereas performance of both anodes improved on time. Multidimensional scaling analyses based on DGGE profiles revealed the anolytic and biofilm communities of the SPEEK-MFC had developed differently from those of the Nafion-MFC. Clone library analyses indicated that Geobacter spp. represented 6.3% of the biofilm bacterial community in the Nafion-MFC but not detected in the SPEEK-MFC. Interestingly, the clone closely related to Acetobacterium malicum strain HAAP-1, belonging to the homoacetogens, became dominant in both anolytic and biofilm communities of the SPEEK-MFC. It was suggested that the lower proton conductivity of SPEEK-MEA allowed the bacteria closely related to strain HAAP-1 to be dominant specifically in SPEEK-MFC. These results indicated that Nafion-MFC ranked with SPEEK-MFC and that MEAs had strong selective pressure for electricity-producing bacterial community.

  12. Comparison of electrochemical and microbiological characterization of microbial fuel cells equipped with SPEEK and Nafion membrane electrode assemblies.

    PubMed

    Suzuki, Kei; Owen, Rubaba; Mok, Joann; Mochihara, Hiroki; Hosokawa, Takuya; Kubota, Hiroko; Sakamoto, Hisatoshi; Matsuda, Atsunori; Tashiro, Yosuke; Futamata, Hiroyuki

    2016-09-01

    Microbial fuel cells equipped with SPEEK-MEA (SPEEK-MFC) and Nafion-MEA (Nafion-MFC) were constructed with organic waste as electron donor and lake sediment as inoculum and were then evaluated comprehensively by electrochemical and microbial analyses. The proton conductivity of SPEEK was several hundreds-fold lower than that of Nafion 117, whereas the oxygen mass and diffusion transfer coefficients of SPEEK were 10-fold lower than those of Nafion 117. It was difficult to predict which was better membrane for MFC based on the feature of membrane. Analyses of polarization curves indicated that the potential of electricity production was similar in both MFCs, as the SPEEK-MFC produced 50-80% of the practical current density generated by the Nafion-MFC. Chronopotentiometry analyses indicated that the Nafion-MEA kept the performance longer than the SPEEK-MEA for long period, whereas performance of both anodes improved on time. Multidimensional scaling analyses based on DGGE profiles revealed the anolytic and biofilm communities of the SPEEK-MFC had developed differently from those of the Nafion-MFC. Clone library analyses indicated that Geobacter spp. represented 6.3% of the biofilm bacterial community in the Nafion-MFC but not detected in the SPEEK-MFC. Interestingly, the clone closely related to Acetobacterium malicum strain HAAP-1, belonging to the homoacetogens, became dominant in both anolytic and biofilm communities of the SPEEK-MFC. It was suggested that the lower proton conductivity of SPEEK-MEA allowed the bacteria closely related to strain HAAP-1 to be dominant specifically in SPEEK-MFC. These results indicated that Nafion-MFC ranked with SPEEK-MFC and that MEAs had strong selective pressure for electricity-producing bacterial community. PMID:27215833

  13. Material properties of the Pt electrode deposited on nafion membrane by the impregnation-reduction method.

    PubMed

    Rashid, Muhammad; Jun, Tae-Sun; Kim, Yong Shin

    2013-05-01

    Platinum nanoparticles (Pt NPs) were chemically deposited on a Nafion polymer electrolyte membrane by the impregnation-reduction (I-R) procedure to prepare an active electrode for solid electrochemical sensors. Various analysis methods such as SEM, EDX, XRD and cyclic voltammogram (CV) measurements were employed in order to characterize microstructures and electrochemical properties of the Pt layer. At the conditions ([Pt(NH3)4Cl2] = 10 mM, [NaBH4] = 60 mM, 50 degrees C), the porous Pt thin-film, consisting of sphere-like particles formed by the agglomeration of primary polycrystalline Pt NPs with an average crystal size of 13-18 nm, was obtained and confirmed to have a large surface area (roughness factor = 267) and strong adhesion due to the formation of interfacial Pt-Nafion composites. The secondary globular particles were found to have an average diameter of 215 nm and irregular protuberances on the surface. Furthermore, this electrode exhibited well-resolved CV peaks for the hydrogen redox reactions in an acid solution, suggesting the existence of different adsorption sites and good electrochemical behaviors. Pt/Nafion electrodes were prepared under different conditions in [Pt(NH3)4Cl2], [NaBH4] and reaction temperature, and their material properties were discussed from the viewpoint of a Pt growth mechanism. PMID:23858916

  14. Preparation of gradually componential metal electrode on solution-casted Nafion membrane.

    PubMed

    Chung, Ren-Jei; Chin, Tsung-Shune; Chen, Li-Chun; Hsieh, Ming-Fa

    2007-11-01

    A typical ionic polymer-metal composite consists of a thin perfluorinated ionomer membrane and noble metal electrodes plated on both surfaces. It undergoes a large bending motion when an electric field is applied hence exhibits deformation by a certain amount of cation. With proper arrangement and package, a great number of "smart devices" are anticipated. In this study, a solution-cast route was used to prepare the electro-active polymer membrane and platinum electrodes were fabricated onto the membrane through electro-less plating. The ionic polymer used is the commercial Nafion, the perfluoro-sulfonated ionomer membrane, developed by DuPont Co. Nafion membrane was cast by the solution-casting route and then loaded with different weights simultaneously. The optimized processing conditions, membrane properties and electrodes behaviors were investigated. The results of shift in WAXD peaks showed that weights delineated the crystallinity of the solution-cast membranes. The number and size of the crystalline domains of solution-cast membrane decrease as studied by SAXS. The Young's modulus of solution-cast membrane decreases as increasing weight because of the loss of crystallinity (180-140 MPa). A finely dispersed platinum particle deeper and gradient penetrating within the near-boundary region with a smaller average particle size and more uniform distribution could be obtained through a reverse electro-less plating. Its surface roughness is 3 nm comparing to 52 nm of a typical process. But its surface resistance is too high (3.5 Omega) to activate the bending motion. To solve this problem, we coated the second Pt electrodes by a typical electro-less plating, and the resistance decreased to 0.7 Omega. The results depicted that the fabricated IPMC shows longer bending lifetime than typical IPMC. In a 0.09% NaCl solution, the device was able to vibrate for 8h under a 5 V, 0.1 Hz actuation.

  15. Experimental determination of the transport number of water in Nafion 117 membrane

    SciTech Connect

    Fuller, T.F.; Newman, J. . Dept. of Chemical Engineering)

    1992-05-01

    The transport number of water in Nafion 117 membrane over a wide range of water contents is determined experimentally using a concentration cell. The transport number of water, the ratio f[sup m][sub o]/Z[sub o], is about 1.4 for a membrane equilibrated with saturated water vapor at 25[degrees]C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the concentration of water approaches zero. In this paper, the relationship between the transference number, the transport number, and the electro-osmotic drag coefficient is presented, and their relevance to water management is solid-polymer-electrolyte fuel cells is discussed. Results are compared with other data available in the literature and with the theoretical maximum.

  16. Performance improvement of passive direct methanol fuel cells with surface-patterned Nafion® membranes

    NASA Astrophysics Data System (ADS)

    Pu, Longjuan; Jiang, Jingjing; Yuan, Ting; Chai, Jieshi; Zhang, Haifeng; Zou, Zhiqing; Li, Xue-Mei; Yang, Hui

    2015-02-01

    Nafion® 115 membrane, patterned by thermal imprint lithography on the anode side, is used for passive direct methanol fuel cells (DMFCs). The membrane roughness factor, defined as the ratio between the actual and projected membrane surface area, was investigated for its effects on the performance of the DMFCs. When the anode Pt-Ru (1:1) catalyst loading is 1.0 mg cm-2, the maximum power density of the DMFC with a surface-patterned membrane (roughness factor: 5.4) using 3.0 M methanol as the fuel at 25 ± 1 °C reaches 27.2 ± 0.3 mW cm-2, an increase of ∼57.2% in comparison to DMFC using the pristine membrane (roughness factor: ∼1.0). Further, electrochemical characterization indicates that increased roughness factor of the membrane results in increased electrochemically active surface area and reduced charge transfer resistance in the cell. These performance improvements are ascribed to the increased surface roughness which enlarges the membrane/catalyst interface, possibly facilitating mass transport of the fuel and improving anode catalyst utilization. Thus, patterned membranes have great potential in improving the performance of fuel cells and reducing catalyst loading.

  17. Effect of various concentration of sulfuric acid for Nafion membrane activation on the performance of fuel cell

    NASA Astrophysics Data System (ADS)

    Pujiastuti, Sri; Onggo, Holia

    2016-02-01

    This work proposes an activation treatment to Nafion 117 membrane with sulfuric acid in various concentrations. The main goal of this study is to increase the Nafion 117 membrane performance, which is determined by proton number in the membrane and membrane performance in Polymer Electrolyte Membrane Fuel Cell (PEMFC). This work was developed using sulfuric acids in four different concentrations: 1, 2, 3, and 4 M. The surface morphology and functional groups of activated membranes were studied using Scanning Electron Microscope and Fourier Transform Infrared, respectively. The proton number absorbed in membranes was observed by gravimetric measurements. The performances of activated membranes in PEMFC were studied by single cell measurements with H2/O2 operation. The experimental results showed that activation of Nafion membrane did not change its surface morphology and functional groups. The proton number increased when the concentration of sulfuric acid is increased from 1 to 3 M and from 1 to 4 M. On the other hand, there is no significant increase when the concentration of sulfuric acid was increased from 1 to 2 M. Similar trends were observed when testing activated membrane performance in PEMFC, especially for current density at 0.6 V and maximum power. It is assumed that there is a correlation between the increase of sulfuric acid concentration in activation process with the increase of proton number in the membrane that are available for facilitating of transfer protons from the anode to the cathode.

  18. Coating of Nafion membranes with polyelectrolyte multilayers to achieve high monovalent/divalent cation electrodialysis selectivities.

    PubMed

    White, Nicholas; Misovich, Maria; Yaroshchuk, Andriy; Bruening, Merlin L

    2015-04-01

    Electrodialysis (ED) membranes typically exhibit modest selectivities between monovalent and divalent ions. This paper reports a dramatic enhancement of the monovalent/divalent cation selectivities of Nafion 115 membranes through coating with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. Remarkably, K(+)/Mg(2+) ED selectivities reach values >1000, and similar monovalent/divalent cation selectivities occur with feed solutions containing K(+) and Ca(2+). For comparison, the corresponding K(+)/Mg(2+) selectivity of bare Nafion 115 is only 1.8 ± 0.1. However, with 0.01 M KNO3 and 0.01 M Mg(NO3)2 in the source phase, as the applied current density increases from 1.27 to 2.54 mA cm(-2), the K(+)/Mg(2+) selectivities of coated membranes decrease from >1000 to 22. Water-splitting at strongly overlimiting current densities may lead to a local pH increase close to the membrane surface and alter film permeability or allow passage of Mg(OH)x species to decrease selectivity. When the source phase contains 0.1 M KNO3 and 0.1 M Mg(NO3)2, the K(+) transference number approaches unity and the K(+)/Mg(2+) selectivity is >20,000, presumably because the applied current is below the limiting value for K(+) and H(+) transport is negligible at this high K(+) concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions.

  19. Highly selective dopamine electrochemical sensor based on electrochemically pretreated graphite and nafion composite modified screen printed carbon electrode.

    PubMed

    Ku, Shuhao; Palanisamy, Selvakumar; Chen, Shen-Ming

    2013-12-01

    Herein, we report a highly selective dopamine electrochemical sensor based on electrochemically pretreated graphite/nafion composite modified screen printed carbon (SPC) electrode. Electrochemically activated graphite/nafion composite was prepared by using a simple electrochemical method. Scanning electron microscope (SEM) used to characterize the surface morphology of the fabricated composite electrode. The SEM result clearly indicates that the graphitic basal planes were totally disturbed and leads to the formation of graphite nanosheets. The composite modified electrode showed an enhanced electrocatalytic activity toward the oxidation of DA when compared with either electrochemical pretreated graphite or nafion SPC electrodes. The fabricated composite electrode exhibits a good electrocatalytic oxidation toward DA in the linear response range from 0.5 to 70 μM with the detection limit of 0.023 μM. The proposed sensor also exhibits very good selectivity and stability, with the appreciable sensitivity. In addition, the proposed sensor showed satisfactory recovery results toward the commercial pharmaceutical DA samples.

  20. Electrochemical performance and transport properties of a Nafion membrane in a hydrogen-bromine cell environment

    NASA Technical Reports Server (NTRS)

    Baldwin, Richard S.

    1987-01-01

    The overall energy conversion efficiency of a hydrogen-bromine energy storage system is highly dependent upon the characteristics and performance of the ion-exchange membrane utilized as a half-cell separator. The electrochemical performance and transport properties of a duPont Nafion membrane in an aqueous HBr-Br2 environment were investigated. Membrane conductivity data are presented as a function of HBr concentration and temperature for the determination of ohmic voltage losses across the membrane in an operational cell. Diffusion-controlled bromine permeation rates and permeabilities are presented as functions of solution composition and temperature. Relationships between the degree of membrane hydration and the membrane transport characteristics are discussed. The solution chemistry of an operational hydrogen-bromine cell undergoing charge from 45% HBr to 5% HBr is discussed, and, based upon the experimentally observed bromine permeation behavior, predicted cell coulombic losses due to bromine diffusion through the membrane are presented as a function of the cell state-of-charge.

  1. A flexible all-inorganic fuel cell membrane with conductivity above Nafion, and durable operation at 150 °C

    NASA Astrophysics Data System (ADS)

    Ansari, Y.; Tucker, T. G.; Huang, W.; Klein, I. S.; Lee, S.-Y.; Yarger, J. L.; Angell, C. A.

    2016-01-01

    The search for fuel cell membranes has focused on carbon backbone polymers, among which Nafion seems to best survive the most severe of the degradation mechanisms - attack by peroxide radicals. Less attention has been given to inorganic membranes because of their generally inflexible nature and lower conductivity, though some SiO2-Nafion composites have shown improved properties. Nafion dominates, despite needing hydration, which then restricts operation to below 100 °C (so CO poisoning problems persist). Described herein is a low cost, flexible, and all-inorganic fiberglass reinforced gel membrane with conductivity exceeding that of Nafion at any temperature above 60 °C. Using Teflon fuel cells, maximum currents > 1 Acm-2 and OCV of 1.03 V at 150 °C are demonstrated. No detectable loss of cell potential was observed over 24 h during 50 mAcm-2 constant current operation at 120 °C while, at 150 °C and maximum power, the degradation rate is intermediate among other high conductivity H3PO4-PBI type membranes. The structure of the membrane is deduced, mainly from 29Si solid state-NMR. The -115 ppm resonance, which is extreme for Q4 Si(O) structures, identifies a zeolite-like SiO2 network, which is "floppy". 31P and 1H NMR establish nano-permeating H3PO4 as the source of the exceptional conductivity.

  2. Tailoring of interfacial mechanical shear strength by surface chemical modification of silicon microwires embedded in Nafion membranes.

    PubMed

    Gallant, Betar M; Gu, X Wendy; Chen, David Z; Greer, Julia R; Lewis, Nathan S

    2015-05-26

    The interfacial shear strength between Si microwires and a Nafion membrane has been tailored through surface functionalization of the Si. Acidic (-COOH-terminated) or basic (-NH2-terminated) surface-bound functionality was introduced by hydrosilylation reactions to probe the interactions between the functionalized Si microwires and hydrophilic ionically charged sites in the Nafion polymeric side chains. Surfaces functionalized with SiOx, Si-H, or Si-CH3 were also synthesized and investigated. The interfacial shear strength between the functionalized Si microwire surfaces and the Nafion matrix was quantified by uniaxial wire pull-out experiments in an in situ nanomechanical instrument that allowed simultaneous collection of mechanical data and visualization of the deformation process. In this process, an axial load was applied to the custom-shaped top portions of individual wires until debonding occurred from the Nafion matrix. The shear strength obtained from the nanomechanical measurements correlated with the chemical bond strength and the functionalization density of the molecular layer, with values ranging from 7 MPa for Si-CH3 surfaces to ∼16-20 MPa for oxygen-containing surface functionalities. Hence surface chemical control can be used to influence the mechanical adhesion forces at a Si-Nafion interface. PMID:25872455

  3. Ionic cluster size distributions of swollen nafion/sulfated beta-cyclodextrin membranes characterized by nuclear magnetic resonance cryoporometry.

    PubMed

    Jeon, Jae-Deok; Kwak, Seung-Yeop

    2007-08-16

    Nafion/sb-CD membranes were prepared by mixing 5 wt% Nafion solution with H+-form sulfated beta-cyclodextrin (sb-CD), and their water uptakes, ion exchange capacities (IECs), and ionic cluster size distributions were measured. Gravimetric and thermogravimetric measurements showed that the water uptake of the membranes increased with increases in their sb-CD content. The IECs of the membrane were measured with acid-base titration and found to increase with increases in the sb-CD content, reaching 0.96 mequiv/g for NC5 ("NCx" denotes a Nafion/sb-CD composite membrane containing x wt% of sb-CD). The cluster-correlation peaks and ionic cluster size distributions of the water-swollen membranes were determined using small-angle X-ray scattering (SAXS) and 1H nuclear magnetic resonance (NMR) cryoporometry, respectively. The SAXS experiments confirmed that increases in the sb-CD content of the membranes shifted the maximum SAXS peaks to lower angles, indicating an increase in the cluster correlation peak. NMR cryoporometry is based on the theory of the melting point depression, Delta Tm, of a liquid confined within a pore, which is dependent on the pore diameter. The melting point depression was determined by analyzing the variation of the NMR signal intensity with temperature. Our analysis of the intensity-temperature (IT) curves showed that the ionic cluster size distribution gradually became broader with increases in the membrane sb-CD content due to the increased water content, indicating an increase in the ionic cluster size. This result indicates that the presence of sb-CD with its many sulfonic acid sites in the Nafion membranes results in increases in the ionic cluster size as well as in the water uptake and the IEC. We conclude that NMR cryoporometry provides a method for determining the ionic cluster size on the nanometer scale in an aqueous environment, which cannot be obtained using other methods.

  4. Magnetic resonance imaging of water content across the Nafion membrane in an operational PEM fuel cell.

    PubMed

    Zhang, Ziheng; Martin, Jonathan; Wu, Jinfeng; Wang, Haijiang; Promislow, Keith; Balcom, Bruce J

    2008-08-01

    Water management is critical to optimize the operation of polymer electrolyte membrane fuel cells. At present, numerical models are employed to guide water management in such fuel cells. Accurate measurements of water content variation in polymer electrolyte membrane fuel cells are required to validate these models and to optimize fuel cell behavior. We report a direct water content measurement across the Nafion membrane in an operational polymer electrolyte membrane fuel cell, employing double half k-space spin echo single point imaging techniques. The MRI measurements with T2 mapping were undertaken with a parallel plate resonator to avoid the effects of RF screening. The parallel plate resonator employs the electrodes inherent to the fuel cell to create a resonant circuit at RF frequencies for MR excitation and detection, while still operating as a conventional fuel cell at DC. Three stages of fuel cell operation were investigated: activation, operation and dehydration. Each profile was acquired in 6 min, with 6 microm nominal resolution and a SNR of better than 15.

  5. Ultrasonic-assisted synthesis of ZrO2 nanoparticles and their application to improve the chemical stability of Nafion membrane in proton exchange membrane (PEM) fuel cells.

    PubMed

    Taghizadeh, Mohammad Taghi; Vatanparast, Morteza

    2016-12-01

    Zirconium dioxide (ZrO2) nanoparticles were fabricated successfully via ultrasonic-assisted method using ZrO(NO3)2·H2O, ethylenediamine and hydrazine as precursors in aqueous solution. Morphology, structure and composition of the obtained products were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FT-IR) and diffuse reflectance spectroscopy (DRS). Then, the synthesized nanoparticles were used to prepare Nafion/ZrO2 nanocomposite membranes. The properties of the membranes were studied by ion exchange capacity (IEC) proton conductivity (σ), thermal stability and water uptake measurements. The ex-situ Fenton's test was used to investigate the chemical stability of the membranes. From our results, compared with Nafion membrane, the nanocomposite membrane exhibited lower fluoride release and weight loss. Therefore, it can concluded that Nafion/ZrO2 nanocomposite exhibit more chemical stability than the pure Nafion membrane. ATR-FTIR spectra and SEM surface images of membranes also confirm these results. PMID:27544443

  6. Ultrasonic-assisted synthesis of ZrO2 nanoparticles and their application to improve the chemical stability of Nafion membrane in proton exchange membrane (PEM) fuel cells.

    PubMed

    Taghizadeh, Mohammad Taghi; Vatanparast, Morteza

    2016-12-01

    Zirconium dioxide (ZrO2) nanoparticles were fabricated successfully via ultrasonic-assisted method using ZrO(NO3)2·H2O, ethylenediamine and hydrazine as precursors in aqueous solution. Morphology, structure and composition of the obtained products were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FT-IR) and diffuse reflectance spectroscopy (DRS). Then, the synthesized nanoparticles were used to prepare Nafion/ZrO2 nanocomposite membranes. The properties of the membranes were studied by ion exchange capacity (IEC) proton conductivity (σ), thermal stability and water uptake measurements. The ex-situ Fenton's test was used to investigate the chemical stability of the membranes. From our results, compared with Nafion membrane, the nanocomposite membrane exhibited lower fluoride release and weight loss. Therefore, it can concluded that Nafion/ZrO2 nanocomposite exhibit more chemical stability than the pure Nafion membrane. ATR-FTIR spectra and SEM surface images of membranes also confirm these results.

  7. Small-angle X-ray and neutron scattering study of Nafion-SiO2 hybrid membranes prepared in different solvent media

    NASA Astrophysics Data System (ADS)

    Dresch, M. A.; Matos, B. R.; Fonseca, F. C.; Santiago, E. I.; Carmo, M.; Lanfredi, A. J. C.; Balog, S.

    2015-01-01

    Nafion-SiO2 hybrid electrolytes were synthesized by sol-gel reaction. The homogeneity, structural properties, and proton conductivity of the hybrid membranes were studied. Small-angle scattering analyses indicate that the Nafion structural matrix was preserved on the nanoscale, and the growth of silica particles occurred both in the ionic and nonionic domains of Nafion, which resulted in hybrids with characteristic morphologies. The water uptake and the weight fraction of the inorganic phase were found to be dependent on the alcohol solvent used for the sol-gel synthesis. Nafion-silica hybrids with homogeneous distribution of the inorganic phase were obtained using methanol as the solvent for the sol-gel reaction. The observed microstructural properties of the Nafion-silica membranes were related to enhanced proton conductivity at high temperatures and low relative humidity conditions.

  8. Large-scale atomistic and quantum-mechanical simulations of a Nafion membrane: Morphology, proton solvation and charge transport

    PubMed Central

    Komarov, Pavel V; Khokhlov, Alexei R

    2013-01-01

    Summary Atomistic and first-principles molecular dynamics simulations are employed to investigate the structure formation in a hydrated Nafion membrane and the solvation and transport of protons in the water channel of the membrane. For the water/Nafion systems containing more than 4 million atoms, it is found that the observed microphase-segregated morphology can be classified as bicontinuous: both majority (hydrophobic) and minority (hydrophilic) subphases are 3D continuous and organized in an irregular ordered pattern, which is largely similar to that known for a bicontinuous double-diamond structure. The characteristic size of the connected hydrophilic channels is about 25–50 Å, depending on the water content. A thermodynamic decomposition of the potential of mean force and the calculated spectral densities of the hindered translational motions of cations reveal that ion association observed with decreasing temperature is largely an entropic effect related to the loss of low-frequency modes. Based on the results from the atomistic simulation of the morphology of Nafion, we developed a realistic model of ion-conducting hydrophilic channel within the Nafion membrane and studied it with quantum molecular dynamics. The extensive 120 ps-long density functional theory (DFT)-based simulations of charge migration in the 1200-atom model of the nanochannel consisting of Nafion chains and water molecules allowed us to observe the bimodality of the van Hove autocorrelation function, which provides the direct evidence of the Grotthuss bond-exchange (hopping) mechanism as a significant contributor to the proton conductivity. PMID:24205452

  9. Characterization of the thermolysis products of Nafion membrane: A potential source of perfluorinated compounds in the environment

    NASA Astrophysics Data System (ADS)

    Feng, Mingbao; Qu, Ruijuan; Wei, Zhongbo; Wang, Liansheng; Sun, Ping; Wang, Zunyao

    2015-05-01

    The thermal decomposition of Nafion N117 membrane, a typical perfluorosulfonic acid membrane that is widely used in various chemical technologies, was investigated in this study. Structural identification of thermolysis products in water and methanol was performed using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). The fluoride release was studied using an ion-chromatography system, and the membrane thermal stability was characterized by thermogravimetric analysis. Notably, several types of perfluorinated compounds (PFCs) including perfluorocarboxylic acids were detected and identified. Based on these data, a thermolysis mechanism was proposed involving cleavage of both the polymer backbone and its side chains by attack of radical species. This is the first systematic report on the thermolysis products of Nafion by simulating its high-temperature operation and disposal process via incineration. The results of this study indicate that Nafion is a potential environmental source of PFCs, which have attracted growing interest and concern in recent years. Additionally, this study provides an analytical justification of the LC/ESI-MS/MS method for characterizing the degradation products of polymer electrolyte membranes. These identifications can substantially facilitate an understanding of their decomposition mechanisms and offer insight into the proper utilization and effective management on these membranes.

  10. Characterization of the thermolysis products of Nafion membrane: A potential source of perfluorinated compounds in the environment.

    PubMed

    Feng, Mingbao; Qu, Ruijuan; Wei, Zhongbo; Wang, Liansheng; Sun, Ping; Wang, Zunyao

    2015-01-01

    The thermal decomposition of Nafion N117 membrane, a typical perfluorosulfonic acid membrane that is widely used in various chemical technologies, was investigated in this study. Structural identification of thermolysis products in water and methanol was performed using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). The fluoride release was studied using an ion-chromatography system, and the membrane thermal stability was characterized by thermogravimetric analysis. Notably, several types of perfluorinated compounds (PFCs) including perfluorocarboxylic acids were detected and identified. Based on these data, a thermolysis mechanism was proposed involving cleavage of both the polymer backbone and its side chains by attack of radical species. This is the first systematic report on the thermolysis products of Nafion by simulating its high-temperature operation and disposal process via incineration. The results of this study indicate that Nafion is a potential environmental source of PFCs, which have attracted growing interest and concern in recent years. Additionally, this study provides an analytical justification of the LC/ESI-MS/MS method for characterizing the degradation products of polymer electrolyte membranes. These identifications can substantially facilitate an understanding of their decomposition mechanisms and offer insight into the proper utilization and effective management on these membranes.

  11. Hepatic Transcriptome Responses in Mice (Mus musculus) Exposed to the Nafion Membrane and Its Combustion Products

    PubMed Central

    Feng, Mingbao; Qu, Ruijuan; Habteselassie, Mussie; Wu, Jun; Yang, Shaogui; Sun, Ping; Huang, Qingguo; Wang, Zunyao

    2015-01-01

    Nafion 117 membrane (N117), an important polymer electrolyte membrane (PEM), has been widely used for numerous chemical technologies. Despite its increasing production and use, the toxicity data for N117 and its combustion products remain lacking. Toxicity studies are necessary to avoid problems related to waste disposal in landfills and incineration that may arise. In this study, we investigated the histopathological alterations, oxidative stress biomarker responses, and transcriptome profiles in the liver of male mice exposed to N117 and its combustion products for 24 days. An ion-chromatography system and liquid chromatography system coupled to a hybrid quadrupole time-of-flight mass spectrometry were used to analyze the chemical compositions of these combustion products. The transcriptomics analysis identified several significantly altered molecular pathways, including the metabolism of xenobiotics, carbohydrates and lipids; signal transduction; cellular processes; immune system; and signaling molecules and interaction. These studies provide preliminary data for the potential toxicity of N117 and its combustion products on living organisms and may fill the information gaps in the toxicity databases for the currently used PEMs. PMID:26057616

  12. Prediction of the effective conductivity of Nafion in the catalyst layer of a proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Hongsirikarn, Kitiya; Mo, Xunhua; Liu, Zhiming; Goodwin, James G.

    In a previous study, a simple acid catalyzed reaction (esterification) was found to predict excellently conductivity of a membrane contaminated with NH 4 + or Na +. Since measurement of the conductivity of Nafion in a catalyst layer is problematic, being able to predict this conductivity for various formulations and fuel cell conditions would be advantageous. In this study, the same methodology as before was used to examine the proton availabilities of supported Nafion (Nafion on carbon and on Pt/C), as exists in the catalyst layer used in a PEMFC, during impurity exposure (e.g., NH 3) as a means for prediction of its conductivity. It was found that the effect of NH 3 exposure on the proton composition (yH+) of supported Nafion was similar to that of N-211 under the same conditions. Determined values of yH+ were then used to estimate the effective conductivity of an ammonium-poisoned cathode layer using the correlation developed and the agglomerate model. The predicted conductivities were matched with the results available in the literature. This technique would be useful for the optimization of catalyst design and for fuel cell simulation, since it provides many benefits over conventional performance test procedures.

  13. Voltammetric Determination of Codeine on Glassy Carbon Electrode Modified with Nafion/MWCNTs

    PubMed Central

    Piech, Robert; Rumin, Martyna; Paczosa-Bator, Beata

    2015-01-01

    A glassy carbon electrode modified with a Nafion/MWCNTs composite is shown to enable the determination of codeine using differential pulse voltammetry in phosphate buffer of pH 3.0. At a preconcentration time of 15 s, the calibration graph is linear in the 0.5 µM (0.15 mg·L−1) to 15 µM (4.5 mg·L−1) concentration range with a correlation coefficient of 0.998. The detection limit at a preconcentration time of 120 s is as low as 4.5 μg·L−1. The repeatability of the method at a 0.6 μg·L−1 concentration level, expressed as the RSD, is 3.7% (for n = 5). The method was successfully applied and validated by analyzing codeine in drug, human plasma, and urine samples. PMID:25741451

  14. Magnetically modified polymer electrolyte fuel cells and low temperature effects on polymer electrolyte Nafion

    NASA Astrophysics Data System (ADS)

    Dunwoody, Drew Christian

    Polymer electrolyte fuel cell power systems are a promising technology which may provide clean and efficient electrical power in the future. Though the technology is promising, challenging technical issues must be overcome to make the technology a practical alternative to existing power sources. Fuel cell power systems are often touted as possible replacements for combustion engines. Materials used in these power systems must be able to withstand a wide range of environmental conditions including both extremes of heat and cold. An evaluation of fuel cell materials under these extreme conditions is warranted. Also, the expense of a fuel cell power system with comparable power output to more traditional power sources such as batteries and combustion engines is on the order of seven fold. Reductions in the costs of materials and methods to increase the overall efficiency of the power systems need to be identified. Here, the electrochemical behavior of the polymer electrolyte Nafion is investigated as a function of temperature from room temperature to significantly below the freezing point of water. The type of intercalant and electrolyte solution dictates the temperature at which electrochemical properties change and also impacts polymer integrity. Magnetic modification of electrode surfaces has been shown to enhance electrochemical flux up to 3600% over that of nonmagnetic electrodes. Here, polymer electrolyte fuel cells are tested for enhanced performance over nonmagnetic cells. Under certain conditions, an increase in performance is observed for magnetic modification. Descriptions of the methods used to construct magnetically modified fuel cells and special considerations to heed when operating these cells are included.

  15. Preparation and characterization of water-soluble carbon nanotube reinforced Nafion membranes and so-based ionic polymer metal composite actuators

    NASA Astrophysics Data System (ADS)

    Ru, Jie; Wang, Yanjie; Chang, Longfei; Chen, Hualing; Li, Dichen

    2016-09-01

    In this paper, we developed a new kind of ionic polymer metal composite (IPMC) actuator by doping water-soluble sulfonated multi-walled carbon nanotube (sMWCNT) into Nafion matrix to overcome some major drawbacks of traditional IPMCs, such as relatively low bending deformation and carring capacity at low driving voltages. Firstly, sMWCNT was synthesized via diazotization coupling reaction, and then doped into Nafion matrix by casting method. Subsequently, the electrochemical and electromechanical properties of sMWCNT-reinforced Nafion membranes and the corresponding IPMCs were investigated. Finally, the effects of sMWCNT on the performances of IPMCs were evaluated and analyzed systematacially. The results showed that sMWCNT was homogeneously dispersed in Nafion matrix without any entangled structure or obvious agglomeration. The main factors for superior actuation performances, like water-uptake ratio, proton conductivity and elastic modulus, increased significantly. Compared to the pure Nafion IPMC and MWCNT/Nafion IPMC, much superior electrochemical and electromechanical performances were achieved in the sMWCNT/Nafion IPMC, which were attributed to the numerous insertion sites, high surface conductivity and excellent mechanical strength as well as the homogeneous dispersity of the incorporated sMWCNT. Herein, a trace amount of sMWCNT can improve the performances of IPMCs significantly for realistic applications.

  16. Wettability of Nafion and Nafion/Vulcan carbon composite films.

    PubMed

    Li, Xiaoan; Feng, Fangxia; Zhang, Ke; Ye, Siyu; Kwok, Daniel Y; Birss, Viola

    2012-04-24

    The wettability of the Pt/carbon/Nafion catalyst layer in proton exchange membrane fuel cells is critical to their performance and durability, especially the cathode, as water is needed for the transport of protons to the active sites and is also involved in deleterious Pt nanoparticle dissolution and carbon corrosion. Therefore, the focus of this work has been on the first-time use of the water droplet impacting method to determine the wettability of 100% Nafion films, as a benchmark, and then of Vulcan carbon (VC)/Nafion composite films, both deposited by spin-coating in the Pt-free state. Pure Nafion films, shown by SEM analysis to have a nanochanneled structure, are initially hydrophobic but become hydrophilic as the water droplet spreads, likely due to reorientation of the sulfonic acid groups toward water. The wettability of VC/Nafion composite films depends significantly on the VC/Nafion mass ratios, even though Nafion is believed to be preferentially oriented (sulfonate groups toward VC) in all cases. At low VC contents, a significant water droplet contact angle hysteresis is seen, similar to pure Nafion films, while at higher VC contents (>30%), the films become hydrophobic, also exhibiting superhydrophobicity, with surface roughness playing a significant role. At >80% VC, the surfaces become wettable again as there is insufficient Nafion loading present to fully cover the carbon surface, allowing the calculation of the Nafion:carbon ratio required for a full coverage of carbon by Nafion.

  17. Atomistic simulation of water percolation and proton hopping in Nafion fuel cell membrane.

    PubMed

    Devanathan, Ram; Venkatnathan, Arun; Rousseau, Roger; Dupuis, Michel; Frigato, Tomaso; Gu, Wei; Helms, Volkhard

    2010-11-01

    We have performed a detailed analysis of water clustering and percolation in hydrated Nafion configurations generated by classical molecular dynamics simulations. Our results show that at low hydration levels H(2)O molecules are isolated and a continuous hydrogen-bonded network forms as the hydration level is increased. Our quantitative analysis has established a hydration level (λ) between 5 and 6 H(2)O/SO(3)(-) as the percolation threshold of Nafion. We have also examined the effect of such a network on proton transport by studying the structural diffusion of protons using the quantum hopping molecular dynamics method. The mean residence time of the proton on a water molecule decreases by 2 orders of magnitude when the λ value is increased from 5 to 15. The proton diffusion coefficient in Nafion at a λ value of 15 is about 1.1 × 10(-5) cm(2)/s in agreement with experiment. The results provide quantitative atomic-level evidence of water network percolation in Nafion and its effect on proton conductivity.

  18. Atomistic Simulation of Water Percolation and Proton Hopping in Nafion Fuel Cell Membrane

    SciTech Connect

    Devanathan, Ramaswami; Venkatnathan, Arun; Rousseau, Roger J.; Dupuis, Michel; Frigato, Tomaso; Gu, Wei; Helms, Volkhard H.

    2010-11-04

    We have performed a detailed analysis of water clustering and percolation in hydrated Nafion configurations generated by classical molecular dynamics simulations. Our results show that at low hydration levels H2O molecules are isolated and a continuous hydrogen-bonded network forms as the hydration level is increased. Our quantitative analysis has established a hydration level (λ) between 5 and 6 H2O/SO3- as the percolation threshold of Nafion. We have also examined the effect of such a network on proton transport by studying the structural diffusion of protons using the quantum hopping molecular dynamics method. The mean residence time of the proton on a water molecule decreases by two orders of magnitude when the λ value is increased from 5 to 15. The proton diffusion coefficient in Nafion at a λ value of 15 is about 1.1x10-5 cm2/s in agreement with experiment. The results provide quantitative atomic-level evidence of water network percolation in Nafion and its effect on proton conductivity.

  19. Esterification as a diagnostic tool to predict proton conductivity affected by impurities on Nafion components for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Hongsirikarn, Kitiya; Mo, Xunhua; Goodwin, James G.

    Quantitative data of the effect of contaminants on individual components of a PEMFC is limited and difficult to acquire, especially for the ionomer in the catalyst layer. In this paper, we propose the use of an acid-catalysed reaction (esterification) as a method to quantitatively investigate the effect of contaminants on proton availability and conductivity of Nafion components, since proton sites in Nafion are also active as Brønsted acid sites for catalysis. It was found that at typical fuel cell conditions, ammonia adsorption decreased both conductivity and esterification activity of Nafion in a uniform manner. Because of the linear relationship between the number of proton/acid sites and both the conductivity and the esterification activity, a correlation between the two could be developed taking into account differences in the effect of humidity on the conductivity/activity of the poisoned Nafion. The methodology and correlation developed were also shown to predict accurately the effect of another impurity species (Na +) on Nafion conductivity. The results demonstrate the application of esterification as a means to quantify the number of proton sites poisoned by adsorbing impurities, permitting the prediction of Nafion conductivity. This method would be applicable to both the membrane and ionomer in the catalyst layer.

  20. Photocatalytic Water Oxidation Using Manganese Compounds Immobilized in Nafion Polymer Membranes

    PubMed Central

    Young, Karin J.; Gao, Yunlong; Brudvig, Gary W.

    2011-01-01

    Robust water oxidation catalysts using earth abundant metals are required as part of an overall scheme to convert sunlight into fuels. Here, we report the immobilization of [Mn4IVO5(terpy)4(H2O)2](ClO4)6 (terpy = 2,2′;6′,2″-terpyridine), [Mn4O6(tacn)4](ClO4)4 (tacn = 1,4,7-triazacyclononane), and manganese dioxide nanoparticles in Nafion on fluorine-doped tin oxide conducting glass electrodes. The electrodes are illuminated with white light in the presence of an applied potential and the resulting photocurrent is assigned to the oxidation of solvent water. Photodecomposition of the tetrameric complexes results in a material that is more active for light-driven electrooxidation of water. The reactivity, wavelength dependence, and stability of the compounds in Nafion under illumination are discussed. PMID:22140273

  1. Effect of SiO2 on relaxation phenomena and mechanism of ion conductivity of [Nafion/(SiO2)x] composite membranes.

    PubMed

    Di Noto, Vito; Gliubizzi, Rocco; Negro, Enrico; Pace, Giuseppe

    2006-12-14

    This report describes a study of the effect of SiO2 nanopowders on the mechanism of ionic motion and interactions taking place in hybrid inorganic-organic membranes based on Nafion. Five nanocomposite membranes of the formula [Nafion/(SiO2)x] with SiO2 ranging from 0 to 15 wt % were prepared by a solvent casting procedure. TG measurements demonstrated that the membranes are thermally stable up to 170 degrees C but with the loss water it changes the cluster environments and changes the conductivity properties. MDSC investigations in the 90-300 degrees C temperature range revealed the presence of three intense overlapping endothermal peaks indicated as I, II, and III. Peak I measures the order-disorder molecular rearrangement in hydrophilic polar clusters, II corresponds to the endothermic decomposition of -SO3 groups, and III describes the melting process in microcrystalline regions of hydrophobic fluorocarbon domains of the Nafion moiety. ESEM with EDAX measurements revealed that the membranes are homogeneous materials with smooth surfaces. DMA studies allowed us to measure two relaxation modes. The mechanical relaxation detected at ca. 100 degrees C is attributed to the motion of cluster aggregates of side chains and is diagnostic for R-SO3H...SiO2 nanocluster interactions. DMA disclosed that at SiO2/-SO3H (psi) molar ratios lower than 1.9, the oxoclusters act to restrict chain mobility of hydrophobic domains of Nafion and the dynamics inside polar cages of [Nafion/(SiO2)x] systems; at psi higher than 1.9, the oxoclusters reduce the cohesiveness of hydrophilic polar domains owing to a reduction in the density of cross-links. FT-IR and FT-Raman studies of the [Nafion/(SiO2)x] membranes indicated that the fluorocarbon chains of Nafion hydrophobic domains assume the typical helical conformation structure with a D(14pi/15) symmetry. These analyses revealed four different species of water domains embedded inside polar cages and their interconnecting channels: (a) bulk

  2. Electrochemical Detection of p-Aminophenol by Flexible Devices Based on Multi-Wall Carbon Nanotubes Dispersed in Electrochemically Modified Nafion

    PubMed Central

    Scandurra, Graziella; Antonella, Arena; Ciofi, Carmine; Saitta, Gaetano; Lanza, Maurizio

    2014-01-01

    A conducting composite prepared by dispersing multi-walled carbon nanotubes (MWCNTs) into a host matrix consisting of Nafion, electrochemically doped with copper, has been prepared, characterized and used to modify one of the gold electrodes of simply designed electrochemical cells having copier grade transparency sheets as substrates. Electrical measurements performed in deionized water show that the Au/Nafion/Au-MWCNTs–Nafion:Cu cells can be successfully used in order to detect the presence of p-aminophenol (PAP) in water, without the need for any supporting electrolyte. The intensity of the redox peaks arising when PAP is added to deionized water is found to be linearly related to the analyte in the range from 0.2 to 1.6 μM, with a detection limit of 90 nM and a sensitivity of 7 μA·(μM−1)·cm−2. PMID:24854357

  3. Optimization of a Nafion Membrane-Based System for Removal of Chloride and Fluoride from Lunar Regolith-Derived Water

    NASA Technical Reports Server (NTRS)

    Anthony, Stephen M.; Santiago-Maldonado, Edgardo; Captain, James G.; Pawate, Ashtamurthy S.; Kenis, Paul J. A.

    2012-01-01

    A long-term human presence in space will require self-sustaining systems capable of producing oxygen and potable water from extraterrestrial sources. Oxygen can be extracted from lunar regolith, and water contaminated with hydrochloric and hydrofluoric acids is produced as an intermediate in this process. We investigated the ability of Nafion proton exchange membranes to remove hydrochloric and hydrofluoric acids from water. The effect of membrane thickness, product stream flow rate, and acid solution temperature and concentration on water flux, acid rejection, and water and acid activity were studied. The conditions that maximized water transport and acid rejection while minimizing resource usage were determined by calculating a figure of merit. Water permeation is highest at high solution temperature and product stream flow rate across thin membranes, while chloride and fluoride permeation are lowest at low acid solution temperature and concentration across thin membranes. The figure of merit varies depending on the starting acid concentration; at low concentration, the figure of merit is highest across a thin membrane, while at high concentration, the figure of merit is highest at low solution temperature. In all cases, the figure of merit increases with increasing product stream flow rate.

  4. The Application of Nafion Metal Catalyst Free Carbon Nanotube Modified Gold Electrode: Voltammetric Zinc Detection in Serum

    PubMed Central

    Yue, Wei; Bange, Adam; Riehl, Bill L.; Johnson, Jay M.; Papautsky, Ian; Heineman, William R.

    2013-01-01

    Metal catalyst free carbon nanotube (MCFCNT) whiskers were first used as an electrode modification material on a gold electrode surface for zinc voltammetric measurements. A composite film of Nafion and MCFCNT whiskers was applied to a gold electrode surface to form a mechanically stable sensor. The sensor was then used for zinc detection in both acetate buffer solution and extracted bovine serum solution. A limit of detection of 53 nM was achieved for a 120 s deposition time. The zinc in bovine serum was extracted via a double extraction procedure using dithizone in chloroform as a zinc chelating ligand. The modified electrode was found to be both reliable and sensitive for zinc measurements in both matrices. PMID:24436574

  5. Molecular modeling of the morphology and transport properties of two direct methanol fuel cell membranes: phenylated sulfonated poly(ether ether ketone ketone) versus Nafion

    SciTech Connect

    Devanathan, Ramaswami; Idupulapati, Nagesh B.; Dupuis, Michel

    2012-08-14

    We have used molecular dynamics simulations to examine membrane morphology and the transport of water, methanol and hydronium in phenylated sulfonated poly ether ether ketone ketone (Ph-SPEEKK) and Nafion membranes at 360 K for a range of hydration levels. At comparable hydration levels, the pore diameter is smaller, the sulfonate groups are more closely packed, the hydronium ions are more strongly bound to sulfonate groups, and the diffusion of water and hydronium is slower in Ph-SPEEKK relative to the corresponding properties in Nafion. The aromatic carbon backbone of Ph-SPEEKK is less hydrophobic than the fluorocarbon backbone of Nafion. Water network percolation occurs at a hydration level ({lambda}) of {approx}8 H{sub 2}O/SO{sub 3}{sup -}. At {lambda} = 20, water, methanol and hydronium diffusion coefficients were 1.4 x 10{sup -5}, 0.6 x 10{sup -5} and 0.2 x 10{sup -5} cm{sup 2}/s, respectively. The pore network in Ph-SPEEKK evolves dynamically and develops wide pores for {lambda} > 20, which leads to a jump in methanol crossover and ion transport. This study demonstrates the potential of aromatic membranes as low-cost challengers to Nafion for direct methanol fuel cell applications and the need to develop innovative strategies to combat methanol crossover at high hydration levels.

  6. Low-temperature synthesis of nano-TiO2 anatase on nafion membrane for using on DMFC

    NASA Astrophysics Data System (ADS)

    Tuan, Nguyen Manh; Thanh Nha, Ngo; Hoang Tuyen, Nguyen

    2009-09-01

    Low-temperature synthesis of 60-70°C of anatase nanocrystalline titanium dioxide TiO2 using sol-gel technique on Nafion membrane is investigated and characterized. Titan tetraisopropoxide (TTIP) is used as precursor and ethanol as the solvent. The best precursor to solvent weight ratio has been used for the synthesis of nano-TiO2 particles. The X-ray diffractograms and TEM images show the formation of anatase structure of nanocrystalline TiO2 at low temperatures as shown with average particle size below 12 nm. The films deposited by spin coating technique using these nanoparticles show the crystalline and porous nature of the films. The nano-TiO2 film as shown can be used to reduce the cross-over permeation of methanol through the PEM and increase electric power of the DMFC.

  7. ATR-FTIR study of water in Nafion membrane combined with proton conductivity measurements during hydration/dehydration cycle.

    PubMed

    Kunimatsu, Keiji; Bae, Byungchan; Miyatake, Kenji; Uchida, Hiroyuki; Watanabe, Masahiro

    2011-04-21

    We have conducted combined time-resolved attenuated total reflection Fourier transform infrared (ATR-FTIR) and proton conductivity measurements of Nafion NRE211 membrane during hydration/dehydration cycles at room temperature. Conductivity change was interpreted in terms of different states of water in the membrane based on its δ(HOH) vibrational spectra. It was found that hydration of a dry membrane leads first to complete dissociation of the sulfonic acid groups to liberate hydrated protons, which are isolated from each other and have δ(HOH) vibrational frequency around 1740 cm(-1). The initial hydration is not accompanied by a significant increase of the proton conductivity. Further hydration gives rise to a rapid increase of the conductivity in proportion to intensity of a new δ(HOH) band around 1630 cm(-1). This was interpreted in terms of formation of channels of weakly hydrogen-bonded water to combine the isolated hydrophilic domains containing hydrated protons and hydrated sulfonate ions produced during the initial stage of hydration. Upon dehydration, proton conductivity drops first very rapidly due to loss of the weakly hydrogen bonded water from the channels to leave hydrophilic domains isolated in the membrane. Dehydration of the protons proceeds very slowly after significant loss of the proton conductivity.

  8. A novel tridentate bis(phosphinic acid)phosphine oxide based europium(III)-selective Nafion membrane luminescent sensor.

    PubMed

    Sainz-Gonzalo, F J; Popovici, C; Casimiro, M; Raya-Barón, A; López-Ortiz, F; Fernández, I; Fernández-Sánchez, J F; Fernández-Gutiérrez, A

    2013-10-21

    A new europium(III) membrane luminescent sensor based on a new tridentate bis(phosphinic acid)phosphine oxide (3) system has been developed. The synthesis of this new ligand is described and its full characterization by NMR, IR and elemental analyses is provided. The luminescent complex formed between europium(III) chloride and ligand 3 was evaluated in solution, observing that its spectroscopic and chemical characteristics are excellent for measuring in polymer inclusion membranes. Included in a Nafion membrane, all the parameters (ligand and ionic additives) that can affect the sensitivity and selectivity of the sensing membrane as well as the instrumental conditions were carefully optimized. The best luminescence signal (λexc = 229.06 nm and λem = 616.02 nm) was exhibited by the sensing film having a Nafion : ligand composition of 262.3 : 0.6 mg mL(-1). The membrane sensor showed a short response time (t95 = 5.0 ± 0.2 min) and an optimum working pH of 5.0 (25 mM acetate buffer solution). The membrane sensor manifested a good selectivity toward europium(III) ions with respect to other trivalent metals (iron, chromium and aluminium) and lanthanide(III) ions (lanthanum, samarium, terbium and ytterbium), although a small positive interference of terbium(III) ions was observed. It provided a linear range from 1.9 × 10(-8) to 5.0 × 10(-6) M with a very low detection limit (5.8 × 10(-9) M) and sensitivity (8.57 × 10(-7) a.u. per M). The applicability of this sensing film has been demonstrated by analyzing different kinds of spiked water samples obtaining recovery percentages of 95-97%.

  9. Nafion-modified MoOx as effective room-temperature hole injection layer for stable, high-performance inverted organic solar cells.

    PubMed

    Qiu, Weiming; Müller, Robert; Voroshazi, Eszter; Conings, Bert; Carleer, Robert; Boyen, Hans-Gerd; Turbiez, Mathieu; Froyen, Ludo; Heremans, Paul; Hadipour, Afshin

    2015-02-18

    We present a hole injection layer processed from solution at room temperature for inverted organic solar cells. Bis(2,4-pentanedionato) molybdenum(VI) dioxide (MoO2(acac)2) is used as the precursor for MoOx. Small amounts of Nafion in the precursor solution allow it to form continuous films with good wetting onto the active layers. The hydrolysis of MoO2(acac)2 and the effects of adding Nafion to the precursor solution are studied by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The devices with solution-processed MoOx including Nafion exhibited comparable performance to the reference devices based on the commonly used hole injection layers such as poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) or evaporated MoO3. Inverted poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester devices with Nafion-modified MoOx maintain 80% of their initial power conversion efficiency upon exposure to ambient air for ∼5000 h, outperforming devices with PEDOT:PSS or with evaporated MoO3.

  10. Fast Water Diffusion and Long-Term Polymer Reorganization during Nafion Membrane Hydration Evidenced by Time-Resolved Small-Angle Neutron Scattering.

    PubMed

    Fumagalli, M; Lyonnard, S; Prajapati, G; Berrod, Q; Porcar, L; Guillermo, A; Gebel, G

    2015-06-11

    We report a small-angle neutron scattering study of liquid water sorption in Nafion membranes. The swelling of hydrophilic domains was measured on the nanoscale by combining in situ time-resolved and long-term static experiments, yielding kinetic curves recorded over an unprecedented time scale, from hundreds of milliseconds to several years. At low water content, typically below 5 water molecules per ionic group, a limited subdiffusive regime was observed and ascribed to nanoconfinement and local interactions between charged species and water molecules. Further ultrafast and thermally activated swelling due to massive liquid water sorption was observed and analyzed by using Fick's equation. The extracted mutual water diffusion coefficients are in good agreement with pulsed field gradient NMR self-diffusion coefficient values, evidencing a water diffusion-driven process due to concentration gradients within the Nafion membrane. Finally, after completion of the ultrafast regime, the kinetic swelling curves exhibit a remarkable long-term behavior scaling as the logarithm of time, showing that the polymer membrane can continuously accommodate additional water molecules upon hydration stress. The present nanoscale kinetics results provide insights into the vapor-versus-liquid sorption mechanisms, the nanostructure of Nafion, and the role of polymer reorganization modes, highlighting that the membrane can never reach a steady state.

  11. Investigations on transfer of water and vanadium ions across Nafion membrane in an operating vanadium redox flow battery

    NASA Astrophysics Data System (ADS)

    Sun, Chenxi; Chen, Jian; Zhang, Huamin; Han, Xi; Luo, Qingtao

    Diffusion coefficients of the vanadium ions across Nafion 115 (Dupont) in a vanadium redox flow battery (VRFB) are measured and found to be in the order of V 2+ > VO 2+ > VO 2 + > V 3+. It is found that both in self-discharge process and charge-discharge cycles, the concentration difference of vanadium ions between the positive electrolyte (+ve) and negative electrolyte (-ve) is the main reason causing the transfer of vanadium ions across the membrane. In self-discharge process, the transfer of water includes the transfer of vanadium ions with the bound water and the corresponding transfer of protons with the dragged water to balance the charges, and the transfer of water driven by osmosis. In this case, about 75% of the net transfer of water is caused by osmosis. In charge-discharge cycles, except those as mentioned in the case of self-discharge, the transfer of protons with the dragged water across the membrane during the electrode reaction for the formation of internal electric circuit plays the key role in the water transfer. But in the long-term cycles of charge-discharge, the net transfer of water towards +ve is caused by the transfer of vanadium ions with the bound water and the transfer of water driven by osmosis.

  12. Design of a multiwalled carbon nanotube-Nafion-cysteamine modified tyrosinase biosensor and its adaptation of dopamine determination.

    PubMed

    Canbay, Erhan; Akyilmaz, Erol

    2014-01-01

    In this work, a multiwalled carbon nanotube (MWCNT)-Nafion-cysteamine (CA) modified tyrosinase biosensor brings a new and original perspective to biosensor technology intended for the development of dopamine determination. Dopamine measurements were done at 0.2V with the amperometric method by the developed biosensor system. In addition, in this study dopamine determination was carried out by using the differential pulse voltammetry method between potentials of 0.4 and -0.15 V. In the optimization studies of the biosensor, some parameters such as optimal pH, optimal temperature, optimal enzyme amount, and effect of MWCNT concentration were investigated. Afterward, in the characterization studies, some parameters such as linearity and reproducibility were determined. In the reproducibility experiment, an average value of 1.026 μM, a standard deviation of ±0.03975, and a coefficient of variation of 3.8% were determined for a 1-μM dopamine concentration (n=15). Determination of dopamine was carried out in drug samples by the developed biosensor.

  13. Electrochemical detection of DNA damage induced by acrylamide and its metabolite at the graphene-ionic liquid-Nafion modified pyrolytic graphite electrode.

    PubMed

    Qiu, Yanyan; Qu, Xiangjin; Dong, Jing; Ai, Shiyun; Han, Ruixia

    2011-06-15

    A new electrochemical biosensor for directly detecting DNA damage induced by acrylamide (AA) and its metabolite was presented in this work. The graphene-ionic liquid-Nafion modified pyrolytic graphite electrode (PGE) was prepared, and then horseradish peroxidase (HRP) and natural double-stranded DNA were alternately assembled on the modified electrode by the layer-by-layer method. The PGE/graphene-ionic liquid-Nafion and the construction of the (HRP/DNA)(n) film were characterized by electrochemical impedance spectroscopy. With the guanine signal in DNA as an indicator, the damage of DNA was detected by differential pulse voltammetry after PGE/graphene-ionic liquid-Nafion/(HRP/DNA)(n) was incubated in AA solution or AA+H(2)O(2) solution at 37°C. This method provides a new model to mimic and directly detect DNA damage induced by chemical pollutants and their metabolites in vitro. The results indicated that, in the presence of H(2)O(2), HRP was activated and catalyzed the transformation of AA to glycidamide, which could form DNA adducts and induce more serious damage of DNA than AA. In order to further verify these results, UV-vis spectrophotometry was also used to investigate DNA damage induced by AA and its metabolites in solution and the similar results were obtained.

  14. Genistein Modified Polymer Blends for Hemodialysis Membranes

    NASA Astrophysics Data System (ADS)

    Chang, Teng; Kyu, Thein; Define, Linda; Alexander, Thomas

    2012-02-01

    A soybean-derived phytochemical called genistein was used as a modifying agent to polyether sulfone/polyvinyl pyrrolidone (PES/PVP) blends to produce multi-functional hemodialysis membranes. With the aid of phase diagrams of PES/PVP/genistein blends, asymmetric porous membranes were fabricated by coagulating in non-solvent. Both unmodified and genistein modified PES/PVP membranes were shown to be non-cytotoxic to the blood cells. Unmodified PES/PVP membranes were found to reduce reactive oxygen species (ROS) levels, whereas the genistein modified membranes exhibited suppression for ˜60% of the ROS levels. Also, the genistein modified membranes revealed significant suppression of pro-inflammatory cytokines: IL-1β, IL-6, and TNF-α. Moreover, addition of PVP to PES showed the reduced trend of platelet adhesion and then leveled off. However, the modified membranes exhibited suppression of platelet adhesion at low genistein loading, but beyond 15 wt%, the platelet adhesion level rised up.

  15. Gold-nanoparticle-embedded nafion composite modified on glassy carbon electrode for highly selective detection of arsenic(III).

    PubMed

    Huang, Jing-Fang; Chen, Hsiao-Hua

    2013-11-15

    A Cu(I)-ion-mediating Au reduction is proposed for preparing an Au-nanoparticle-embedded nafion (NF(Aunano)) composite. The NF(Aunano) composite consisted of highly dense, well-dispersed, and protecting-agent-free Au nanocrystals with a narrow particle size (4.8±0.1 nm) distribution. The NF(Aunano) composite was characterized as a function of composition and particle size distribution using powder X-ray diffraction, transmission electron microscopy, and electrochemical measurements. It was demonstrated that the NF(Aunano) composite provided high activity in the redox behavior of As(III), and was used as a potential sensing material with low Au loading for As(III) detection. An NF(Aunano)-composite-modified electrode is easy to prepare and regenerate. The dynamic range of a calibration curve from 0.1 to 12.0 μg L(-1) (from 1.3 to 160 nM), y=23.98x (in μA μM(-1))+0.42 (R(2)=0.999), showed linear behavior with a slope of 23.98 μA μM(-1). The detection limit is as low as 0.047 μg L(-1) (0.63 nM). The chelating agent ethylenediaminetetraacetate (EDTA) can selectively chelate with interfering metal ions, forming bulky complexes or bulky anions that are excluded from the NF film. The presence of EDTA effectively eliminated interference from several metal ions, particularly Cu(II) and Hg(II), which are generally considered to be major interferents in the electroanalysis of As(III). This method was applicable to As(III) analysis in three real water samples, namely groundwater, lake, and drinking waters.

  16. Sensitive HIV-1 detection in a homogeneous solution based on an electrochemical molecular beacon coupled with a nafion-graphene composite film modified screen-printed carbon electrode.

    PubMed

    Li, Bo; Li, Zhengliang; Situ, Bo; Dai, Zong; Liu, Qinlan; Wang, Qian; Gu, Dayong; Zheng, Lei

    2014-02-15

    A novel electrochemical sensing assay for sensitive determination of HIV-1 in a homogeneous solution has been developed using an electrochemical molecular beacon combined with a nafion-graphene composite film modified screen-printed carbon electrode (nafion-graphene/SPCE). The electrochemical molecular beacon (CAs-MB), comprising a special recognition sequence for the conserved region of the HIV-1 gag gene and a pair of carminic acid molecules as a marker, can indicate the presence of the HIV-1 target by its on/off electrochemical signal behavior. It is suitable for direct, electrochemical determination of HIV-1, thereby simplifying the detection procedure and improving the signal-to-noise (S/N) ratio. To further improve the sensitivity, the nafion-graphene/SPCE was used to monitor changes in the CAs-MB, which has notable advantages, such as being ultrasensitive, inexpensive, and disposable. Under optimized conditions, the peak currents showed a linear relationship with the logarithm of target oligonucleotide concentrations ranging from 40 nM to 2.56 μM, with a detection limit of 5 nM (S/N=3). This sensing assay also displays a good stability, with a recovery of 88-106.8% and RSD<7% (n=5) in real serum samples. This work may lead to the development of an effective method for early point-of-care diagnosis of HIV-1 infection. PMID:24099877

  17. Sensitive HIV-1 detection in a homogeneous solution based on an electrochemical molecular beacon coupled with a nafion-graphene composite film modified screen-printed carbon electrode.

    PubMed

    Li, Bo; Li, Zhengliang; Situ, Bo; Dai, Zong; Liu, Qinlan; Wang, Qian; Gu, Dayong; Zheng, Lei

    2014-02-15

    A novel electrochemical sensing assay for sensitive determination of HIV-1 in a homogeneous solution has been developed using an electrochemical molecular beacon combined with a nafion-graphene composite film modified screen-printed carbon electrode (nafion-graphene/SPCE). The electrochemical molecular beacon (CAs-MB), comprising a special recognition sequence for the conserved region of the HIV-1 gag gene and a pair of carminic acid molecules as a marker, can indicate the presence of the HIV-1 target by its on/off electrochemical signal behavior. It is suitable for direct, electrochemical determination of HIV-1, thereby simplifying the detection procedure and improving the signal-to-noise (S/N) ratio. To further improve the sensitivity, the nafion-graphene/SPCE was used to monitor changes in the CAs-MB, which has notable advantages, such as being ultrasensitive, inexpensive, and disposable. Under optimized conditions, the peak currents showed a linear relationship with the logarithm of target oligonucleotide concentrations ranging from 40 nM to 2.56 μM, with a detection limit of 5 nM (S/N=3). This sensing assay also displays a good stability, with a recovery of 88-106.8% and RSD<7% (n=5) in real serum samples. This work may lead to the development of an effective method for early point-of-care diagnosis of HIV-1 infection.

  18. Characterization of perfluorinated cation-exchange membranes MF-4SC surface modified with halloysite nanotubes

    NASA Astrophysics Data System (ADS)

    Filippov, A.; Afonin, D.; Kononenko, N.; Shkirskaya, S.

    2015-10-01

    The electrical conductivity and diffusion permeability through perfluorinated cation-exchange membranes MF-4SC (Russian analog of the Nafion-type membrane), whose surface is modified by nanotubes of halloysite using short exposures of low temperature microwave plasma, are theoretically investigated using the Nernst-Planck approach. The method of quantitative evaluation of physicochemical parameters (individual and averaged diffusion coefficients and averaged distribution coefficients of ion pairs in the membrane) of the systems `electrolyte solution - bi-layer ion-exchange membrane - water/electrolyte solution', which was proposed by us earlier, is further developed. The aforementioned parameters of modified MF-4SC/halloysite membranes were found using the least squares method. For this purpose we used electrical conductivity as well as diffusion permeability data experimentally obtained for NaCl and HCl solutions of different concentration. A new model of bi-layer membrane system can be used for refining the calculated results by taking into account the difference between co- and counter-ion diffusivities inside the membrane layers. We showed that grafting the layer of halloysite nanotubes onto the membrane surface noticeably affects the exchange capacity as well as the structural and transport characteristics of the original perfluorinated membrane. In particular, such a membrane may show weak asymmetry of diffusion permeability when its position inside a measuring cell is changed. Hybrid MF-4SC/halloysite membranes can thus be productively used in fuel cells and catalysis.

  19. Induced-charge electrokinetics, bipolar current, and concentration polarization in a microchannel-Nafion-membrane system

    NASA Astrophysics Data System (ADS)

    Park, Sinwook; Yossifon, Gilad

    2016-06-01

    The presence of a floating electrode array located within the depletion layer formed due to concentration polarization across a microchannel-membrane interface device may produce not only induced-charge electro-osmosis (ICEO) but also bipolar current resulting from the induced Faradaic reaction. It has been shown that there exists an optimal thickness of a thin dielectric coating that is sufficient to suppress bipolar currents but still enables ICEO vortices that stir the depletion layer, thereby affecting the system's current-voltage response. In addition, the use of alternating-current electro-osmosis by activating electrodes results in further enhancement of the fluid stirring and opens new routes for on-demand spatiotemporal control of the depletion layer length.

  20. Induced-charge electrokinetics, bipolar current, and concentration polarization in a microchannel-Nafion-membrane system.

    PubMed

    Park, Sinwook; Yossifon, Gilad

    2016-06-01

    The presence of a floating electrode array located within the depletion layer formed due to concentration polarization across a microchannel-membrane interface device may produce not only induced-charge electro-osmosis (ICEO) but also bipolar current resulting from the induced Faradaic reaction. It has been shown that there exists an optimal thickness of a thin dielectric coating that is sufficient to suppress bipolar currents but still enables ICEO vortices that stir the depletion layer, thereby affecting the system's current-voltage response. In addition, the use of alternating-current electro-osmosis by activating electrodes results in further enhancement of the fluid stirring and opens new routes for on-demand spatiotemporal control of the depletion layer length. PMID:27415327

  1. Voltammetric analysis with the use of a novel electro-polymerised graphene-nafion film modified glassy carbon electrode: simultaneous analysis of noxious nitroaniline isomers.

    PubMed

    Lin, Xiaoyun; Ni, Yongnian; Kokot, Serge

    2012-12-01

    A new modified electrode was constructed by the electro-polymerization of 7-[(2,4-dihydroxy-5-carboxybenzene)azo]-8-hydroxyquinoline-5-sulfonic acid (DHCBAQS) at a graphene-nafion modified glassy carbon electrode (GCE). The construction process was performed stepwise and at each step the electrochemical characteristics were investigated particularly with respect to the oxidation of the three noxious analytes, 2-nitroaniline (2-NA), 3-nitroaniline (3-NA), 4-nitroaniline (4-NA); the electrode treated with the fluorescence reagent DHCBAQS performed best. At this electrode, the differential pulse voltammetry peak currents of the three isomers increased linearly with their concentrations in the range of 0.05-0.60 μg mL(-1), respectively, and their corresponding limits of detection (LODs) were all about 0.022 μg mL(-1). Furthermore, satisfactory results were obtained when this electrode was applied for the simultaneous quantitative analysis of the nitroaniline isomer mixtures by Principal component regression (PCR) and Partial least squares (PLS) as calibration methods (relative prediction error (PRE(T)) - 9.04% and 9.23%) and average recoveries (101.0% and 101.7%), respectively. The above novel poly-DHCBAQS/graphene-nafion/GCE was successfully employed for the simultaneous analysis of the three noxious nitroaniline isomers in water and sewage samples.

  2. A colourimetric sensor for the simultaneous determination of oxidative status and antioxidant activity on the same membrane: N,N-dimethyl-p-phenylene diamine (DMPD) on Nafion.

    PubMed

    Çekiç, Sema Demirci; Avan, Asli Neslihan; Uzunboy, Seda; Apak, Reşat

    2015-03-20

    A colourimetric sensor capable of simultaneously measuring oxidative status (OS) in terms of the hazard produced by reactive oxygen species (ROS) and antioxidant activity (AOA) in regard to ROS-scavenging ability of antioxidant compounds was developed. The coloured cationic semi-quinone derivatives, caused by ROS oxidative degradation of N,N-dimethyl-p-phenylene diamine hydrochloride (DMPD) in pH 5.7 acetate-buffered medium, were formed in solution and immobilized on a perfluorosulfonate-based Nafion membrane. ROS, namely hydroxyl (·OH) and superoxide (O2(·-)) radicals, were produced by Fenton/UV and xanthine/xanthine oxidase methods, respectively. The pink-coloured, (+)-charged chromophore (referred to as DMPD-quinone or DMPDQ), resulting from the reaction between DMPD and ROS, could be completely retained on the solid membrane sensor by electrostatic interaction with the anionic sulfonate groups of Nafion. After equilibration, the Nafion membrane surface was homogeneously coloured enabling an absorbance measurement at 514 nm, while the aqueous phase completely lacked colour. Antioxidants, when present, caused an absorbance decrease on the membrane due to their ROS scavenging action, giving rise to less DMPDQ production. The absorbance decrease on the sensor was linearly dependent on antioxidant concentration over a reasonable concentration range, enabling the simultaneous determination of OS and AOA-against ROS. The proposed antioxidant sensing method was tested in synthetic and real antioxidant mixtures, and validated against standard antioxidant capacity assays (i.e. ABTS and CUPRAC) for a variety of polyphenolic and antioxidant compounds. The dynamic linear ranges of antioxidants with the DMPD sensor in protection against hydroxyl and superoxide radicals generally varied within the micromolar to a few tens of micromolar concentration interval over one order-of-magnitude. Choosing three representative compounds in the high (epigallocatechin gallate), medium

  3. Simultaneous voltammetric determination of paracetamol and ascorbic acid using a boron-doped diamond electrode modified with Nafion and lead films.

    PubMed

    Tyszczuk-Rotko, Katarzyna; Bęczkowska, Ilona; Wójciak-Kosior, Magdalena; Sowa, Ireneusz

    2014-11-01

    The paper describes the fabrication and application of a novel sensor (a boron-doped diamond electrode modified with Nafion and lead films) for the simultaneous determination of paracetamol and ascorbic acid by differential pulse voltammetry. The main advantage of the lead film and polymer covered boron-doped diamond electrode is that the sensitivity of the stripping responses is increased and the separation of paracetamol and ascorbic acid signals is improved due to the modification of the boron-doped diamond surface by the lead layer. Additionally, the repeatability of paracetamol and ascorbic acid signals is improved by the application of the Nafion film coating. In the presence of oxygen, linear calibration curves were obtained in a wide concentration range from 5×10(-7) to 2×10(-4) mol L(-1) for paracetamol and from 1×10(-6) to 5×10(-4) mol L(-1) for ascorbic acid. The analytical utility of the differential pulse voltammetric method elaborated was tested in the assay of paracetamol and ascorbic acid in commercially available pharmaceutical formulations and the method was validated by high performance liquid chromatography coupled with diode array detector.

  4. Structure-relaxation interplay of a new nanostructured membrane based on tetraethylammonium trifluoromethanesulfonate ionic liquid and neutralized nafion 117 for high-temperature fuel cells.

    PubMed

    Di Noto, Vito; Negro, Enrico; Sanchez, Jean-Yves; Iojoiu, Christina

    2010-02-24

    In this report, the electrical performance at T > 100 degrees C and low relative humidity of proton-conducting Nafion-based membranes was improved by preparing new materials based on Nafion 117 (N117) neutralized with triethylammonium (TEA(+)) and doped with the ionic liquid (IL) trifluoromethanesulfonate of triethylammonium (TEA-TF). In particular, a new two-step protocol for the preparation of [N117(x-)(TEA(+))(x)/(TEA-TF)(y)] is proposed. [N117(x-)(TEA(+))(x)/(TEA-TF)(y)] membrane is composed of ca. 30 wt % of TEA-TF. The structure of the different nanophases composing the materials and their interactions were investigated by FT-IR ATR and micro-Raman spectroscopy. The thermal stability, water uptake, and mechanical properties of the membranes were studied by thermogravimetric analysis and dynamic mechanical analysis measurements. With respect to pristine N117, the thermal and mechanical properties of the proposed materials were improved. The electric response of [N117(x-)(TEA(+))(x)/(TEA-TF)(y)] was studied by broad band dielectric spectroscopy in the frequency range from 10(-2) Hz to 10 MHz and for temperatures between 5 and 155 degrees C. In comparison to the N117 reference, the following was observed: (a) the stability range of conductivity (SRC) of the [N117(x-)(TEA(+))(x)] membrane increases up to 155 degrees C, while its sigma(DC) at T = 100 degrees C is lowered by ca. 2 orders of magnitude; (b) the SRC of [N117(x-)(TEA(+))(x)/(TEA-TF)(y)] is similar to that of [N117(x-)(TEA(+))(x)], while the sigma(DC) at 145 degrees C decreases in the order 7.3 x 10(-3) > 6.1 x 10(-3) > 9.7 x 10(-4) S x cm(-1) for [N117(x-)(TEA(+))(x)/(TEA-TF)(y)], N117, and [N117(x-)(TEA(+))(x)] membranes, respectively. In conclusion, the lower water uptake, the improved thermal and mechanical stability, and the good conductivity make [N117(x-)(TEA(+))(x)/(TEA-TF)(y)] a promising membrane to improve for application in proton exchange membrane fuel cells operating under anhydrous

  5. Performance of Nafion® N115, Nafion® NR-212, and Nafion® NR-211 in a 1 kW Class All Vanadium Mixed Acid Redox Flow Battery

    SciTech Connect

    Reed, David M.; Thomsen, Edwin C.; Wang, Wei; Nie, Zimin; Li, Bin; Wei, Xiaoliang; Koeppel, Brian J.; Sprenkle, Vincent L.

    2015-07-01

    Three Nafion membranes of similar composition but different thicknesses were operated in a 3-cell 1kW class all vanadium mixed acid redox flow battery. The influence of current density on the charge/discharge characteristics, coulombic and energy efficiency, capacity fade, operating temperature and pressure drop in the flow circuit will be discussed and correlated to the Nafion membrane thickness. Material costs associated with the Nafion membranes, ease of handling the membranes, and performance impacts will also be discussed.

  6. Modification for Uniform Surface of Nafion Ultrathin Film Deposited by Inkjet Printing.

    PubMed

    Guo, Yanglu; Ono, Yutaro; Nagao, Yuki

    2015-09-22

    A lack of knowledge about the features of Nafion confined to ultrathin films at the interface has motivated additional examinations to promote the performance of polymer electrolyte membrane fuel cells (PEMFCs). In this work, we demonstrated the utilization of practical film-forming technique inkjet printing to fabricate a Nafion ultrathin film less than 10 nm thickness. However, the well-known "coffee-ring" effect caused poor quality of the printed pattern, which has restricted its application. This report describes a systematic investigation of necessary parameters such as ink concentration, substrate type, pitch, and offset for printing processes. Furthermore, post-treatment in an ethanol vapor atmosphere exhibited a significant effect on flattening and homogenizing the film surface morphology. Results show that the well-distributed Nafion ultrathin film modified by ethanol vapor annealing manifested much-improved proton conductivity. PMID:26327333

  7. Quasireversible Process of Dopamine on Copper-Nickel Hydroxide Composite/Nitrogen Doped Graphene/Nafion Modified GCE and Its Electrochemical Application

    PubMed Central

    Liu, Chuan-yin; Liu, Zhong-yong; Peng, Rong; Zhong, Zhi-cheng

    2014-01-01

    Cu-Ni(OH)2/N-GR/Nafion/GCE has been prepared by electrodeposition and activation with NaOH. The proposed modified GCE was studied by electrochemical methods. It is found that dopamine shows favorable redox cyclic voltammetric response on the proposed modified GCE with peak separation of 25 mV and large current compared with on single-component modified GCE. The kinetic of electrode process has also been investigated with rate constant of 6.618 × 10−3 cm/s, which can be deduced to be a quasireversible or near-reversible process. The proposed method has been used for DA detection with linear range of 1.0 × 10−7 mol/L to 4.6 × 10−5 mol/L, and the detection limit is 3.3 × 10−8 mol/L. The proposed method has favorable stability and reproducibility and has also been used to determine DA in simulated samples and DA injections with favorable recoveries of 98.4% to 102.6%. PMID:25024866

  8. Quasireversible Process of Dopamine on Copper-Nickel Hydroxide Composite/Nitrogen Doped Graphene/Nafion Modified GCE and Its Electrochemical Application.

    PubMed

    Liu, Chuan-Yin; Liu, Zhong-Yong; Peng, Rong; Zhong, Zhi-Cheng

    2014-01-01

    Cu-Ni(OH)2/N-GR/Nafion/GCE has been prepared by electrodeposition and activation with NaOH. The proposed modified GCE was studied by electrochemical methods. It is found that dopamine shows favorable redox cyclic voltammetric response on the proposed modified GCE with peak separation of 25 mV and large current compared with on single-component modified GCE. The kinetic of electrode process has also been investigated with rate constant of 6.618 × 10(-3) cm/s, which can be deduced to be a quasireversible or near-reversible process. The proposed method has been used for DA detection with linear range of 1.0 × 10(-7) mol/L to 4.6 × 10(-5) mol/L, and the detection limit is 3.3 × 10(-8) mol/L. The proposed method has favorable stability and reproducibility and has also been used to determine DA in simulated samples and DA injections with favorable recoveries of 98.4% to 102.6%. PMID:25024866

  9. Mediated proton transport through Nafion 117 membranes imbibed with varying concentrations of aqueous VOSO4 (VO2+) and NH4VO3 (VO2+) in 2 M H2SO4

    NASA Astrophysics Data System (ADS)

    Suarez, Sophia; Paterno, Domenec

    2016-11-01

    We performed an extensive study on Nafion 117 membrane imbibed with various concentrations of aqueous ammonium metavanadate (NH4VO3), and vanadyl sulfate (VOSO4), in 2 M H2SO4 over the temperature range of 20-100 °C, using 1H NMR and AC Impedance spectroscopies. The objective was to determine the effect of the tetravalent (VO2+) and pentavalent (VO2+) vanadium ions on the proton transport of Nafion 117.1H NMR chemical shift and linewidth data show greater short-range proton transport for the VO2+ imbibed membranes compared with the VO2+. However, the local environments seem to differ in that while the data for VO2+ imbibed membranes seem to follow more the trends observed for water hydrated Nafion 117, those for the VO2+ followed the trend of its aqueous bulk vanadium solvents, indicating that viscosity plays a larger role for the VO2+ imbibed membranes compared to the VO2+.

  10. Enhanced electromechanical response of Ionic Polymer-Metal Composite (IPMC) actuators by various Nafion roughening levels

    NASA Astrophysics Data System (ADS)

    Wang, Yanjie; Liu, Jiayu; Chen, Hualing

    2016-04-01

    Recently, Ionic polymer metal composites (IPMCs), becoming an increasingly popular material, are used as soft actuators for its inherent properties of light weight, flexibility, softness, especial efficient transformation from electrical energy to mechanical energy with large bending strain response to low activation voltage. This paper mainly focuses on the suitable conditions for surface-roughening of Nafion 117 membrane. The surfaces of Nafion membrane were pretreated and optimized by sandblasting, mainly considering the change of sandblasting time and powder size. The modified surfaces are characterized in terms of their topography from the confocal laser scanning microscope (CLSM) and SEM. Then, the detailed change in surface and interfacial electrodes and performances for IPMC actuators prepared by the roughened membranes, were measured and discussed. The results show that an optimized roughening condition with large interface area (capacitance) can effectively increases the electromechanical responses of IPMC.

  11. Sensitive voltammetric sensor based on isopropanol-Nafion-PSS-GR nanocomposite modified glassy carbon electrode for determination of clenbuterol in pork.

    PubMed

    Wang, Ling; Yang, Ran; Chen, Jing; Li, Jianjun; Qu, Lingbo; de B Harrington, Peter

    2014-12-01

    In the present study, poly(sodium 4-styrenesulfonate) (PSS) functionalized graphene (GR) was synthesised via a simple one-step chemical reduction of exfoliated graphite oxides in the presence of PSS. Characterisation of as-made nanocomposite using Fourier transform infrared spectroscopy (FT-IR) and ultraviolet and visible spectroscopy (UV-vis) clearly demonstrate the successful attachment of PSS to graphene sheets. A novel clenbuterol (CLB) electrochemical sensor was fabricated based on isopropanol-Nafion-PSS-GR composite film modified glassy carbon electrode. In the Britton-Robinson buffer (pH 1.2), the sensor exhibited superior electrocatalytic activity towards the oxidation of CLB. Applying linear sweep voltammetry, a good linear relationship of the oxidation peak current with respect to concentrations of CLB cross the range of 7.5 × 10(-8)-2.5 × 10(-5)mol L(-1) and a detection limit of 2.2 × 10(-8) mol L(-1) were achieved. The proposed method was successfully applied for the determination of CLB in pork.

  12. Photoelectrochemistry of photosystem I bound in nafion.

    PubMed

    Baker, David R; Simmerman, Richard F; Sumner, James J; Bruce, Barry D; Lundgren, Cynthia A

    2014-11-18

    Developing a solid state Photosystem I (PSI) modified electrode is attractive for photoelectrochemical applications because of the quantum yield of PSI, which approaches unity in the visible spectrum. Electrodes are constructed using a Nafion film to encapsulate PSI as well as the hole-scavenging redox mediator Os(bpy)2Cl2. The photoactive electrodes generate photocurrents of 4 μA/cm(2) when illuminated with 1.4 mW/cm(2) of 676 nm band-pass filtered light. Methyl viologen (MV(2+)) is present in the electrolyte to scavenge photoelectrons from PSI in the Nafion film and transport charges to the counter electrode. Because MV(2+) is positively charged in both reduced and oxidized states, it is able to diffuse through the cation permeable channels of Nafion. Photocurrent is produced when the working electrode is set to voltages negative of the Os(3+)/Os(2+) redox potential. Charge transfer through the Nafion film and photohole scavenging at the PSI luminal surface by Os(bpy)2Cl2 depends on the reduction of Os redox centers to Os(2+) via hole scavenging from PSI. The optimal film densities of Nafion (10 μg/cm(2) Nafion) and PSI (100 μg/cm(2) PSI) are determined to provide the highest photocurrents. These optimal film densities force films to be thin to allow the majority of PSI to have productive electrical contact with the backing electrode. PMID:25341002

  13. Property modification of Nafion via polymer blending with ethylene vinyl alcohol "polyimide" (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Hwang, Taeseon; Nam, Jungsoo; Shen, Qi; Trabia, Sarah; Suhr, Jonghwan; Lee, Dong-Chan; Kim, Kwang Jin

    2016-04-01

    The blended ion exchange membrane between Nafion and ethylene vinyl alcohol (EVOH) was used for fabrication of the ionic polymer-metal composite (IPMC) to redeem inherent drawbacks of Nafion such as high cost or environment-unfriendliness. EVOH solution was blended in Nafion solution by a volume ratio of 15 and 30 % membranes were prepared through solution casting method. The prepared blended Nafion membranes can be fabricated IPMCs with deposition of platinum electrode onto its surface without crack or delamination. The surface resistance of all prepared IPMCs is measured through 2 point probe. This study investigated the chemical structure and thermal properties of prepared membranes. Moreover, we characterized the cross-section morphology and studied the electromechanical performances (displacement and blocking force) of prepared IPMC actuators. The IPMC actuators with proposed blended Nafion membranes were demonstrated comparable electromechanical performance by significantly reducing the content of Nafion.

  14. Electrochemical sensors for the simultaneous determination of zinc, cadmium and lead using a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode.

    PubMed

    Chaiyo, Sudkate; Mehmeti, Eda; Žagar, Kristina; Siangproh, Weena; Chailapakul, Orawon; Kalcher, Kurt

    2016-04-28

    A simple, low cost, and highly sensitive electrochemical sensor, based on a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode (N/IL/G/SPCE) was developed to determine zinc (Zn(II)), cadmium (Cd(II)), and lead (Pb(II)) simultaneously. This disposable electrode shows excellent conductivity and fast electron transfer kinetics. By in situ plating with a bismuth film (BiF), the developed electrode exhibited well-defined and separate peaks for Zn(II), Cd(II), and Pb(II) by square wave anodic stripping voltammetry (SWASV). Analytical characteristics of the BiF/N/IL/G/SPCE were explored with calibration curves which were found to be linear for Zn(II), Cd(II), and Pb(II) concentrations over the range from 0.1 to 100.0 ng L(-1). With an accumulation period of 120 s detection limits of 0.09 ng mL(-1), 0.06 ng L(-1) and 0.08 ng L(-1) were obtained for Zn(II), Cd(II) and Pb(II), respectively using the BiF/N/IL/G/SPCE sensor, calculated as 3σ value of the blank. In addition, the developed electrode displayed a good repeatability and reproducibility. The interference from other common ions associated with Zn(II), Cd(II) and Pb(II) detection could be effectively avoided. Finally, the proposed analytical procedure was applied to detect the trace metal ions in drinking water samples with satisfactory results which demonstrates the suitability of the BiF/N/IL/G/SPCE to detect heavy metals in water samples and the results agreed well with those obtained by inductively coupled plasma mass spectrometry. PMID:27046207

  15. Electrochemical sensors for the simultaneous determination of zinc, cadmium and lead using a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode.

    PubMed

    Chaiyo, Sudkate; Mehmeti, Eda; Žagar, Kristina; Siangproh, Weena; Chailapakul, Orawon; Kalcher, Kurt

    2016-04-28

    A simple, low cost, and highly sensitive electrochemical sensor, based on a Nafion/ionic liquid/graphene composite modified screen-printed carbon electrode (N/IL/G/SPCE) was developed to determine zinc (Zn(II)), cadmium (Cd(II)), and lead (Pb(II)) simultaneously. This disposable electrode shows excellent conductivity and fast electron transfer kinetics. By in situ plating with a bismuth film (BiF), the developed electrode exhibited well-defined and separate peaks for Zn(II), Cd(II), and Pb(II) by square wave anodic stripping voltammetry (SWASV). Analytical characteristics of the BiF/N/IL/G/SPCE were explored with calibration curves which were found to be linear for Zn(II), Cd(II), and Pb(II) concentrations over the range from 0.1 to 100.0 ng L(-1). With an accumulation period of 120 s detection limits of 0.09 ng mL(-1), 0.06 ng L(-1) and 0.08 ng L(-1) were obtained for Zn(II), Cd(II) and Pb(II), respectively using the BiF/N/IL/G/SPCE sensor, calculated as 3σ value of the blank. In addition, the developed electrode displayed a good repeatability and reproducibility. The interference from other common ions associated with Zn(II), Cd(II) and Pb(II) detection could be effectively avoided. Finally, the proposed analytical procedure was applied to detect the trace metal ions in drinking water samples with satisfactory results which demonstrates the suitability of the BiF/N/IL/G/SPCE to detect heavy metals in water samples and the results agreed well with those obtained by inductively coupled plasma mass spectrometry.

  16. Biocompatibility studies of polyacrylonitrile membranes modified with carboxylated polyetherimide.

    PubMed

    Senthilkumar, S; Rajesh, S; Jayalakshmi, A; Mohan, D

    2013-10-01

    Poly (ether-imide) (PEI) was carboxylated and used as the hydrophilic modification agent for the preparation of polyacrylonitrile (PAN) membranes. Membranes were prepared with different blend compositions of PAN and CPEI by diffusion induced precipitation. The modified membranes were characterized by thermo gravimetric analysis (TGA), mechanical analysis, scanning electron microscopy (SEM) and contact angle measurement to understand the influence of CPEI on the properties of the membranes. The biocompatibility studies exhibited reduced plasma protein adsorption, platelet adhesion and thrombus formation on the modified membrane surface. The complete blood count (CBC) results of CPEI incorporated membranes showed stable CBC values and significant decrease in the complement activation were also observed. In addition to good cytocompatibility, monocytes cultured on these modified membranes exhibited improved functional profiles in 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide (MTT) assay. Thus it could be concluded that PAN/CPEI membranes with excellent biocompatibility can be useful for hemodialysis. PMID:23910257

  17. Performance of Nafion® N115, Nafion® NR-212, and Nafion® NR-211 in a 1 kW class all vanadium mixed acid redox flow battery

    NASA Astrophysics Data System (ADS)

    Reed, David; Thomsen, Edwin; Wang, Wei; Nie, Zimin; Li, Bin; Wei, Xiaoliang; Koeppel, Brian; Sprenkle, Vincent

    2015-07-01

    Three Nafion® membranes of similar composition but different thicknesses were operated in a 3-cell 1 kW class all vanadium mixed acid redox flow battery. The influence of current density on the charge/discharge characteristics, coulombic and energy efficiency, capacity fade, operating temperature and pressure drop in the flow circuit will be discussed and correlated to the Nafion® membrane thickness. Material costs associated with the Nafion® membranes, ease of handling the membranes, and performance impacts will also be discussed.

  18. Water-Nafion equilibria. absence of Schroeder's paradox.

    PubMed

    Onishi, Lisa M; Prausnitz, John M; Newman, John

    2007-08-30

    Water-Nafion phase equilibria and proton conductivities were measured in two ways. First, Nafion was in contact with saturated water vapor. Second, Nafion was in contact with liquid water at the same temperature. At 29 degrees C, for preboiled, vapor-equilibrated Nafion exposed to water with an activity = 1 and air pressures ranging from 0 to 0.96 bar, the water content was lambda = 23 +/- 1 mol H(2)O/mol SO3-. For the preboiled, liquid-equilibrated membrane, lambda = 24 +/- 2. At 100% relative humidity (RH), the water content of preboiled Nafion decreased as the temperature rose from 30 to 80 degrees C but did not recover its initial water content when the temperature returned to 30 degrees C. The water content of predried Nafion at 1 atm and 30 degrees C was lambda = 13.7 +/- 0.2 when vapor-equilibrated and lambda = 13.1 +/- 0.5 when liquid-equilibrated. A Nafion membrane originally boiled in water had much higher liquid- and 100% RH vapor-equilibrated proton conductivities than the same membrane originally dried at 110 degrees C with a RH less than 2%. The liquid-equilibrated and 100% RH vapor-equilibrated membrane conductivities were the same when the membrane had the same thermal history. The conductivity data was fit to a model, and the water content was determined at different temperatures. The predried membrane water content increased with temperature, and the preboiled membrane's water content changed slightly with temperature. Both water sorption and proton-conductivity data do not exhibit Schroeder's paradox. These studies and previous results suggest that Schroeder's paradox is resolved when attention is given to the thermal history of the absorbing polymer.

  19. Novel composite proton-exchange membrane based on proton-conductive glass powders and sulfonated poly (ether ether ketone)

    NASA Astrophysics Data System (ADS)

    Di, Zhigang; Xie, Qiang; Li, Haibin; Mao, Dali; Li, Ming; Zhou, Daowu; Li, Lu

    2015-01-01

    The SiO2-Nafion/sulfonated poly (ether ether ketone) (SPEEK) composite membranes are fabricated by using the simple mechanical ball-milling process to combine SiO2 glass powders with small portion of Nafion, in which SiO2 glass powders are prepared by modified sol-gel progress and Nafion is embedded in situ into a highly porous silica network. The morphology, thermal and mechanical properties, pore structure, proton conductivity and fuel cell performance of the SiO2-Nafion/SPEEK composite membranes are investigated. The poor miscibility of Nafion and sulfonated aromatic polymer is solved by fixing Nafion into SiO2 glass powders. The composite membranes perform well even if the proportion of inorganic component in membranes is as high as 40 wt.%. A maximum of proton conductivity, 0.018 S cm-1, is obtained from the membrane of 4(8Si-2N)/6SPEEK at 80 °C and 90% relative humidity, which is owing to its enhanced hygroscopicity and highly dispersed Nafion clusters. In addition, a single fuel cell equipped with the composite membrane shows a peak power density of 589.2 mW cm-2 at 70 °C.

  20. NMR and Electrochemical Investigation of the Transport Properties of Methanol and Water in Nafion and Clay-Nanocomposites Membranes for DMFCs

    PubMed Central

    Nicotera, Isabella; Angjeli, Kristina; Coppola, Luigi; Aricò, Antonino S.; Baglio, Vincenzo

    2012-01-01

    Water and methanol transport behavior, solvents adsorption and electrochemical properties of filler-free Nafion and nanocomposites based on two smectite clays, were investigated using impedance spectroscopy, DMFC tests and NMR methods, including spin-lattice relaxation and pulsed-gradient spin-echo (PGSE) diffusion under variable temperature conditions. Synthetic (Laponite) and natural (Swy-2) smectite clays, with different structural and physical parameters, were incorporated into the Nafion for the creation of exfoliated nanocomposites. Transport mechanism of water and methanol appears to be influenced from the dimensions of the dispersed platelike silicate layers as well as from their cation exchange capacity (CEC). The details of the NMR results and the effect of the methanol solution concentration are discussed. Clays particles, and in particular Swy-2, demonstrate to be a potential physical barrier for methanol cross-over, reducing the methanol diffusion with an evident blocking effect yet nevertheless ensuring a high water mobility up to 130 °C and for several hours, proving the exceptional water retention property of these materials and their possible use in the DMFCs applications. Electrochemical behavior is investigated by cell resistance and polarization measurements. From these analyses it is derived that the addition of clay materials to recast Nafion decreases the ohmic losses at high temperatures extending in this way the operating range of a direct methanol fuel cell. PMID:24958179

  1. Composite polymer membranes for proton exchange membrane fuel cells operating at elevated temperatures and reduced humidities

    NASA Astrophysics Data System (ADS)

    Zhang, Tao

    -ethylene/butylene-styrene triblock copolymer (sSEBS) was investigated as an alternate membrane candidate. sSEBS was modified through introduction of polymer crosslinks using benzephenone as a photoinitiator and addition of a titania co-phase. A photocrosslinked membrane initially containing 15% benzophenone and 3% titania laminated with a 10 mum Nafion layer was found to produce the best PEMFC performance (120°C, 50%RH).

  2. Effect of bound state of water on hydronium ion mobility in hydrated Nafion using molecular dynamics simulations

    SciTech Connect

    Mabuchi, Takuya; Tokumasu, Takashi

    2014-09-14

    We have performed a detailed analysis of the structural properties of the sulfonate groups in terms of isolated and overlapped solvation shells in the nanostructure of hydrated Nafion membrane using classical molecular dynamics simulations. Our simulations have demonstrated the correlation between the two different areas in bound water region, i.e., the first solvation shell, and the vehicular transport of hydronium ions at different water contents. We have employed a model of the Nafion membrane using the improved force field, which is newly modified and validated by comparing the density and water diffusivity with those obtained experimentally. The first solvation shells were classified into the two types, the isolated area and the overlapped area. The mean residence times of solvent molecules explicitly showed the different behaviors in each of those areas in terms of the vehicular transport of protons: the diffusivity of classical hydronium ions in the overlapped area dominates their total diffusion at lower water contents while that in the isolated area dominates for their diffusion at higher water contents. The results provided insights into the importance role of those areas in the solvation shells for the diffusivity of vehicular transport of hydronium ions in hydrated Nafion membrane.

  3. A method for the quantification of low concentration sulfamethazine residues in milk based on molecularly imprinted clean-up and surface preconcentration at a Nafion-modified glassy carbon electrode.

    PubMed

    Guzmán-Vázquez de Prada, A; Reviejo, A J; Pingarrón, J M

    2006-02-13

    An electrochemical method for the determination of sulfamethazine at a low concentration level (25 microgl(-1)) in milk is reported. The method involves sample clean-up and selective preconcentration of sulfamethazine with a molecularly imprinted polymer (MIP), and a further electrode surface preconcentration of the analyte at a Nafion-coated glassy carbon electrode (GCE). Square wave (SW) oxidative voltammetry of accumulated sulfamethazine was employed for its quantification. Sulfamethazine electrode preconcentration was carried out in 0.1 moll(-1) Britton-Robinson buffer of pH 1.5, and by applying 5 min of accumulation at open circuit. A linear calibration graph was obtained for sulfamethazine at the Nafion-modified GCE over the 1.0x10(-8) to 1.0x10(-6)moll(-1) concentration range, with a detection limit of 6.8x10(-9)moll(-1) (1.9 microgl(-1)). This detection limit is remarkably better than those reported previously in the literature using electroanalytical techniques. Although the detection limit achieved was sufficient to allow the direct determination of sulfamethazine at the concentration level required in milk, a sample clean-up was shown to be necessary to obtain analytically useful SW voltammograms. This was accomplished by processing the deproteinized milk through a cartridge containing a molecularly imprinted polymer for sulfamethazine, also allowing a selective preconcentration of the analyte. Elution of the analyte from the MIP cartridges was carried out with 2 ml of a (9:1) MeOH:acetic acid mixture. Determination of sulfamethazine in milk samples was accomplished by interpolation into a calibration graph constructed with sulfamethazine standard solutions which were subjected to the same procedure than the deproteinized milk samples. Results obtained for five samples, spiked at the 25 microgl(-1) level, showed a mean recovery of (100+/-3)%.

  4. Chemically modified opals as thin permselective nanoporous membranes.

    PubMed

    Newton, Michael R; Bohaty, Andrew K; White, Henry S; Zharov, Ilya

    2005-05-25

    Thin-film opals comprising three layers of 440 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with amino groups on the silica surface. Diffusion of anionic, cationic, and neutral redox species through the opals was studied by cyclic voltammetry. The chemically modified opal membranes demonstrate high molecular throughput and, at low pH, selectively block transport of a cationic redox species relative to that of anionic and neutral redox species. This permselective behavior is attributed to the electrostatic interactions that are enhanced by the tortuous pathway within the opal and by the high surface area of the chemically modified spheres.

  5. Electrochemiluminescence sensor for melamine based on a Ru(bpy)₃²⁺-doped silica nanoparticles/carboxylic acid functionalized multi-walled carbon nanotubes/Nafion composite film modified electrode.

    PubMed

    Chen, Xiaomei; Lian, Sai; Ma, Ying; Peng, Aihong; Tian, Xiaotian; Huang, Zhiyong; Chen, Xi

    2016-01-01

    In this work, a sensitive electrochemiluminescence (ECL) sensor for the determination of melamine (MEL) was developed based on a Ru(bpy)3(2+)-doped silica nanoparticles (RUDS)/carboxylic acid functionalized multi-walled carbon nanotubes (CMWCNTs)/Nafion composite film modified electrode. The homogeneous spherical RUDS were synthesized by a reverse microemulsion method. As Ru(bpy)3(2+) were encapsulated in the RUDS, Ru(bpy)3(2+) dropping from the modified electrode can be greatly prevented, which is helpful for obtaining a stable ECL signal. Moreover, to improve the conductivity of the film and promote the electron transfer rate on electrode surface, CMWCNTs with excellent electrical conductivity and large surface area were applied in the construction of the sensing film. As CMWCNTs acted as electron bridges making more Ru(bpy)3(2+) participate in the reaction, the ECL intensity was greatly enhanced. Under the optimum conditions, the relative ECL signal (△IECL) was proportional to the logarithmic MEL concentration ranging from 5×10(-13) to 1×10(-7) mol L(-1) with a detection limit of 1×10(-13) mol L(-1). To verify the reliability, the thus-fabricated ECL sensor was applied to determine the concentration of MEL in milk. Based on these investigations, the proposed ECL sensor exhibited good feasibility and high sensitivity for the determination of MEL, promising the applicability of this sensor in practical analysis.

  6. The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

    NASA Technical Reports Server (NTRS)

    Parthasarathy, Arvind; Dave, Bhasker; Srinivasan, Supramaniam; Appleby, John A.; Martin, Charles R.

    1992-01-01

    The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

  7. Membrane and MEA Development in Polymer Electrolyte Fuel Cells

    NASA Astrophysics Data System (ADS)

    Trogadas, Panagiotis; Ramani, Vijay

    The polymer electrolyte fuel cell (PEFC) is based on Nafion polymer membranes operating at a temperature of 80°C. The main characteristics (structure and properties) and problems of Nafion-based PEFC technology are discussed. The primary drawbacks of Nafion membranes are poor conductivity at low relative humidities (and consequently at temperatures >100°C and ambient pressure) and large crossover of methanol in direct methanol fuel cell (DMFC) applications. These drawbacks have prompted an extensive effort to improve the properties of Nafion and identify alternate materials to replace Nafion. Polymer electrolyte membranes (PEMs) are classified in modified Nafion, membranes based on functionalized non-fluorinated backbones and acid-base polymer systems. Perhaps the most widely employed approach is the addition of inorganic additives to Nafion membranes to yield organic/inorganic composite membranes. Four major types of inorganic additives that have been studied (zirconium phosphates, heteropolyacids, metal hydrogen sulfates, and metal oxides) are reviewed in the following. DMFC and H2/O2 (air) cells based on modified Nafion membranes have been successfully operated at temperatures up to 120°C under ambient pressure and up to 150°C under 3-5 atm. Membranes based on functionalized non-fluorinated backbones are potentially promising for high-temperature operation. High conductivities have been obtained at temperatures up to 180°C. The final category of polymeric PEMs comprises non-functionalized polymers with basic character doped with proton-conducting acids such as phosphoric acid. The advanced features include high CO tolerance and thermal management. The advances made in the fabrication of electrodes for PEM fuel cells from the PTFE-bound catalyst layers of almost 20 years ago to the present technology are briefly discussed. There are two widely employed electrode designs: (1) PTFE-bound, and (2) thin-film electrodes. Emerging methods include those featuring

  8. Ion exchange capacity of Nafion and Nafion composites

    SciTech Connect

    Chen, T.Y.; Leddy, J.

    2000-03-21

    The ion exchange capacity of recast Nafion films and composites of Nafion and polystyrene microbeads is determined by titration. Composite formation enhances exchange capacity; exchange capacity increases with the surface area microbeads in the composite. For recast films, an equivalent weight of 996 {+-} 24 is found, whereas the lowest equivalent weight (highest exchange capacity) found for composite is 878 {+-} 8. This suggests that {approx_gt} 13% of the exchange sites within recast films are inaccessible for ion exchange; for 1,100 equivalent weight material, {approx_gt} 25% of the sulfonates are inaccessible. Equivalent weight results are consistent with an ordered interfacial domain between Nafion and the microbeads. A fractal model based on microbead radii, microbead fraction, and interfacial domain thickness provides a predictive model for designing composites with increased exchange capacity and cation transport.

  9. Modified cellulosic dialyzer membranes: an investigative tool in thrombogenicity studies.

    PubMed

    Mahiout, A; Meinhold, H; Kessel, M; Vienken, J; Baurmeister, U

    1988-01-01

    We have previously demonstrated that chemical modification of cellulosic membranes with dimethyl-amino-ethyl (DEAE) groups significantly improves membrane properties in terms of biocompatibility. Here, we show that DEAE substitution also alters the membrane's thrombogenic properties, and cellulosic membranes with various amounts of DEAE substitution were produced. Clinical dialyzers were constructed using two experimental membrane materials: modified cellulose-low (MC-low) and MC-high; standard unsubstituted cellulose was used as a control. Six patients were treated for a period of 3 weeks with each type of dialyzer and a heparin dose of less than 6000 IU/treatment. MC-low exhibited less extracorporeal beta-thromboglobulin and thromboxane B2 release than MC-high or Cuprophan. In addition, residual blood volume after clinical use was lower in the MC-low type. MC-low and MC-high induced less complement activation than Cuprophan, as characterized by extracorporeal C5a and C3a plasma concentrations (75% less C5a generation and 50 to 70% less C3a generation than unsubstituted cellulose).

  10. Electrospun fiber membranes enable proliferation of genetically modified cells

    PubMed Central

    Borjigin, Mandula; Eskridge, Chris; Niamat, Rohina; Strouse, Bryan; Bialk, Pawel; Kmiec, Eric B

    2013-01-01

    Polycaprolactone (PCL) and its blended composites (chitosan, gelatin, and lecithin) are well-established biomaterials that can enrich cell growth and enable tissue engineering. However, their application in the recovery and proliferation of genetically modified cells has not been studied. In the study reported here, we fabricated PCL-biomaterial blended fiber membranes, characterized them using physicochemical techniques, and used them as templates for the growth of genetically modified HCT116-19 colon cancer cells. Our data show that the blended polymers are highly miscible and form homogenous electrospun fiber membranes of uniform texture. The aligned PCL nanofibers support robust cell growth, yielding a 2.5-fold higher proliferation rate than cells plated on standard plastic plate surfaces. PCL-lecithin fiber membranes yielded a 2.7-fold higher rate of proliferation, while PCL-chitosan supported a more modest growth rate (1.5-fold higher). Surprisingly, PCL-gelatin did not enhance cell proliferation when compared to the rate of cell growth on plastic surfaces. PMID:23467983

  11. The use of Nafion{reg_sign} as an ionic conductor in fuel cells

    SciTech Connect

    Grot, W.G.

    1993-12-31

    The properties of Nafion will be discussed in relation to its application as an electrolyte in fuel cells and as a component of fuel cell electrodes. The primary factors influencing its application as a membrane are its water uptake and its mechanical strength. The properties of Nafion {open_quotes}solutions,{close_quotes} specifically morphological changes during casting, will be described in relation to application in electrodes.

  12. A fabrication method of unique Nafion® shapes by painting for ionic polymer–metal composites

    NASA Astrophysics Data System (ADS)

    Trabia, Sarah; Hwang, Taeseon; Kim, Kwang J.

    2016-08-01

    Ionic polymer–metal composites (IPMC) are useful actuators because of their ability to be fabricated in different shapes and move in various ways. However, producing unique or intricate shapes can be difficult based upon the current fabrication techniques. Presented here is a fabrication method of producing the Nafion® membrane or thin film through a painting method. Using an airbrush, a Nafion water dispersion is sprayed onto an acrylonitrile butadiene styrene surface with a stencil of the desired shape. To verify that this method of fabrication produces a Nafion membrane similar to that which is commercially available, a sample that was made using the painting method and Nafion 117 purchased from DuPont™ were tested for various characteristics and compared. The results show promising similarities. The painted Nafion sample was chemically plated with platinum and compared with a traditional IPMC for its displacement and blocking force capabilities. The painted IPMC sample showed comparable results.

  13. A fabrication method of unique Nafion® shapes by painting for ionic polymer-metal composites

    NASA Astrophysics Data System (ADS)

    Trabia, Sarah; Hwang, Taeseon; Kim, Kwang J.

    2016-08-01

    Ionic polymer-metal composites (IPMC) are useful actuators because of their ability to be fabricated in different shapes and move in various ways. However, producing unique or intricate shapes can be difficult based upon the current fabrication techniques. Presented here is a fabrication method of producing the Nafion® membrane or thin film through a painting method. Using an airbrush, a Nafion water dispersion is sprayed onto an acrylonitrile butadiene styrene surface with a stencil of the desired shape. To verify that this method of fabrication produces a Nafion membrane similar to that which is commercially available, a sample that was made using the painting method and Nafion 117 purchased from DuPont™ were tested for various characteristics and compared. The results show promising similarities. The painted Nafion sample was chemically plated with platinum and compared with a traditional IPMC for its displacement and blocking force capabilities. The painted IPMC sample showed comparable results.

  14. Nafion-stabilised bimetallic Pt–Cr nanoparticles as electrocatalysts for proton exchange membrane fuel cells (PEMFCs)† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra16025e Click here for additional data file.

    PubMed Central

    Gupta, G.; Sharma, S.

    2016-01-01

    The current study investigated the unique combination of alloying (Pt with Cr) and Nafion stabilisation to reap the benefits of catalyst systems with enhanced catalytic activity and improved durability in PEMFCs. Pt–Cr alloy nanoparticles stabilised with Nafion were chosen in the current study owing to their higher stability in acidic and oxidising media at high temperatures compared to other Pt-transition metal alloys (e.g. Pt–Ni, Pt–Co). Two different precursor : reducing agent (1 : 10 and 1 : 20) ratios were used in order to prepare two different alloys, denoted as Pt–Cr 10 and Pt–Cr 20. The Pt–Cr 20 alloy system (with composition Pt80Cr20) demonstrated higher electrocatalytic activity for the oxygen reduction reaction compared to commercial Pt/C (TKK) catalysts. Accelerated stress tests and single cell tests revealed that Nafion stabilised alloy catalyst systems displayed significantly enhanced durability (only ∼20% loss of ECSA) compared with Pt/C (50% loss of ECSA) due to improved catalyst–ionomer interaction. Furthermore, the Pt–Cr 20 alloy system demonstrated a current density comparable to that of Pt/C making them promising potential electrocatalysts for proton exchange membrane fuel cells. PMID:27774145

  15. Laccase-based biocathodes: Comparison of chitosan and Nafion.

    PubMed

    El Ichi-Ribault, S; Zebda, A; Laaroussi, A; Reverdy-Bruas, N; Chaussy, D; Belgacem, M N; Suherman, A L; Cinquin, P; Martin, D K

    2016-09-21

    Chitosan and Nafion(®) are both reported as interesting polymers to be integrated into the structure of 3D electrodes for biofuel cells. Their advantage is mainly related to their chemical properties, which have a positive impact on the stability of electrodes such as the laccase-based biocathode. For optimal function in implantable applications the biocathode requires coating with a biocompatible semi-permeable membrane that is designed to prevent the loss of enzyme activity and to protect the structure of the biocathode. Since such membranes are integrated into the electrodes ultimately implanted, they must be fully characterized to demonstrate that there is no interference with the performance of the electrode. In the present study, we demonstrate that chitosan provides superior stability compared with Nafion(®) and should be considered as an optimum solution to enhance the biocompatibility and the stability of 3D bioelectrodes. PMID:27590544

  16. Visualization of ion transport in Nafion using electrochemical strain microscopy

    SciTech Connect

    Kim, Suran; No, Kwangsoo; Hong, Seungbum

    2015-12-24

    The electromechanical response of a Nafion membrane immersed in water was probed using electrochemical strain microscopy (ESM) to redistribute protons and measure the resulting local strain that is caused by the movement of protons. We also measured the relaxation of protons from the surface resulting from proton diffusion. Using this technique, we can visualize and analyze the local strain change resulting from the redistribution and relaxation of hydrated protons.

  17. Photo Induced Membrane Separation for Water Purification and Desalination Using Azobenzene Modified Anodized Alumina Membranes.

    PubMed

    Fujiwara, Masahiro; Imura, Tatsuki

    2015-06-23

    Water purification and desalination to produce end-use water are important agendas in 21st century, because the global water shortage is becoming increasingly serious. Those processes using light energy, especially solar energy, without the consumption of fossil fuels are desired for creating sustainable society. For these earth-friendly water treatments, nanoporous materials and membranes are expected to provide new technologies. We have reported before that the repetitive photo isomerization of azobenzene groups between the trans and cis isomers induced by the simultaneous irradiation of UV and visible lights accelerates the molecular movement of nearby molecules in nanoporous materials. After further studies, we recently found that the permeation of water through azobenzene modified anodized alumina membranes as a photo responsive nanoporous membrane was achieved by the simultaneous irradiation of UV and visible lights, while no water penetration occurred under no light, only single UV or visible light. The photo induced permeation of water was promoted by the vaporization of water with the repetitive photo isomerization of azobenzene. This membrane permeation achieved the purification of water solutions, because dye molecules and a protein dissolved in aqueous solutions were not involved in the photo induced penetrated water. When 3.5% of sodium chloride solution as model seawater was employed for this membrane separation, the salt content of the permeated water was less than 0.01% to accomplish the complete desalination of seawater.

  18. Photo Induced Membrane Separation for Water Purification and Desalination Using Azobenzene Modified Anodized Alumina Membranes.

    PubMed

    Fujiwara, Masahiro; Imura, Tatsuki

    2015-06-23

    Water purification and desalination to produce end-use water are important agendas in 21st century, because the global water shortage is becoming increasingly serious. Those processes using light energy, especially solar energy, without the consumption of fossil fuels are desired for creating sustainable society. For these earth-friendly water treatments, nanoporous materials and membranes are expected to provide new technologies. We have reported before that the repetitive photo isomerization of azobenzene groups between the trans and cis isomers induced by the simultaneous irradiation of UV and visible lights accelerates the molecular movement of nearby molecules in nanoporous materials. After further studies, we recently found that the permeation of water through azobenzene modified anodized alumina membranes as a photo responsive nanoporous membrane was achieved by the simultaneous irradiation of UV and visible lights, while no water penetration occurred under no light, only single UV or visible light. The photo induced permeation of water was promoted by the vaporization of water with the repetitive photo isomerization of azobenzene. This membrane permeation achieved the purification of water solutions, because dye molecules and a protein dissolved in aqueous solutions were not involved in the photo induced penetrated water. When 3.5% of sodium chloride solution as model seawater was employed for this membrane separation, the salt content of the permeated water was less than 0.01% to accomplish the complete desalination of seawater. PMID:26005901

  19. Preparation and characterization of sulfonated carbon nanotube/Nafion IPMC actuators

    NASA Astrophysics Data System (ADS)

    Ru, Jie; Wang, Yanjie; Chang, Longfei; Chen, Hualing; Li, Bo; Jia, Shuhai

    2016-04-01

    In this paper, we developed a new kind of ionic polymer metal composite (IPMC) actuator by doping sulfonated carbon nanotube (SCNT) into Nafion matrix to overcome some major drawbacks, such as low output force and short air-operation time, which restrict applications of conventional Nafion IPMC actuators. Firstly, SCNT was synthesized by coupled reaction of multi-walled carbon nanotubes and azo compounds and then doped into Nafion matrix by casting method. Subsequently, several key parameters of the SCNT-reinforced Nation matrix, water uptake ratio and equivalent stiffness, were revealed and the inner morphology of the membranes were observed by scanning electron microscopy. Finally, the effects of the SCNT on the electromechanical properties of IPMC actuators, especially the actuating performance, were evaluated experimentally and analyzed systematically. The results showed that SCNT was evenly dispersed in Nafion matrix and a small amount of SCNT could improve the performance of IPMC actuators significantly.

  20. Nafion as Cosurfactant: Solubilization of Nafion in Water in the Presence of Pluronics

    SciTech Connect

    Kelarakis, Antonios; Giannelis, Emmanuel P.

    2011-01-18

    Incorporation of Nafion to aqueous solutions of Pluronics adversely impacts micellization due to extensive Nafion/copolymer interactions. Light scattering and zeta potential measurements provide evidence for the formation of sizable and stable Nafion/copolymer complexes, in expense of the neat copolymer micelles. At high copolymer concentrations, the overall interaction diagram of Nafion/copolymer reflects the competitive action of the release of packing constraints due to micellar destabilization induced by Nafion on one hand and the gelator nature of the Nafion on the other. Measurements using a quartz crystal microbalance (QCM-D) show that aqueous solutions of Pluronics (even at very low concentration) can dissolve the Nafion coating on the crystal resonator, while typical low molecular weight ionic surfactants fail to induce similar effects. These studies demonstrate that complexation with this class of copolymers is a facile route to impart dispersibility to Nafion in aqueous environments that otherwise can be achieved through tedious and harsh treatments.

  1. Silver Nafion for Thermogalvanic Applications

    NASA Astrophysics Data System (ADS)

    Chang, William; Popere, Bhooshan; Evans, Chris; Russ, Boris; Segalman, Rachel

    2015-03-01

    Thermogalvanics convert a temperature gradient, typically from waste heat, into electrical power using a reversible electrochemical reaction. The conversion efficiency in thermogalvanics, like with thermoelectrics, are governed by the Seebeck coefficient, the carrier conductivity and the thermal conductivity of the material. We demonstrate that the material systems silver Nafion and silver poly-styrenesulfonate are air-stable, water processable materials that demonstrate extremely high Seebeck coefficients and moderate carrier conductivities. These power factors, when coupled with the low thermal conductivities inherent in polymers, results in materials with excellent thermogalvanic figure of merits. We show the dependence of these three material properties to material composition and processing. In this talk, we show how the Seebeck coefficient in silver Nafion and silver polystyrene-sulfonate are opposite in sign, allowing construction of a thermogalvanic device. With these ion conductors, we hope to open up a flexible pathway to waste heat recovery using materials typically studied for electrochemical applications.

  2. Azobenzene Modified Polymer Electrolyte Membrane for Ion Gating

    NASA Astrophysics Data System (ADS)

    Piedrahita, Camilo; Mballa, Mireille; He, Ruixuan; Kyu, Thein

    By virtue of ion concentration gradient across cell membranes, neuron cells are highly polarized driving electrical potential difference (e.g., Gibbs law). To regulate and control ion movement, living cells have specific channels with gates that are permeable to cations, enabling or excluding them via charge polarity and size. This mechanism for generating and transmitting signals from one neuron to another controls body movement via brain function. By virtue of trans-cis isomerization, azobenzene derivative (AZO) has been heavily sought for ion-gating in biological cells as a means of signal generation and transmission through nervous systems. In this work, PEM consisted of PEGDA/SCN/LiTFSI was modified with AZO derivatives for gating of lithium ions. At low concentrations of azobenzene of 3 wt Supported by NSF-DMR 1502543.

  3. FY08 MEMBRANE CHARACTERIZATION REPORT FOR HYBRID SULFUR ELECTROLYZER

    SciTech Connect

    Hobbs, D; Hector Colon-Mercado, H; Mark Elvington, M

    2008-09-01

    This report summarizes results from all of the membrane testing completed to date at the Savannah River National Laboratory (SRNL) for the sulfur dioxide-depolarized electrolyzer (SDE). Several types of commercially-available membranes have been analyzed for ionic resistance and sulfur dioxide transport including perfluorinated sulfonic acid (PFSA), sulfonated polyether-ketone-ketone (SPEKK), and polybenzimidazole membranes (PBI). Of these membrane types, the poly-benzimidazole membrane, Celtec-L, exhibited the best combination of characteristics for use in an SDE. Several experimental membranes have also been analyzed including hydrated sulfonated Diels-Alder polyphenylenes (SDAPP) membranes from Sandia National Laboratory, perfluorosulfonimide (PFSI) and sulfonated perfluorocyclobutyl aromatic ether (S-PFCB) prepared by Clemson University, hydrated platinum-treated PFSA prepared by Giner Electrochemical Systems (GES) and Pt-Nafion{reg_sign} 115 composites prepared at SRNL. The chemical stability, SO{sub 2} transport and ionic conductivity characteristics have been measured for several commercially available and experimental proton-conducting membranes. Commercially available PFSA membranes such as the Nafion{reg_sign} series exhibited excellent chemical stability and ionic conductivity in sulfur dioxide saturated sulfuric acid solutions. Sulfur dioxide transport in the Nafion{reg_sign} membranes varied proportionally with the thickness and equivalent weight of the membrane. Although the SO{sub 2} transport in the Nafion{reg_sign} membranes is higher than desired, the excellent chemical stability and conductivity makes this membrane the best commercially-available membrane at this time. Initial results indicated that a modified Nafion{reg_sign} membrane incorporating Pt nanoparticles exhibited significantly reduced SO{sub 2} transport. Reduced SO{sub 2} transport was also measured with commercially available PBI membrane and several experimental membranes produced

  4. Purification and proteomics of pathogen-modified vacuoles and membranes

    PubMed Central

    Herweg, Jo-Ana; Hansmeier, Nicole; Otto, Andreas; Geffken, Anna C.; Subbarayal, Prema; Prusty, Bhupesh K.; Becher, Dörte; Hensel, Michael; Schaible, Ulrich E.; Rudel, Thomas; Hilbi, Hubert

    2015-01-01

    Certain pathogenic bacteria adopt an intracellular lifestyle and proliferate in eukaryotic host cells. The intracellular niche protects the bacteria from cellular and humoral components of the mammalian immune system, and at the same time, allows the bacteria to gain access to otherwise restricted nutrient sources. Yet, intracellular protection and access to nutrients comes with a price, i.e., the bacteria need to overcome cell-autonomous defense mechanisms, such as the bactericidal endocytic pathway. While a few bacteria rupture the early phagosome and escape into the host cytoplasm, most intracellular pathogens form a distinct, degradation-resistant and replication-permissive membranous compartment. Intracellular bacteria that form unique pathogen vacuoles include Legionella, Mycobacterium, Chlamydia, Simkania, and Salmonella species. In order to understand the formation of these pathogen niches on a global scale and in a comprehensive and quantitative manner, an inventory of compartment-associated host factors is required. To this end, the intact pathogen compartments need to be isolated, purified and biochemically characterized. Here, we review recent progress on the isolation and purification of pathogen-modified vacuoles and membranes, as well as their proteomic characterization by mass spectrometry and different validation approaches. These studies provide the basis for further investigations on the specific mechanisms of pathogen-driven compartment formation. PMID:26082896

  5. Purification and proteomics of pathogen-modified vacuoles and membranes.

    PubMed

    Herweg, Jo-Ana; Hansmeier, Nicole; Otto, Andreas; Geffken, Anna C; Subbarayal, Prema; Prusty, Bhupesh K; Becher, Dörte; Hensel, Michael; Schaible, Ulrich E; Rudel, Thomas; Hilbi, Hubert

    2015-01-01

    Certain pathogenic bacteria adopt an intracellular lifestyle and proliferate in eukaryotic host cells. The intracellular niche protects the bacteria from cellular and humoral components of the mammalian immune system, and at the same time, allows the bacteria to gain access to otherwise restricted nutrient sources. Yet, intracellular protection and access to nutrients comes with a price, i.e., the bacteria need to overcome cell-autonomous defense mechanisms, such as the bactericidal endocytic pathway. While a few bacteria rupture the early phagosome and escape into the host cytoplasm, most intracellular pathogens form a distinct, degradation-resistant and replication-permissive membranous compartment. Intracellular bacteria that form unique pathogen vacuoles include Legionella, Mycobacterium, Chlamydia, Simkania, and Salmonella species. In order to understand the formation of these pathogen niches on a global scale and in a comprehensive and quantitative manner, an inventory of compartment-associated host factors is required. To this end, the intact pathogen compartments need to be isolated, purified and biochemically characterized. Here, we review recent progress on the isolation and purification of pathogen-modified vacuoles and membranes, as well as their proteomic characterization by mass spectrometry and different validation approaches. These studies provide the basis for further investigations on the specific mechanisms of pathogen-driven compartment formation.

  6. A new force field for molecular dynamics studies of Li + and Na +-nafion

    NASA Astrophysics Data System (ADS)

    Soolo, Endel; Liivat, Anti; Kasemägi, Heiki; Tamm, Tarmo; Brandell, Daniel; Aabloo, Alvo

    2008-03-01

    Nafion is widely known as one of the most popular membrane materials for low temperature fuel cell applications. However, the particular exchange membrane material properties make it also valuable for other applications. One of the electroactive polymer (EAP) subclasses, ionic polymer metal composites (IPMC) commonly exploits Nafion as the ion exchange polymer membrane. The ion conducting properties of Nafion are extremely important for IPMCs. Although, ion conductivity depends strongly on the structural properties of the polymer matrix, there has been very little insight at the atomistic level. Molecular dynamics simulations are one of the possibilities to study the ion conduction mechanism at atomistic level. So far, the simulation results have been rather contradictory and very much dependent from the force fields and polymer matrix setup used. In the present work, new force field parameters for Li + and Na + - nafion based on DFT calculations are presented. The developed potentials and the force field were tested by molecular dynamics simulations. It can be concluded that Li + and Na + ions are coordinated to different Nafion side-chain terminal group (SO 3 -) oxygens and to very few water molecules. One cation is coordinated to three different side-chains. Oxygens of SO 3 groups and cations form complicated multi-header systems. In the equilibrium state, no cations dissociated from side chains were found.

  7. A Mechanistic Study of Chemically Modified Inorganic Membranes for Gas and Liquid Separations

    SciTech Connect

    Way, J Douglas

    2011-01-21

    This final report will summarize the progress made during the period August 1, 1993 - October 31, 2010 with support from DOE grant number DE-FG03-93ER14363. The objectives of the research have been to investigate the transport mechanisms in micro- and mesoporous, metal oxide membranes and to examine the relationship between the microstructure of the membrane, the membrane surface chemistry, and the separation performance of the membrane. Examples of the membrane materials under investigation are the microporous silica hollow fiber membrane manufactured by PPG Industries, chemically modified mesoporous oxide membranes, and polymer membranes containing microporous oxides (mixed matrix membranes). Analytical techniques such as NMR, FTIR and Raman spectroscopy, thermal analysis, and gas adsorption were used to investigate membrane microstructure and to probe the chemical interactions occurring at the gas-membrane interface.

  8. Donnan dialysis of transition metal ions using anion exchange membrane modified with Xylenol Orange

    SciTech Connect

    Sawicka, B.; Brajter, K.; Trojanowicz, M.; Kado, B. )

    1991-01-01

    A chelating ion-exchange membrane was obtained by modification of a PTFE-based anion-exchange membrane with Xylenol Orange. Its utility for dialysis of Cu(II), Ni(II), Mn(II), and Zn(II) was investigated by using receiver solutions without and with iminodiacetate. 1,2-diaminocyclohexanetetraacetic acid, and tetraethylenepentamine. In comparison to commercial PTFE cation-exchange membranes, modified chelating membranes exhibit for the metal ions investigated a larger differentiation of retention in the membrane phase and transport-to-receiver solution depending on the modifier used and the composition of the receiver solution.

  9. Sea cucumber-like hydroxyapatite: cation exchange membrane-assisted synthesis and its application in ultra-sensitive heavy metal detection.

    PubMed

    Zhang, Ying; Liu, Yong; Ji, Xiaobo; Banks, Craig E; Zhang, Wei

    2011-04-14

    Sea cucumber-like hydroxyapatite fabricated with the aid of a Nafion N-117 cation exchange membrane was applied to the detection of lead(II) and cadmium(II) in ultra-trace concentration levels. The proposed HAp-modified carbon paste electrode has significantly lower linear ranges and exhibits a larger sensitivity than those reported previously.

  10. Characterization of modified PVDF membrane by gamma irradiation for non-potable water reuse.

    PubMed

    Lim, Seung Joo; Kim, Tak-Hyun; Shin, In Hwan

    2015-01-01

    Poly(vinylidene fluorine) (PVDF) membranes were grafted by gamma-ray irradiation and were sulfonated by sodium sulfite to modify the surface of the membranes. The characteristics of the modified PVDF membranes were evaluated by the data of Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscope (FE-SEM), the contact angle of the membrane surface and the water permeability. From the results of FT-IR, XPS and FE-SEM, it was shown that the modified membranes were successfully grafted by gamma-ray irradiation and were sulfonated. The content of oxygen and sulfur increased with the monomer concentration, while the content of fluorine sharply decreased. The pore size of the modified membranes decreased after gamma-ray irradiation. The contact angle and the water permeability showed that the hydrophilicity of the modified membranes played a role in determining the membrane performance. The feasibility study of the modified PVDF membranes for using non-potable water reuse were carried out using a laboratory-scale microfiltration system. Grey wastewater was used as the influent in the filtration unit, and permeate quality satisfied non-potable water reuse guidelines in the Republic of Korea. PMID:25812106

  11. Peptide-modified PELCL electrospun membranes for regulation of vascular endothelial cells.

    PubMed

    Zhou, Fang; Jia, Xiaoling; Yang, Yang; Yang, Qingmao; Gao, Chao; Zhao, Yunhui; Fan, Yubo; Yuan, Xiaoyan

    2016-11-01

    The efficiency of biomaterials used in small vascular repair depends greatly on their ability to interact with vascular endothelial cells (VECs). Rapid endothelialization of the vascular grafts is a promising way to prevent thrombosis and intimal hyperplasia. In this work, modification of electrospun membranes of poly(ethylene glycol)-b-poly(l-lactide-co-ε-caprolactone) (PELCL) by three different peptides for regulation of VECs were studied in order to obtain ideal bioactive biomaterials as small diameter vascular grafts. QK (a mimetic peptide to vascular endothelial growth factor), Arg-Glu-Asp-Val (REDV, a specific adhesive peptide to VECs) and Val-Ala-Pro-Gly (VAPG, a specific adhesive peptide to vascular smooth muscle cells) were investigated. Surface properties of the modified membranes and the response of VECs were verified. It was found that protein adsorption and platelet adhesion were effectively suppressed with the introduction of QK, REDV or VAPG peptides on the PELCL electrospun membranes. Both QK- and REDV-modified electrospun membranes could accelerate the proliferation of VECs in the first 9days, and the QK-modified electrospun membrane promoted cell proliferation more significantly than the REDV-modified one. The REDV-modified PELCL membrane was the most favorable for VECs adhesion than QK- and VAPG-modified membranes. It was suggested that QK- or REDV-modified PELCL electrospun membranes may have great potential applications in cardiovascular biomaterials for rapid endothelialization in situ. PMID:27524062

  12. Peptide-modified PELCL electrospun membranes for regulation of vascular endothelial cells.

    PubMed

    Zhou, Fang; Jia, Xiaoling; Yang, Yang; Yang, Qingmao; Gao, Chao; Zhao, Yunhui; Fan, Yubo; Yuan, Xiaoyan

    2016-11-01

    The efficiency of biomaterials used in small vascular repair depends greatly on their ability to interact with vascular endothelial cells (VECs). Rapid endothelialization of the vascular grafts is a promising way to prevent thrombosis and intimal hyperplasia. In this work, modification of electrospun membranes of poly(ethylene glycol)-b-poly(l-lactide-co-ε-caprolactone) (PELCL) by three different peptides for regulation of VECs were studied in order to obtain ideal bioactive biomaterials as small diameter vascular grafts. QK (a mimetic peptide to vascular endothelial growth factor), Arg-Glu-Asp-Val (REDV, a specific adhesive peptide to VECs) and Val-Ala-Pro-Gly (VAPG, a specific adhesive peptide to vascular smooth muscle cells) were investigated. Surface properties of the modified membranes and the response of VECs were verified. It was found that protein adsorption and platelet adhesion were effectively suppressed with the introduction of QK, REDV or VAPG peptides on the PELCL electrospun membranes. Both QK- and REDV-modified electrospun membranes could accelerate the proliferation of VECs in the first 9days, and the QK-modified electrospun membrane promoted cell proliferation more significantly than the REDV-modified one. The REDV-modified PELCL membrane was the most favorable for VECs adhesion than QK- and VAPG-modified membranes. It was suggested that QK- or REDV-modified PELCL electrospun membranes may have great potential applications in cardiovascular biomaterials for rapid endothelialization in situ.

  13. Lipid-membrane modified electrodes to study quinone oxidoreductases

    PubMed Central

    Weiss, Sophie A.; Jeuken, Lars J. C.

    2013-01-01

    Quinone oxidoreductases are a class of membrane enzymes that catalyse the oxidation or reduction of membrane-bound quinols/quinones. The conversion of quinone/quinol by these enzymes is difficult to study due to the hydrophobic nature of the enzymes and their substrates. We describe some biochemical properties of quinones and quinone oxidoreductases and then look in more detail at two model membranes that can be used to study quinone oxidoreductases in a native-like membrane environment with their native lipophylic quinone substrates. The results obtained with these model membranes are compared to classical enzyme assays that use water-soluble quinone analogues. PMID:19614580

  14. Insulin-induced changes in mechanical characteristics of lipid bilayers modified by liver plasma membrane fragments.

    PubMed

    Hianik, T; Kavecanský, J; Zórad, S; Macho, L

    1988-04-01

    Insulin interaction with BLM with incorporated fragments of rat liver plasma membranes, containing hormone receptors, was studied by determining Young modulus of elasticity of bilayer lipid membranes in direction perpendicular to the surface, E. The presence of membrane proteins in a concentration of 60 micrograms.ml-1 induced a significant decrease in parameter E (to approx. 50%) as compared with values obtained in non-modified membranes during insulin action (concentration interval 10(-11)-10(-9) mol.l-1). The extent of the effect was dependent on the initial phase state of the membrane, on cholesterol content in BLM as well as on membrane proteins concentration in lipid bilayer.

  15. A method to modify PVDF microfiltration membrane via ATRP with low-temperature plasma pretreatment

    NASA Astrophysics Data System (ADS)

    Han, Yu; Song, Shuijun; Lu, Yin; Zhu, Dongfa

    2016-08-01

    The hydrophilic modification of a polyvinylidene fluoride (PVDF) microfiltration membrane via pretreatment with argon plasma and direct surface-initiated atom transfer radical polymerization (ATRP) was studied. Both modified and unmodified PVDF membranes were characterized by Fourier transform infrared spectroscopy (FTIR), water contact angle, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and pore size distribution measurements. FTIR and XPS spectra confirmed that sulfobetaine methacrylate (SBMA) had been grafted onto the membrane surface. The initial contact angle decreased from 87.0° to 29.8° and a water drop penetrated into the modified membrane completely in 8 s. The pore size distribution of the modified membrane exhibited a smaller mean value than that of the original membrane. The antifouling properties of the modified PVDF membrane were evaluated by a filtration test using bovine serum albumin (BSA) solution. The results showed that the initial flux of the modified membrane increased from 2140.1 L/m2 h to 2812.7 L/m2 h and the equilibrium flux of BSA solution increased from 31 L/m2 h to 53 L/m2 h.

  16. Enhancing the performance of nanofiltration membranes by modifying the active layer with aramide dendrimers.

    PubMed

    de Jubera, Ana M Saenz; Gao, Yuan; Moore, Jeffrey S; Cahill, David G; Mariñas, Benito J

    2012-09-01

    The fully aromatic polyamide active layer of a commercial nanofiltration membrane was modified with three generations (G1, G2, and G3) of aramide dendrimers, all with oligoethylene glycol chains on their peripheries. Permeation experiments revealed that the rejection of Rhodamine WT, used as a surrogate for organic contaminants, improved 1-2 orders of magnitude for membranes modified with G2 and G3 dendrimers at loadings of 0.7-3.5 μg/cm(2) (dendrimer layer thicknesses of ~1-6 nm) compared to the performance of unmodified membranes. In contrast, the corresponding water permeability of dendrimer-modified membranes decreased by only ~30%. Although an enhancement in the rejection of H(3)AsO(3), NaCl, and BaCl(2) was also observed for dendritic membranes, the effect was less pronounced than that for rhodamine WT. Characterization of membranes modified with 3.5 μg/cm(2) dendrimers G2 and G3 by Rutherford backscattering spectrometry with the aid of heavy ion probes (Ag(+) and Ba(2+)) revealed that accessibility of the larger Ba(2+) probe to carboxylate groups on the active layer decreased for the membranes modified with dendrimers.

  17. Drug Delivery via Cell Membrane Fusion Using Lipopeptide Modified Liposomes

    PubMed Central

    2016-01-01

    Efficient delivery of drugs to living cells is still a major challenge. Currently, most methods rely on the endocytotic pathway resulting in low delivery efficiency due to limited endosomal escape and/or degradation in lysosomes. Here, we report a new method for direct drug delivery into the cytosol of live cells in vitro and invivo utilizing targeted membrane fusion between liposomes and live cells. A pair of complementary coiled-coil lipopeptides was embedded in the lipid bilayer of liposomes and cell membranes respectively, resulting in targeted membrane fusion with concomitant release of liposome encapsulated cargo including fluorescent dyes and the cytotoxic drug doxorubicin. Using a wide spectrum of endocytosis inhibitors and endosome trackers, we demonstrate that the major site of cargo release is at the plasma membrane. This method thus allows for the quick and efficient delivery of drugs and is expected to have many invitro, ex vivo, and invivo applications. PMID:27725960

  18. Polypiperazine-amide Nanofiltration Membrane Modified by Different Functionalized Multiwalled Carbon Nanotubes (MWCNTs).

    PubMed

    Xue, Shuang-Mei; Xu, Zhen-Liang; Tang, Yong-Jian; Ji, Chen-Hao

    2016-07-27

    In this work, three modified multiwalled carbon nanotubes (MWCNTs) with carboxyl (MWCNT-COOH), hydroxyl (MWCNT-OH) and amino groups (MWCNT-NH), respectively, were added into the aqueous phase containing piperazine (PIP) to fabricate the nanocomposite nanofiltration (NF) membranes via interfacial polymerization. The influences of functional groups of MWCNTs on the performance of modified NF membrane were investigated. The MWCNTs were characterized by TEM, FT-IR and TGA; meanwhile, the properties of the membranes were evaluated by XPS, TEM, AFM and contact angle. The XPS results proved the successful incorporation of MWCNT in the active layer of modified NF membrane. When the MWCNT concentration is 0.01% (w/v), all the nanocomposite membranes possessed the optimal separation properties, among which the membrane incorporated with MWCNT-OH demonstrated the highest water flux of 41.4 L·m(-2)·h(-1) and the Na2SO4 rejection of 97.6% whereas the one with MWCNT-COOH had the relative lowest rejection of 96.6%. Furthermore, the increased hydrophilicity of functional groups in modified MWCNTs resulted in different nodular surface morphologies, thicknesses and hydrophilicities of the nanocomposite membranes. All the membranes possessed a molecular weight cutoff (MWCO) within 300 Da and good operation stability. PMID:27387192

  19. SEPARATION PROPERTIES OF SURFACE MODIFIED SILICA SUPPORTED LIQUID MEMBRANES FOR DIVALENT METAL REMOVAL/RECOVERY

    EPA Science Inventory

    The synthesis and separation properties of a mesoporous silica supported liquid membrane (SLM) were studied. The membranes consisted of a silica layer, from dip-coated colloidal silica, on a a-alumina support, modified with DCDMS (dichlorodimethyl silane) to add surface methyl g...

  20. Evaluation of the oleophilicity of different alkoxysilane modified ceramic membranes through wetting dynamic measurements

    NASA Astrophysics Data System (ADS)

    Gao, Nengwen; Ke, Wei; Fan, Yiqun; Xu, Nanping

    2013-10-01

    Wettability has been recognized as one of the most important properties of porous materials for both fundamental and practical applications. In this study, the oleophilicity of Al2O3 membranes modified by four alkoxysilanes with different length of alkyl group was investigated through oil wetting dynamic test. Fourier transform infrared spectroscopy (FTIR), thermogravimertric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were measured to confirm that ceramic membrane surfaces have been grafted with alkoxysilanes without changing the membrane morphology. A high speed video camera was used to record the spreading and imbibition process of oil on the modified membrane surface. The value of oil contact angle and its change during the wetting process were used to characterize the membrane oleophilicity. Characterization results showed that the oleophilicity of the modified membranes increased along with the increasing of the silane alkyl group. The influence of oleophilicity on the filtration performance of water-in-oil (W/O) emulsions was experimentally studied. A higher oil flux was obtained for membranes grafted with a longer alkyl group, indicating that increase oleophilicity can increase the membrane antifouling property. This work presents a valuable route to the surface oleophilicity control and testing of ceramic membranes in the filtration of non-polar organic solvents.

  1. Separation of macromolecular proteins and removal of humic acid by cellulose acetate modified UF membranes.

    PubMed

    Kanagaraj, P; Nagendran, A; Rana, D; Matsuura, T

    2016-08-01

    Surface modifying macromolecules (SMMs) were synthesized with various polyurethane pre polymers end-capped with different groups and blended into the casting solution of cellulose acetate (CA) to prepare surface modified ultra-filtration (UF) membranes for water filtration applications. The surface modification of the CA membranes was confirmed by the FTIR and static contact angle (SCA) measurements. The membranes so prepared had the typical characteristics of UF membranes as confirmed by scanning electron microscopy (SEM). Membrane properties were studied in terms of membrane compaction, percentage water content (%WC), pure water flux (PWF), membrane hydraulic resistance (Rm), molecular weight cut-off (MWCO), average pore size and porosity. The result showed that PWF, %WC, MWCO and pore size increased whereas the Rm decreased by the addition of SMMs. The significant effect of SMMs on the fouling by humic acid (HA) was also observed. It was found that the cSMM-3 membrane, in which SMM was synthesized with diethylene glycol (DEG) and hydroxyl benzene sulfonate (HBS) was blended, had the highest flux recovery ratio FRR (84.6%), as well as the lowest irreversible fouling (15.4%), confirming their improved antifouling properties. Thus, the SMM modified CA membranes had proven, to play an important role in the water treatment by UF. PMID:27118046

  2. Separation of macromolecular proteins and removal of humic acid by cellulose acetate modified UF membranes.

    PubMed

    Kanagaraj, P; Nagendran, A; Rana, D; Matsuura, T

    2016-08-01

    Surface modifying macromolecules (SMMs) were synthesized with various polyurethane pre polymers end-capped with different groups and blended into the casting solution of cellulose acetate (CA) to prepare surface modified ultra-filtration (UF) membranes for water filtration applications. The surface modification of the CA membranes was confirmed by the FTIR and static contact angle (SCA) measurements. The membranes so prepared had the typical characteristics of UF membranes as confirmed by scanning electron microscopy (SEM). Membrane properties were studied in terms of membrane compaction, percentage water content (%WC), pure water flux (PWF), membrane hydraulic resistance (Rm), molecular weight cut-off (MWCO), average pore size and porosity. The result showed that PWF, %WC, MWCO and pore size increased whereas the Rm decreased by the addition of SMMs. The significant effect of SMMs on the fouling by humic acid (HA) was also observed. It was found that the cSMM-3 membrane, in which SMM was synthesized with diethylene glycol (DEG) and hydroxyl benzene sulfonate (HBS) was blended, had the highest flux recovery ratio FRR (84.6%), as well as the lowest irreversible fouling (15.4%), confirming their improved antifouling properties. Thus, the SMM modified CA membranes had proven, to play an important role in the water treatment by UF.

  3. Atomistic Simulations of Hydrated Nafion and Temperature Effects on Hydronium Ion Mobility

    SciTech Connect

    Venkatnathan, Arun; Devanathan, Ram; Dupuis, Michel

    2007-04-06

    The effects of level of hydration and temperature on the nanostructure of an atomistic model of a NafionTM (Du Pont) membrane and the vehicular transport of hydronium ions and water molecules were examined using classical molecular dynamics simulations. Through the determination and analysis of structural and dynamical parameters such as density, radial distribution functions, coordination numbers, means square deviations, and diffusion coefficients, we identify that hydronium ions themselves play a role in modifying the interfacial structure in the membrane at the sulfonate pendants. In the regime of low level of hydration, short hydrogen bonded linkages made of water molecules and also hydronium ions give a more constrained structure to the sulfonate pendants. The diffusion coefficient for water was found to be in good accord with experimental data. The diffusion coefficient for hydronium ions was determined to be much smaller (6 to 10 times) than for water. Temperature was found to have a significant effect on the absolute value of the diffusion coefficients for both water and hydroniums.

  4. Development of a Nafion/MWCNT-SPCE-Based Portable Sensor for the Voltammetric Analysis of the Anti-Tuberculosis Drug Ethambutol

    PubMed Central

    Couto, Rosa A. S.; Quinaz, Maria Beatriz

    2016-01-01

    Herein we describe the development, characterization and application of an electrochemical sensor based on the use of Nafion/MWCNT-modified screen-printed carbon electrodes (SPCEs) for the voltammetric detection of the anti-tuberculosis (anti-TB) drug ethambutol (ETB). The electrochemical behaviour of the drug at the surface of the developed Nafion/MWCNT-SPCEs was studied through cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques. Electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were employed to characterize the modified surface of the electrodes. Results showed that, compared to both unmodified and MWCNTs-modified SPCEs, negatively charged Nafion/MWCNT-SPCEs remarkably enhanced the electrochemical sensitivity and selectivity for ETB due to the synergistic effect of the electrostatic interaction between cationic ETB molecules and negatively charged Nafion polymer and the inherent electrocatalytic properties of both MWCNTs and Nafion. Nafion/MWCNT-SPCEs provided excellent biocompatibility, good electrical conductivity, low electrochemical interferences and a high signal-to-noise ratio, providing excellent performance towards ETB quantification in microvolumes of human urine and human blood serum samples. The outcomes of this paper confirm that the Nafion/MWCNT-SPCE-based device could be a potential candidate for the development of a low-cost, yet reliable and efficient electrochemical portable sensor for the low-level detection of this antimycobacterial drug in biological samples. PMID:27376291

  5. Absorption behavior of vanadium in Nafion®

    NASA Astrophysics Data System (ADS)

    Cho, Hyun-Seok; Ohashi, Masato; Van Zee, J. W.

    2014-12-01

    The absorption of vanadium to Nafion® was investigated through ex-situ isotherm and conductivity measurements at 23 °C. The data show a maximum loss of ion exchange capacity (IEC) of 30% for all four oxidation states of vanadium. The affinity of vanadium for N115 was measured by back titration and atomic absorption (AA) and characterized by isotherms at 23 °C, and the affinity is highest for the divalent species and lowest for the pentavalent species in the following order: VO2+ (V5+) < VO2+ (V4+) < V3+ < V2+. Steric hindrance from the associated water complex may explain the lower absorption of vanadium compared to alkali metals. The conductivity for the VO2+ (minimum affinity)-exchanged membrane was 2-3× lower than the sodium-exchanged membrane at an approximate RH = 100%.

  6. Reverse osmosis performance of modified polyvinyl alcohol thin-film composite membranes

    SciTech Connect

    Lang, K.; Chowdhury, G.; Matsuura, T.; Sourirajan, S. )

    1994-08-01

    Membrane separation characteristics in the nanofiltration (NF) and reverse osmosis (RO) regions of the filtration spectrum are governed by a complex combination of both steric hindrance and surface force interactions. NF and RO membranes having surface charges show unusual selectivity behavior not predicted on the basis of physical pore size alone. Hence, practical characterizations should employ techniques to gain insight on membrane function. In this work, the separation characteristics of an anionically charged modified polyvinyl alcohol (PVA) thin-film composite membrane under different operating pressures were investigated. A qualitative measurement of the surface force interactions between solutes and membrane polymer was conducted using liquid chromatography technique. An attempt was also made to study the chlorine resistance of the composite membrane.

  7. Deposition of metal nanoparticles on phospholipid multilayer membranes modified by gramicidin.

    PubMed

    Han, Won Bae; Kim, Yongdeok; An, Hyeun Hwan; Kim, Hee-Soo; Yoon, Chong Seung

    2013-10-29

    A planar dipalmitoyl phosphatidylcholine (DPPC) multilayer phospholipid membrane was structurally modified by introducing a transmembrane protein, gramicidin (up to 25 mol %), to study its effect on the metal nanoparticles deposited on the membrane. Without gramicidin, when 3-nm-thick Ag, Sn, Al, and Au were deposited, the nanoparticles hardly nucleated on the DPPC membrane in rigid gel state (except for Au); however, the gramicidin addition dramatically enhanced the DPPC membrane surface's affinity for metal atoms so that a dense array of metal (Ag, Sn, and Au) or metal-oxide (Al-oxide) nanoparticles was produced on the membrane surface. The particle sizes ranged from 3 to 15 nm depending on the metal and gramicidin concentration, whereas the particle density was strongly dictated by the gramicidin concentration. The proposed method provides a convenient, generally applicable synthesis route for preparing different metal or metal-oxide nanoparticles on a relatively robust biocompatible membrane.

  8. Using silica nanoparticles for modifying sulfonated poly(phthalazinone ether ketone) membrane for direct methanol fuel cell: A significant improvement on cell performance

    NASA Astrophysics Data System (ADS)

    Su, Yu-Huei; Liu, Ying-Ling; Sun, Yi-Ming; Lai, Juin-Yih; Guiver, Michael D.; Gao, Yan

    Sulfonated poly(phthalazinone ether ketone) (sPPEK) with a degree of sulfonation of 1.23 was mixed with silica nanoparticles to form hybrid materials for using as proton exchange membranes. The nanoparticles were found homogeneously dispersed in the polymer matrix and a high 30 phr (parts per hundred resin) loading of silica nanoparticles can be achieved. The hybrid membranes exhibited improved swelling behavior, thermal stability, and mechanical properties. The methanol crossover behavior of the membrane was also depressed such that these membranes are suitable for a high methanol concentration in feed (3 M) in cell test. The membrane with 5 phr silica nanoparticles showed an open cell potential of 0.6 V and an optimum power density of 52.9 mW cm -2 at a current density of 264.6 mA cm -2, which is better than the performance of the pristine sPPEK membrane and Nafion ® 117.

  9. Characterization of cellulose membranes modified with luminescent silicon quantum dots nanoparticles.

    PubMed

    Campos, B B; Gelde, L; Algarra, M; Esteves da Silva, J C G; Vázquez, M I; Benavente, J

    2016-10-20

    A highly hydrophilic planar membrane fabricated with regenerated cellulose (RC-4 membrane), a biocompatible polymer, was modified by inclusion of water-soluble silicon quantum dot nanoparticles (SiQDs). Both bare SiQDs and SiQDs coated with a PAMAM-OH dendrimer were employed in order to obtain luminescent and thermally stable membrane systems (RC-4/SiQDs and RC-4/SiQDs-PAMAM-OH membranes). Original and SiQDs-modified membranes were characterized by fluorescence spectroscopy (steady and confocal), derivative thermogravimetric analysis and impedance spectroscopy measurements. According to these results, both SiQDs-regenerated cellulose composite membranes present luminescent character as well as higher thermal resistance and conductivity than the original sample, although the dendrimer coverage of the SiQDs might partially shield such effects. Moreover, the permanence of SiQDs nanoparticles in the structure of the cellulosic support in aqueous environments and their effect on diffusive transport were determined by water uptake as well as by membrane potential measurements at different concentrations of a model electrolyte (KCl). These results demonstrate the possible use of these stable nano-engineered membranes, which are based on SiQDs nanoparticles, in electrochemical devices under flow conditions. PMID:27474642

  10. Characterization of cellulose membranes modified with luminescent silicon quantum dots nanoparticles.

    PubMed

    Campos, B B; Gelde, L; Algarra, M; Esteves da Silva, J C G; Vázquez, M I; Benavente, J

    2016-10-20

    A highly hydrophilic planar membrane fabricated with regenerated cellulose (RC-4 membrane), a biocompatible polymer, was modified by inclusion of water-soluble silicon quantum dot nanoparticles (SiQDs). Both bare SiQDs and SiQDs coated with a PAMAM-OH dendrimer were employed in order to obtain luminescent and thermally stable membrane systems (RC-4/SiQDs and RC-4/SiQDs-PAMAM-OH membranes). Original and SiQDs-modified membranes were characterized by fluorescence spectroscopy (steady and confocal), derivative thermogravimetric analysis and impedance spectroscopy measurements. According to these results, both SiQDs-regenerated cellulose composite membranes present luminescent character as well as higher thermal resistance and conductivity than the original sample, although the dendrimer coverage of the SiQDs might partially shield such effects. Moreover, the permanence of SiQDs nanoparticles in the structure of the cellulosic support in aqueous environments and their effect on diffusive transport were determined by water uptake as well as by membrane potential measurements at different concentrations of a model electrolyte (KCl). These results demonstrate the possible use of these stable nano-engineered membranes, which are based on SiQDs nanoparticles, in electrochemical devices under flow conditions.

  11. Electroanalysis of cationic species at membrane-carbon electrodes modified by polysaccharides. Bioaccumulation at microorganism-modified electrodes.

    PubMed

    Lojou, E; Bianco, P

    2000-05-01

    Membrane-carbon electrodes modified with polysaccharides suspensions entrapped between a dialysis membrane and the carbon surface were used for electroanalysis of various cationic species. Cationic complexes of ruthenium and cobalt, metallic cations (Cu(2+), Fe(3+), UO(2)(2+)) as well as methylviologen were considered. By investigating various parameters (concentration of the suspension, pH) binding of the cations by the polysaccharides was demonstrated. Comparison of cations uptake by different kinds of polysaccharides such as alginic acid, polygalacturonic acid, pectin, dextran and agar was performed. This study has been extended to natural biomaterials, alga and lichen, which are known to contain polysaccharides. The interest of the membrane-electrode strategy is described.

  12. Local anesthetics structure-dependently interact with anionic phospholipid membranes to modify the fluidity.

    PubMed

    Tsuchiya, Hironori; Ueno, Takahiro; Mizogami, Maki; Takakura, Ko

    2010-01-01

    While bupivacaine is more cardiotoxic than other local anesthetics, the mechanistic background for different toxic effects remains unclear. Several cardiotoxic compounds act on lipid bilayers to change the physicochemical properties of membranes. We comparatively studied the interaction of local anesthetics with lipid membranous systems which might be related to their structure-selective cardiotoxicity. Amide local anesthetics (10-300 microM) were reacted with unilamellar vesicles which were prepared with different phospholipids and cholesterol of varying lipid compositions. They were compared on the potencies to modify membrane fluidity by measuring fluorescence polarization. Local anesthetics interacted with liposomal membranes to increase the fluidity. Increasing anionic phospholipids in membranes enhanced the membrane-fluidizing effects of local anesthetics with the potency being cardiolipin>phosphatidic acid>phosphatidylglycerol>phosphatidylserine. Cardiolipin was most effective on bupivacaine, followed by ropivacaine. Local anesthetics interacted differently with biomimetic membranes consisting of 10mol% cardiolipin, 50mol% other phospholipids and 40mol% cholesterol with the potency being bupivacaine>ropivacaine>lidocaine>prilocaine, which agreed with the rank order of cardiotoxicity. Bupivacaine significantly fluidized 2.5-12.5mol% cardiolipin-containing membranes at cardiotoxicologically relevant concentrations. Bupivacaine is considered to affect lipid bilayers by interacting electrostatically with negatively charged cardiolipin head groups and hydrophobically with phospholipid acyl chains. The structure-dependent interaction with lipid membranes containing cardiolipin, which is preferentially localized in cardiomyocyte mitochondrial membranes, may be a mechanistic clue to explain the structure-selective cardiotoxicity of local anesthetics.

  13. Electrospun nanofibrous chitosan membranes modified with polyethyleneimine for formaldehyde detection.

    PubMed

    Wang, Na; Wang, Xianfeng; Jia, Yongtang; Li, Xiaoqi; Yu, Jianyong; Ding, Bin

    2014-08-01

    Here we describe a formaldehyde sensor fabricated by coating polyethyleneimine (PEI) functionalized chitosan nanofiber-net-binary structured layer on quartz crystal microbalance (QCM). The chitosan fibrous substrate comprising nanofibers and spider-web-like nano-nets constructed by a facile electro-spinning/netting process provided an ideal structure for the uniform PEI modification and sensing performance enhancement. Benefiting from the fascinating nanostructure, abundant primary amine groups of PEI, and strong adhesive force to the QCM electrode of PEI-chitosan membranes, the developed formaldehyde sensor presented rapid response and low detection limit (5 ppm) at room temperature. These findings have important implications in fabricating multi-dimensional nanostructures on QCM for gas sensing and chemical analysis.

  14. Membrane paradigm of black holes in Chern-Simons modified gravity

    NASA Astrophysics Data System (ADS)

    Zhao, Tian-Yi; Wang, Towe

    2016-06-01

    The membrane paradigm of black hole is studied in the Chern-Simons modified gravity. Derived with the action principle a la Parikh-Wilczek, the stress tensor of membrane manifests a rich structure arising from the Chern-Simons term. The membrane stress tensor, if related to the bulk stress tensor in a special form, obeys the low-dimensional fluid continuity equation and the Navier-Stokes equation. This paradigm is applied to spherically symmetric static geometries, and in particular, the Schwarzschild black hole, which is a solution of a large class of dynamical Chern-Simons gravity.

  15. a Novel Method to Synthesize N-DOPED CNTs Arrays via Chemical Modifying Porous Alumina Membrane

    NASA Astrophysics Data System (ADS)

    Li, Chengyong; He, Lei

    2014-01-01

    N-doped carbon nanotubes (CNTs) arrays were fabricated via simply chemical modifying porous alumina membrane (PAM) with dopamine. The diameter of N-doped CNTs is about 60-70 nm. The N/C atomic ratio is calculated to be 0.05 and the main functionality is pyridone/pyrrole N. This chemical modifying method can be used to fabricate mass of N-doped CNTs arrays in one step with single raw material.

  16. Proteomes of Host Cell Membranes Modified by Intracellular Activities of Salmonella enterica*

    PubMed Central

    Vorwerk, Stephanie; Krieger, Viktoria; Deiwick, Jörg; Hensel, Michael; Hansmeier, Nicole

    2015-01-01

    Intracellular pathogens need to establish a growth-stimulating host niche for survival and replication. A unique feature of the gastrointestinal pathogen Salmonella enterica serovar Typhimurium is the creation of extensive membrane networks within its host. An understanding of the origin and function of these membranes is crucial for the development of new treatment strategies. However, the characterization of this compartment is very challenging, and only fragmentary knowledge of its composition and biogenesis exists. Here, we describe a new proteome-based approach to enrich and characterize Salmonella-modified membranes. Using a Salmonella mutant strain that does not form this unique membrane network as a reference, we identified a high-confidence set of host proteins associated with Salmonella-modified membranes. This comprehensive analysis allowed us to reconstruct the interactions of Salmonella with host membranes. For example, we noted that Salmonella redirects endoplasmic reticulum (ER) membrane trafficking to its intracellular niche, a finding that has not been described for Salmonella previously. Our system-wide approach therefore has the potential to rapidly close gaps in our knowledge of the infection process of intracellular pathogens and demonstrates a hitherto unrecognized complexity in the formation of Salmonella host niches. PMID:25348832

  17. Proteomes of host cell membranes modified by intracellular activities of Salmonella enterica.

    PubMed

    Vorwerk, Stephanie; Krieger, Viktoria; Deiwick, Jörg; Hensel, Michael; Hansmeier, Nicole

    2015-01-01

    Intracellular pathogens need to establish a growth-stimulating host niche for survival and replication. A unique feature of the gastrointestinal pathogen Salmonella enterica serovar Typhimurium is the creation of extensive membrane networks within its host. An understanding of the origin and function of these membranes is crucial for the development of new treatment strategies. However, the characterization of this compartment is very challenging, and only fragmentary knowledge of its composition and biogenesis exists. Here, we describe a new proteome-based approach to enrich and characterize Salmonella-modified membranes. Using a Salmonella mutant strain that does not form this unique membrane network as a reference, we identified a high-confidence set of host proteins associated with Salmonella-modified membranes. This comprehensive analysis allowed us to reconstruct the interactions of Salmonella with host membranes. For example, we noted that Salmonella redirects endoplasmic reticulum (ER) membrane trafficking to its intracellular niche, a finding that has not been described for Salmonella previously. Our system-wide approach therefore has the potential to rapidly close gaps in our knowledge of the infection process of intracellular pathogens and demonstrates a hitherto unrecognized complexity in the formation of Salmonella host niches.

  18. Modified by air plasma polymer tack membranes as drainage material for antiglaucomatous operations

    NASA Astrophysics Data System (ADS)

    Ryazantseva, T. V.; Kravets, L. I.; Elinson, V. M.

    2014-06-01

    The morphological and clinical studies of poly(ethylene terephthalate) track membranes modified by air plasma as drainage materials for antiglaucomatous operations were performed. It was demonstrated their compatibility with eye tissues. Moreover, it was shown that a new drainage has a good lasting hypotensive effect and can be used as operation for refractory glaucoma surgery.

  19. Solution-Membrane Equilibrium at Metal-Deposited Cation-Exchange Membranes: Chronopotentiometric Characterization of Metal-Modified Membranes.

    PubMed

    Shahi; Prakash; Ramachandraiah; Rangarajan; Vasudevan

    1999-08-01

    Copper- and lead-deposited interpolymer cationic membranes have been prepared by electroless plating by an ion-exchange method and characterized by chronopotentiometry and cyclic voltammetry. The parameters such as transition time (tau), Itau1/2, the potential drop (E0) across these membranes immediately after the application of constant current (I), and the height of the potential jump (DeltaE) across the membrane at tau have been measured by chronopotentiometry and compared with those of plain membranes. The approximate percentage of metal coverage and the number of ionic sites masked by the deposited metal in terms of NaCl concentration have been estimated from the differences in Itau1/2 values of plain and metal-deposited membranes. The quantity of metal deposited in a unit area of the membrane surface was measured by differential pulse polarography. The oxidation and reduction peak potentials corresponding to Cu(0)/Cu(II) and Pb(0)/Pb(II) couples were identified by cyclic voltammetry at pH 2.8 and 4.5 of 0.2 M CH3COONa-H2SO4. Copyright 1999 Academic Press. PMID:10395776

  20. Production of bacterial cellulose membranes in a modified airlift bioreactor by Gluconacetobacter xylinus.

    PubMed

    Wu, Sheng-Chi; Li, Meng-Hsun

    2015-10-01

    In this study, a novel bioreactor for producing bacterial cellulose (BC) is proposed. Traditional BC production uses static culture conditions and produces a gelatinous membrane. The potential for using various types of bioreactor, including a stirred tank, conventional airlift, and modified airlift with a rectangular wire-mesh draft tube, in large-scale production has been investigated. The BC obtained from these bioreactors is fibrous or in pellet form. Our proposed airlift bioreactor produces a membrane-type BC from Gluconacetobacter xylinus, the water-holding capacity of which is greater than that of cellulose types produced using static cultivation methods. The Young's modulus of the product can be manipulated by varying the number of net plates in the modified airlift bioreactor. The BC membrane produced using the proposed bioreactor exhibits potential for practical application.

  1. Production of bacterial cellulose membranes in a modified airlift bioreactor by Gluconacetobacter xylinus.

    PubMed

    Wu, Sheng-Chi; Li, Meng-Hsun

    2015-10-01

    In this study, a novel bioreactor for producing bacterial cellulose (BC) is proposed. Traditional BC production uses static culture conditions and produces a gelatinous membrane. The potential for using various types of bioreactor, including a stirred tank, conventional airlift, and modified airlift with a rectangular wire-mesh draft tube, in large-scale production has been investigated. The BC obtained from these bioreactors is fibrous or in pellet form. Our proposed airlift bioreactor produces a membrane-type BC from Gluconacetobacter xylinus, the water-holding capacity of which is greater than that of cellulose types produced using static cultivation methods. The Young's modulus of the product can be manipulated by varying the number of net plates in the modified airlift bioreactor. The BC membrane produced using the proposed bioreactor exhibits potential for practical application. PMID:25823854

  2. Conductivity Analysis of Membranes for High-Temperature PEMFC Applications

    SciTech Connect

    Reed, R.; Turner, J.A.

    2005-01-01

    Low-temperature operation requirements for per-fluorinated membranes are one factor that limits the viability of current fuel cell technology for transportation and other uses. Because of this, high-temperature membrane materials are being researched. The protonic conductivity of organic/inorganic hybrid composites, Nafion® analog material, and heteropoly acid doped Nafion membranes were studied using a BekkTech® conductivity test cell as a hydrogen pump. The goal was to find a high-temperature membrane with sufficient enough conductive properties to replace the currently implemented low-temperature membranes, such as Nafion. Four-point conductivity measurements were taken using a hydrogen pump experiment. Results showed that one of the organic/inorganic membranes that we tested had similar protonic conductivity to Nafion. Nafion analog membranes were shown to have similar to slightly better conductivity than Nafion at high-temperatures. However, like Nafion, performance dropped upon dehydration of the membrane at higher temperatures. Of the heteropoly acid doped Nafion membranes studied, silicotungstic acid was found to be, overall, the most promising for use as a dopant.

  3. Morphology Effect on Proton Dynamics in Nafion® 117 and Sulfonated Polyether Ether Ketone

    NASA Astrophysics Data System (ADS)

    Leong, Jun Xing; Diño, Wilson Agerico; Ahmad, Azizan; Daud, Wan Ramli Wan; Kasai, Hideaki

    2016-09-01

    We report results of our experimental and theoretical studies on the dynamics of proton conductivity in Nafion® 117 and self-fabricated sulfonated polyether ether ketone (SPEEK) membranes. Knowing that the presence of water molecules in the diffusion process results in a lower energy barrier, we determined the diffusion barriers and corresponding tunneling probabilities of Nafion® 117 and SPEEK system using a simple theoretical model that excludes the medium (water molecules) in the initial calculations. We then propose an equation that relates the membrane conductivity to the tunneling probability. We recover the effect of the medium by introducing a correction term into the proposed equation, which takes into account the effect of the proton diffusion distance and the hydration level. We have also experimentally verified that the proposed equation correctly explain the difference in conductivity between Nafion® 117 and SPEEK. We found that membranes that are to be operated in low hydration environments (high temperatures) need to be designed with short diffusion distances to enhance and maintain high conductivity.

  4. Arabidopsis CURVATURE THYLAKOID1 Proteins Modify Thylakoid Architecture by Inducing Membrane Curvature[W

    PubMed Central

    Armbruster, Ute; Labs, Mathias; Pribil, Mathias; Viola, Stefania; Xu, Wenteng; Scharfenberg, Michael; Hertle, Alexander P.; Rojahn, Ulrike; Jensen, Poul Erik; Rappaport, Fabrice; Joliot, Pierre; Dörmann, Peter; Wanner, Gerhard; Leister, Dario

    2013-01-01

    Chloroplasts of land plants characteristically contain grana, cylindrical stacks of thylakoid membranes. A granum consists of a core of appressed membranes, two stroma-exposed end membranes, and margins, which connect pairs of grana membranes at their lumenal sides. Multiple forces contribute to grana stacking, but it is not known how the extreme curvature at margins is generated and maintained. We report the identification of the CURVATURE THYLAKOID1 (CURT1) protein family, conserved in plants and cyanobacteria. The four Arabidopsis thaliana CURT1 proteins (CURT1A, B, C, and D) oligomerize and are highly enriched at grana margins. Grana architecture is correlated with the CURT1 protein level, ranging from flat lobe-like thylakoids with considerably fewer grana margins in plants without CURT1 proteins to an increased number of membrane layers (and margins) in grana at the expense of grana diameter in overexpressors of CURT1A. The endogenous CURT1 protein in the cyanobacterium Synechocystis sp PCC6803 can be partially replaced by its Arabidopsis counterpart, indicating that the function of CURT1 proteins is evolutionary conserved. In vitro, Arabidopsis CURT1A proteins oligomerize and induce tubulation of liposomes, implying that CURT1 proteins suffice to induce membrane curvature. We therefore propose that CURT1 proteins modify thylakoid architecture by inducing membrane curvature at grana margins. PMID:23839788

  5. Performance enhancement of polyvinyl chloride ultrafiltration membrane modified with graphene oxide.

    PubMed

    Zhao, Yuanyuan; Lu, Jiaqi; Liu, Xuyang; Wang, Yudan; Lin, Jiuyang; Peng, Na; Li, Jingchun; Zhao, Fangbo

    2016-10-15

    A novel polyvinyl chloride (PVC) membrane was modified with graphene oxide (GO) via phase inversion method to improve its hydrophilicity and mechanical properties. The GO presented a large amount of hydrophilic groups after the modification through the modified Hummers method. It was observed that with the addition of low fraction of GO powder, the GO/PVC hybrid membranes exhibited a significant enhancement in hydrophilicity, water flux, and mechanical properties. With optimal dosage (0.1wt%), the pure water flux of GO/PVC membrane increased from 232.6L/(m(2)hbar) to 430.0L/(m(2)hbar) and the tensile strength increased from 231.3cN to 305.3cN. The improved properties of the PVC/GO hybrid membranes are mainly attributed to the strong hydrophilicity of functional groups on the GO surface, indicating that GO has a promising candidate for modification of PVC ultrafiltration membranes in wastewater treatment.

  6. Characterization and Evaluation of Reverse Osmosis Membranes Modified with Ag2O Nanoparticles to Improve Performance.

    PubMed

    Al-Hobaib, Abdullah S; Al-Sheetan, Khalid M; Shaik, Mohammed Rafi; Al-Andis, Naser M; Al-Suhybani, M S

    2015-12-01

    The objective of this work was to prepare and characterize a new and highly efficient modified membrane by in situ interfacial polymerization on porous polysulfone supports. The process used m-phenylenediamine and trimesoyl chloride in hexane, incorporating silver oxide Ag2O nanoparticles of varied concentrations from 0.001 to 0.1 wt%. Ag2O nanoparticles were prepared at different sizes varying between 20 and 50 nm. The modified membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), transmission electron microscopy (TEM), and contact angle measurement. The results showed a smooth membrane surface and average surface roughness from 31 to 74 nm. Moreover, hydrophilicity improved and the contact angle decreased to 41° at 0.009 wt% silver oxide. The performances of the developed membranes were investigated by measuring permeate fluxes and salt rejection capability by passing NaCl solutions (2000 ppm) through the membranes at 225 psi. The results showed that the flux increased from 26 to 40.5 L/m(2) h, while the salt rejection was high, at 99 %, with 0.003 wt% Ag2O nanoparticles.

  7. Characterization and Evaluation of Reverse Osmosis Membranes Modified with Ag2O Nanoparticles to Improve Performance

    NASA Astrophysics Data System (ADS)

    Al-Hobaib, Abdullah S.; AL-Sheetan, Khalid M.; Shaik, Mohammed Rafi; Al-Andis, Naser M.; Al-Suhybani, M. S.

    2015-09-01

    The objective of this work was to prepare and characterize a new and highly efficient modified membrane by in situ interfacial polymerization on porous polysulfone supports. The process used m-phenylenediamine and trimesoyl chloride in hexane, incorporating silver oxide Ag2O nanoparticles of varied concentrations from 0.001 to 0.1 wt%. Ag2O nanoparticles were prepared at different sizes varying between 20 and 50 nm. The modified membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), transmission electron microscopy (TEM), and contact angle measurement. The results showed a smooth membrane surface and average surface roughness from 31 to 74 nm. Moreover, hydrophilicity improved and the contact angle decreased to 41° at 0.009 wt% silver oxide. The performances of the developed membranes were investigated by measuring permeate fluxes and salt rejection capability by passing NaCl solutions (2000 ppm) through the membranes at 225 psi. The results showed that the flux increased from 26 to 40.5 L/m2 h, while the salt rejection was high, at 99 %, with 0.003 wt% Ag2O nanoparticles.

  8. Permeability of membranes to amino acids and modified amino acids: mechanisms involved in translocation

    NASA Technical Reports Server (NTRS)

    Chakrabarti, A. C.; Deamer, D. W. (Principal Investigator); Miller, S. L. (Principal Investigator)

    1994-01-01

    The amino acid permeability of membranes is of interest because they are one of the key solutes involved in cell function. Membrane permeability coefficients (P) for amino acid classes, including neutral, polar, hydrophobic, and charged species, have been measured and compared using a variety of techniques. Decreasing lipid chain length increased permeability slightly (5-fold), while variations in pH had only minor effects on the permeability coefficients of the amino acids tested in liposomes. Increasing the membrane surface charge increased the permeability of amino acids of the opposite charge, while increasing the cholesterol content decreased membrane permeability. The permeability coefficients for most amino acids tested were surprisingly similar to those previously measured for monovalent cations such as sodium and potassium (approximately 10(-12)-10(-13) cm s-1). This observation suggests that the permeation rates for the neutral, polar and charged amino acids are controlled by bilayer fluctuations and transient defects, rather than partition coefficients and Born energy barriers. Hydrophobic amino acids were 10(2) more permeable than the hydrophilic forms, reflecting their increased partition coefficient values. External pH had dramatic effects on the permeation rates for the modified amino acid lysine methyl ester in response to transmembrane pH gradients. It was established that lysine methyl ester and other modified short peptides permeate rapidly (P = 10(-2) cm s-1) as neutral (deprotonated) molecules. It was also shown that charge distributions dramatically alter permeation rates for modified di-peptides. These results may relate to the movement of peptides through membranes during protein translocation and to the origin of cellular membrane transport on the early Earth.

  9. Characterization of charge properties of an ultrafiltration membrane modified by surface grafting of poly(allylamine) hydrochloride.

    PubMed

    Dejeu, J; Lakard, B; Fievet, P; Lakard, S

    2009-05-01

    A polyethersulfone ultrafiltration membrane was functionalized by a cationic polyelectrolyte, the poly(allylamine) hydrochloride (PAH). The influence of the time of adsorption of PAH on the membrane charge properties was studied. Several characterization techniques were used to investigate the membrane modification. Tangential and transmembrane streaming potential measurements were conducted to characterize the outer and inner surfaces of the membrane, respectively. Both techniques indicated that the surface modification of the membrane was efficient. The charge of the outer surface was reversed (from negative values for the unmodified membrane to positive values for the modified membrane) and the charge of the inner surface was neutralized after adsorption of the cationic polyelectrolyte onto the pore walls. The modification of both the outer surface of the membrane and the pore walls was also put in evidence with membrane potential measurements. It was found that the charge of the PAH-modified membrane is affected by the time of immersion in PAH solution. Experimental data seem to show a fast modification of the membrane for the first 15 min; nevertheless, the modification was more pronounced after 24 h of PAH adsorption. Diffusion experiments carried out with unmodified and modified membranes for four salts (KCl, NaCl, MgCl, and CaCl(2)) showed a decrease in the salt permeability after functionalization of the membrane. The permeability decrease was greater for 2:1 salts than for 1:1 salts. This decrease was explained by electrostatic interactions. PMID:19215937

  10. Pressure dependence of the oxygen reduction reaction at the platinum microelectrode/nafion interface - Electrode kinetics and mass transport

    NASA Technical Reports Server (NTRS)

    Parthasarathy, Arvind; Srinivasan, Supramaniam; Appleby, A. J.; Martin, Charles R.

    1992-01-01

    The investigation of oxygen reduction kinetics at the platinum/Nafion interface is of great importance in the advancement of proton-exchange-membrane (PEM) fuel-cell technology. This study focuses on the dependence of the oxygen reduction kinetics on oxygen pressure. Conventional Tafel analysis of the data shows that the reaction order with respect to oxygen is unity at both high and low current densities. Chronoamperometric measurements of the transport parameters for oxygen in Nafion show that oxygen dissolution follows Henry's isotherm. The diffusion coefficient of oxygen is invariant with pressure; however, the diffusion coefficient for oxygen is lower when air is used as the equilibrating gas as compared to when oxygen is used for equilibration. These results are of value in understanding the influence of O2 partial pressure on the performance of PEM fuel cells and also in elucidating the mechanism of oxygen reduction at the platinum/Nafion interface.

  11. Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

    NASA Technical Reports Server (NTRS)

    Parthasarathy, Arvind; Srinivasan, Supramanian; Appleby, A. J.; Martin, Charles R.

    1992-01-01

    Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

  12. Radiation-grafted, chemically modified membranes part I - Synthesis of a selective aluminum material

    NASA Astrophysics Data System (ADS)

    Bazante-Yamaguishi, Renata; Moura, Eduardo; Manzoli, José E.; Geraldo, Aurea B. C.

    2014-01-01

    Polymeric membranes were styrene grafted by irradiation methods and the obtained material was chemically modified to become aluminum selective. For this purpose, polymeric substrates of PVC (polyvinyl chloride) and PP (polypropylene) were styrene grafted mutually by gamma and electron beam irradiation. The modification process includes three basic reaction paths: Friedel-Crafts acylation, 2-methylanisole coupling and a final oxidation to achieve aluminum selectivity. Although this specific chemical modification in derivatives of polystyrene is not new, the new challenge is to obtain a selective material where original membrane characteristics (physical shape and mechanical resistance) are minimally conserved after such an aggressive treatment.

  13. Protein adsorption capability on polyurethane and modified-polyurethane membrane for periodontal guided tissue regeneration applications.

    PubMed

    Sheikh, Zeeshan; Khan, Abdul Samad; Roohpour, Nima; Glogauer, Michael; Rehman, Ihtesham U

    2016-11-01

    Periodontal disease if left untreated can result in creation of defects within the alveolar ridge. Barrier membranes are frequently used with or without bone replacement graft materials for achieving periodontal guided tissue regeneration (GTR). Surface properties of barrier membranes play a vital role in their functionality and clinical success. In this study polyetherurethane (PEU) membranes were synthesized by using 4,4'-methylene-diphenyl diisocyanate (MDI), polytetramethylene oxide (PTMO) and 1,4-butane diol (BDO) as a chain extender via solution polymerization. Hydroxyl terminated polydimethylsiloxane (PDMS) due to having inherent surface orientation towards air was used for surface modification of PEU on one side of the membranes. This resulting membranes had one surface being PEU and the other being PDMS coated PEU. The prepared membranes were treated with solutions of bovine serum albumin (BSA) in de-ionized water at 37°C at a pH of 7.2. The surface protein adsorptive potential of PEU membranes was observed using Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), Raman spectroscopy and Confocal Raman spectroscopy. The contact angle measurement, tensile strength and modulus of prepared membranes were also evaluated. PEU membrane (89.86±1.62°) exhibited less hydrophobic behavior than PEU-PDMS (105.87±3.16°). The ultimate tensile strength and elastic modulus of PEU (27±1MPa and 14±2MPa) and PEU-PDMS (8±1MPa and 26±1MPa) membranes was in required range. The spectral analysis revealed adsorption of BSA proteins on the surface of non PDMS coated PEU surface. The PDMS modified PEU membranes demonstrated a lack of BSA adsorption. The non PDMS coated side of the membrane which adsorbs proteins could potentially be used facing towards the defect attracting growth factors for periodontal tissue regeneration. Whereas, the PDMS coated side could serve as an occlusive barrier for preventing gingival epithelial cells from

  14. Protein adsorption capability on polyurethane and modified-polyurethane membrane for periodontal guided tissue regeneration applications.

    PubMed

    Sheikh, Zeeshan; Khan, Abdul Samad; Roohpour, Nima; Glogauer, Michael; Rehman, Ihtesham U

    2016-11-01

    Periodontal disease if left untreated can result in creation of defects within the alveolar ridge. Barrier membranes are frequently used with or without bone replacement graft materials for achieving periodontal guided tissue regeneration (GTR). Surface properties of barrier membranes play a vital role in their functionality and clinical success. In this study polyetherurethane (PEU) membranes were synthesized by using 4,4'-methylene-diphenyl diisocyanate (MDI), polytetramethylene oxide (PTMO) and 1,4-butane diol (BDO) as a chain extender via solution polymerization. Hydroxyl terminated polydimethylsiloxane (PDMS) due to having inherent surface orientation towards air was used for surface modification of PEU on one side of the membranes. This resulting membranes had one surface being PEU and the other being PDMS coated PEU. The prepared membranes were treated with solutions of bovine serum albumin (BSA) in de-ionized water at 37°C at a pH of 7.2. The surface protein adsorptive potential of PEU membranes was observed using Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), Raman spectroscopy and Confocal Raman spectroscopy. The contact angle measurement, tensile strength and modulus of prepared membranes were also evaluated. PEU membrane (89.86±1.62°) exhibited less hydrophobic behavior than PEU-PDMS (105.87±3.16°). The ultimate tensile strength and elastic modulus of PEU (27±1MPa and 14±2MPa) and PEU-PDMS (8±1MPa and 26±1MPa) membranes was in required range. The spectral analysis revealed adsorption of BSA proteins on the surface of non PDMS coated PEU surface. The PDMS modified PEU membranes demonstrated a lack of BSA adsorption. The non PDMS coated side of the membrane which adsorbs proteins could potentially be used facing towards the defect attracting growth factors for periodontal tissue regeneration. Whereas, the PDMS coated side could serve as an occlusive barrier for preventing gingival epithelial cells from

  15. Molecular Composite Coatings on Nafion Using Layer-by-Layer Self-Assembly.

    PubMed

    Lefaux, Christophe J; Kim, Byoung-Suhk; Venkat, Narayanan; Mather, Patrick T

    2015-05-20

    Controlled growth of nanometer-scale multilayered coatings of negatively charged sulfonated poly(benzobisimidazole) (SPBI), complexed with positively charged poly(2-vinylpyridine) (P2VP) on quartz, and Nafion membrane as substrates has been explored. Both polymers, SPBI and P2VP, possess a net charge in methanol as a result of the dissolution of SPBI by complexation with triethylamine (TEA) and the protonation of P2VP with HCl, respectively, and thereby can form a multilayered molecular composite of alternating anionic SPBI and cationic P2VP via an electrostatic layer-by-layer (LbL) self-assembly. UV-vis absorption spectrophotometry was used to monitor the buildup and growth rate of such SPBI/P2VP multilayer films. Atomic force microscopy (AFM) was used to determine the roughness and thickness of the resulting SPBI/P2VP multilayers. As a result, it was found that a steady-state linear growth regime for the LbL self-assembled SPBI/P2VP multilayer films and coatings onto quartz and Nafion membranes was observed after completion of the first few deposition cycles, indicating the successful formation of the SPBI/P2VP multilayered assembly in methanol solutions. In addition, the SPBI/P2VP multilayer films in the perpendicular direction (flat view) demonstrated isotropic orientation distribution on the Nafion membrane, while the SPBI/P2VP multilayer films examined by X-ray scattering in the parallel direction (edge view) revealed anisotropic orientation, the combined observations indicating confinement of SPBI rods to the plane of the coating. We further found that the SPBI/P2VP multilayer coated Nafion possesses good thermal stability, as indicated by isothermal gravimetric analysis at 310 °C, and it was further observed that SPBI/P2VP multilayer coatings using the LbL self-assembly technique on Nafion membrane significantly increased the membrane stiffness, despite the small coating thickness employed. PMID:25923689

  16. Highly conductive polymer electrolyte membranes modified with polyethylene glycol-bis-carbamate

    NASA Astrophysics Data System (ADS)

    Fu, Guopeng; Dempsey, Janel; Kyu, Thein

    By virtue of its non-flammability and chemical stability, polyethylene glycol (PEG) networks have shown potential application in all solid-state polymer electrolyte membranes (PEM). However, room temperature ionic conductivity of these PEG based PEMs is inherently low. Plasticization of these PEMs is needed to improve the ionic conductivity. It was demonstrated by this group that small-molecule plasticizers such as succinonitrile, ethylene carbonate, or urea-carbamate can boost ionic conductivity of solid-state polymer electrolyte membranes. Polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction of polyethylene glycol diamine and ethylene carbonate. The PEGBC modified PEM has shown higher ionic conductivity relative to the unmodified PEM. Moreover, PEGBC modified PEM has a better thermal stability relative to ethylene carbonate based liquid electrolyte with enhanced ionic conductivity. Supported by NSF-DMR 1161070, 1502543 and REU 1359321.

  17. Water permeability of polyethylene terephthalate track membranes modified in plasma of dimethylaniline

    NASA Astrophysics Data System (ADS)

    Kravets, Lyubov; Dmitriev, Serguei; Gilman, Alla; Drachev, Alexander

    2004-09-01

    The surface properties and hydrodynamic characteristics of composite membranes consisting of a porous substrate, on which a polymer layer from a direct current discharge in a mixture of air and vapours of dimethylaniline was deposited, have been investigated. As a substrate, we used poly(ethylene) terephthalate track membrane (PET TM) of the thickness of 10 μ m and the effective pore diameter of 0.215 μ m (pore density is 2\\cdot 10^8 cm-2). The performed researches show that when treating the membranes in plasma, two competing processes are observed: deposition of the polymer layer on a membrane surface, that testifies increase of the mass of sample, and etching of a polymeric matrix which causes growth of effective pore diameter. The last process is stipulated by presence of oxygen in the gas mixture. Decreasing the degree of overweight of the sample at increasing the treatment time leads us to a supposition that a dominating process in this case becomes the process of gas-discharge etching. In all cases, if treating PET TM, a drop of the water contact angle occurs, i.e. hydrophilization of the membrane surface takes place that is connected first of all with a grafting of polymer layer containing polar functional groups. The research in the hydrodynamic characteristics of the initial PET TM and the membranes modified in plasma at neutral and subacid pH value of filtrate leads to a linear dependence of their permeability upon the quantity of applied pressure. It is connected with a viscous character of the flow, that is, when the diameter of the pores of the membrane is much more than the size of the water molecules. This fact shows that the macromolecules of the deposited polymer layer in this case have a compact conformation, which does not hinder the water molecules infiltration. At a lower pH value of the filtrate, the picture cardinally changes. For modified in plasma membranes a diversion from the linear relation is observed. This means that in this case

  18. Interaction study between maltose-modified PPI dendrimers and lipidic model membranes.

    PubMed

    Wrobel, Dominika; Appelhans, Dietmar; Signorelli, Marco; Wiesner, Brigitte; Fessas, Dimitrios; Scheler, Ulrich; Voit, Brigitte; Maly, Jan

    2015-07-01

    The influence of maltose-modified poly(propylene imine) (PPI) dendrimers on dimyristoylphosphatidylcholine (DMPC) or dimyristoylphosphatidylcholine/dimyristoylphosphatidylglycerol (DMPC/DMPG) (3%) liposomes was studied. Fourth generation (G4) PPI dendrimers with primary amino surface groups were partially (open shell glycodendrimers - OS) or completely (dense shell glycodendrimers - DS) modified with maltose residues. As a model membrane, two types of 100nm diameter liposomes were used to observe differences in the interactions between neutral DMPC and negatively charged DMPC/DMPG bilayers. Interactions were studied using fluorescence spectroscopy to evaluate the membrane fluidity of both the hydrophobic and hydrophilic parts of the lipid bilayer and using differential scanning calorimetry to investigate thermodynamic parameter changes. Pulsed-filed gradient NMR experiments were carried out to evaluate common diffusion coefficient of DMPG and DS PPI in D2O when using below critical micelle concentration of DMPG. Both OS and DS PPI G4 dendrimers show interactions with liposomes. Neutral DS dendrimers exhibit stronger changes in membrane fluidity compared to OS dendrimers. The bilayer structure seems more rigid in the case of anionic DMPC/DMPG liposomes in comparison to pure and neutral DMPC liposomes. Generally, interactions of dendrimers with anionic DMPC/DMPG and neutral DMPC liposomes were at the same level. Higher concentrations of positively charged OS dendrimers induced the aggregation process with negatively charged liposomes. For all types of experiments, the presence of NaCl decreased the strength of the interactions between glycodendrimers and liposomes. Based on NMR diffusion experiments we suggest that apart from electrostatic interactions for OS PPI hydrogen bonds play a major role in maltose-modified PPI dendrimer interactions with anionic and neutral model membranes where a contact surface is needed for undergoing multiple H-bond interactions between

  19. Interaction study between maltose-modified PPI dendrimers and lipidic model membranes.

    PubMed

    Wrobel, Dominika; Appelhans, Dietmar; Signorelli, Marco; Wiesner, Brigitte; Fessas, Dimitrios; Scheler, Ulrich; Voit, Brigitte; Maly, Jan

    2015-07-01

    The influence of maltose-modified poly(propylene imine) (PPI) dendrimers on dimyristoylphosphatidylcholine (DMPC) or dimyristoylphosphatidylcholine/dimyristoylphosphatidylglycerol (DMPC/DMPG) (3%) liposomes was studied. Fourth generation (G4) PPI dendrimers with primary amino surface groups were partially (open shell glycodendrimers - OS) or completely (dense shell glycodendrimers - DS) modified with maltose residues. As a model membrane, two types of 100nm diameter liposomes were used to observe differences in the interactions between neutral DMPC and negatively charged DMPC/DMPG bilayers. Interactions were studied using fluorescence spectroscopy to evaluate the membrane fluidity of both the hydrophobic and hydrophilic parts of the lipid bilayer and using differential scanning calorimetry to investigate thermodynamic parameter changes. Pulsed-filed gradient NMR experiments were carried out to evaluate common diffusion coefficient of DMPG and DS PPI in D2O when using below critical micelle concentration of DMPG. Both OS and DS PPI G4 dendrimers show interactions with liposomes. Neutral DS dendrimers exhibit stronger changes in membrane fluidity compared to OS dendrimers. The bilayer structure seems more rigid in the case of anionic DMPC/DMPG liposomes in comparison to pure and neutral DMPC liposomes. Generally, interactions of dendrimers with anionic DMPC/DMPG and neutral DMPC liposomes were at the same level. Higher concentrations of positively charged OS dendrimers induced the aggregation process with negatively charged liposomes. For all types of experiments, the presence of NaCl decreased the strength of the interactions between glycodendrimers and liposomes. Based on NMR diffusion experiments we suggest that apart from electrostatic interactions for OS PPI hydrogen bonds play a major role in maltose-modified PPI dendrimer interactions with anionic and neutral model membranes where a contact surface is needed for undergoing multiple H-bond interactions between

  20. Water sorption, viscoelastic, and optical properties of thin NafionRTM films

    NASA Astrophysics Data System (ADS)

    Petrina, Stephanie Ann

    The hydrogen fuel cell industry continues to make strides in terms of improving device efficiency and performance, yet ion transport within the catalyst layer is not well understood. Thin ionomer films coating the catalytic particles are responsible for proton transport throughout the catalytic layer, yet the basic physical properties of these thin films, which interact with the catalyst surface, are widely unknown. Fundamentally, the material properties of thin polymer films are known to deviate from thick, free-standing membranes composed of the same material based on their interfacial interactions. The work in this dissertation seeks to uncover the properties of thin NafionRTM films to begin to understand their role in catalyst layer performance. By identifying the influence of processing conditions, polymer--substrate interaction, and thickness on water uptake characteristics of thin Nafion RTM films, the proton and oxygen transport parameters that are most relevant to performance in the catalyst layer can be understood. Since the hydration of NafionRTM is relevant for its proton conduction and performance in a fuel cell, water sorption of substrate--supported NafionRTM thin films was characterized via the change in sample mass and thickness as the relative humidity (RH) of the sample environment was varied. Monolithic thin NafionRTM films were characterized for a variety of sample preparation conditions and substrates to identify how processing conditions and other sample parameters may affect water uptake. Spin cast NafionRTM films exhibited low density and refractive index for very thin films due to the higher relative void fraction induced by rapid film formation. The density of hydrated films was observed to decrease beyond the volume additivity limit as RH increased, and the relationship between density and refractive index was confirmed with the Lorentz-Lorenz relationship. The complex refractive indices (N = n + ik) of substrate--supported Nafion RTM

  1. Respiratory epithelial cytotoxicity and membrane damage (holes) caused by amine-modified nanoparticles.

    PubMed

    Ruenraroengsak, Pakatip; Novak, Pavel; Berhanu, Deborah; Thorley, Andrew J; Valsami-Jones, Eugenia; Gorelik, Julia; Korchev, Yuri E; Tetley, Teresa D

    2012-02-01

    The respiratory epithelium is a significant target of inhaled, nano-sized particles, the biological reactivity of which will depend on its physicochemical properties. Surface-modified, 50 and 100 nm, polystyrene latex nanoparticles (NPs) were used as model particles to examine the effect of particle size and surface chemistry on transformed human alveolar epithelial type 1-like cells (TT1). Live images of TT1 exposed to amine-modified NPs taken by hopping probe ion conductance microscopy revealed severe damage and holes on cell membranes that were not observed with other types of NPs. This paralleled induction of cell detachment, cytotoxicity and apoptotic (caspase-3/7 and caspase-9) cell death, and increased release of CXCL8 (IL-8). In contrast, unmodified, carboxyl-modified 50 nm NPs and the 100 nm NPs did not cause membrane damage, and were less reactive. Thus, the susceptibility and membrane damage to respiratory epithelium following inhalation of NPs will depend on both surface chemistry (e.g., cationic) and nano-size. PMID:21352086

  2. NMR and pulsed field gradient NMR approach of water sorption properties in Nafion at low temperature.

    PubMed

    Guillermo, Armel; Gebel, Gérard; Mendil-Jakani, Hakima; Pinton, Eric

    2009-05-14

    The water uptake and the water self-diffusion coefficient were measured in Nafion membranes at subzero temperatures. NMR spectroscopy was used to precisely quantify the actual concentration of water in membranes as a function of the temperature and their hydration rates at room temperature. We find that below 273 K the water concentration decreases with temperature to reach, at around 220 K, a limit value independent of the initial concentration. This regime is observed if the concentration at room temperature is higher than 10%. Below this concentration no membrane deswelling was observed. The water self-diffusion coefficient, measured by pulsed field gradient NMR in function of the temperature, is determined by the actual concentration C(T) whatever the concentration at room temperature. The concentration variation is attributed to a decrease in the relative humidity RH(T) of the water vapor surrounding the membrane induced by the simultaneous presence of supercooled water inside the membrane and ice outside the membrane.

  3. Enhancement of dopamine sensing by layer-by-layer assembly of PVI-dmeOs and Nafion on carbon nanotubes.

    PubMed

    Cui, Hui-Fang; Cui, Yu-Han; Sun, Yu-Long; Zhang, Kuan; Zhang, Wei-De

    2010-05-28

    In this study, carbon nanotubes (CNTs) were modified to further improve their performance in electrochemical sensing of dopamine (DA) levels. After a redox polymer, poly(vinylimidazole) complexed with Os(4, 4'-dimethyl- 2, 2-bipyridine)(2)Cl (termed PVI-dmeOs) was electrodeposited on multi-wall CNTs (MWCNTs), Nafion and PVI-dmeOs films were successfully layer-by-layer (LBL) assembled on the hydrophilic surface of the as-prepared PVI-dmeOs/CNTs nanocomposites through electrostatic interactions. The LBL assembly was proved by scanning electron microscopy (SEM), electrochemistry and UV-vis spectroscopy measurements. LBL assembly of Nafion/PVI-dmeOs films on CNTs significantly enhanced their linear sweep voltammetry (LSV) response sensitivity to DA, with a maximum enhancement for three Nafion/PVI-dmeOs film-modified MWCNTs. The LSV peak current density of (Nafion/PV I-dmeOs)(3)/CNT electrodes in response to 10 and 50 microM DA solutions was about 7.3 and 3.9 times those for bare CNTs. At the (Nafion/PV I-dmeOs)(3)/CNT electrodes, the limit of detection (LOD) (signal-to-noise ratio: 3) was 0.05 microM DA, the linear range was 0.1-10 microM DA (with a linear regression coefficient of 0.97) and the DA-sensing sensitivity was 8.15 microA cm( - 2) microM( - 1). The newly fabricated (Nafion/PV I-dmeOs)(3)/CNT electrodes may be developed as an ideal biosensor for direct and in situ measurement of DA levels. PMID:20431203

  4. Mechanism for degradation of Nafion in PEM fuel cells from quantum mechanics calculations.

    PubMed

    Yu, Ted H; Sha, Yao; Liu, Wei-Guang; Merinov, Boris V; Shirvanian, Pezhman; Goddard, William A

    2011-12-14

    We report results of quantum mechanics (QM) mechanistic studies of Nafion membrane degradation in a polymer electrolyte membrane (PEM) fuel cell. Experiments suggest that Nafion degradation is caused by generation of trace radical species (such as OH(●), H(●)) only when in the presence of H(2), O(2), and Pt. We use density functional theory (DFT) to construct the potential energy surfaces for various plausible reactions involving intermediates that might be formed when Nafion is exposed to H(2) (or H(+)) and O(2) in the presence of the Pt catalyst. We find a barrier of 0.53 eV for OH radical formation from HOOH chemisorbed on Pt(111) and of 0.76 eV from chemisorbed OOH(ad), suggesting that OH might be present during the ORR, particularly when the fuel cell is turned on and off. Based on the QM, we propose two chemical mechanisms for OH radical attack on the Nafion polymer: (1) OH attack on the S-C bond to form H(2)SO(4) plus a carbon radical (barrier: 0.96 eV) followed by decomposition of the carbon radical to form an epoxide (barrier: 1.40 eV). (2) OH attack on H(2) crossover gas to form hydrogen radical (barrier: 0.04 eV), which subsequently attacks a C-F bond to form HF plus carbon radicals (barrier as low as 1.00 eV). This carbon radical can then decompose to form a ketone plus a carbon radical with a barrier of 0.86 eV. The products (HF, OCF(2), SCF(2)) of these proposed mechanisms have all been observed by F NMR in the fuel cell exit gases along with the decrease in pH expected from our mechanism.

  5. [Transport of large organic ions through syringomycin channels in the membranes containing dipole modifiers].

    PubMed

    Efimova, S S; Ostroumova, O S; Malev, V V; Shchagina, L V

    2011-01-01

    The effect of the membrane dipole potential (Phid) on a conductance and a steady-state number of functioning channels formed by cyclic lipodepsipeptide syringomycin E (SRE) in bilayer lipid membranes made from phosphocholine and bathed in 0.4 M solution of sodium salts of aspartate, gluconate and chloride was shown. The magnitude of Phid was varied with the introduction to membrane bathing solutions of phloretin, which reduces the Phid, and RH 421, increasing the Phid. It was established that in all studied systems the increase in the membrane dipole potential cause a decrease in the steady-state number of open channels. In the systems containing sodium salts of aspartate (Asp) or gluconate (Glc), changes in the number of functioning channels are in an order of magnitude smaller than in systems containing sodium chloride. At the same time, the conductance (g) of single SRE-channels on the membranes bathed in NaCI solution increases with the increase in Phid, and in the systems containing NaAsp or NaGlc the conductance of single channels does not depend on the Phid. The latter is due to the lack of cation/anion selectivity of the SRE-channels in these systems. The different channel-forming activity of SRE in the experimental systems is defined by the gating charge of the channel and the partition coefficient of the dipole modifiers between the lipid and aqueous phases.

  6. Blood compatibility comparison for polysulfone membranes modified by grafting block and random zwitterionic copolymers via surface-initiated ATRP.

    PubMed

    Xiang, Tao; Zhang, Li-Sha; Wang, Rui; Xia, Yi; Su, Bai-Hai; Zhao, Chang-Sheng

    2014-10-15

    For blood-contacting materials, good blood compatibility, especially good anticoagulant property is of great importance. Zwitterionic polymers have been proved to be resistant to nonspecific protein adsorption and platelet adhesion; however, their anticoagulant property is always inadequate. In this study, two kinds of zwitterionic copolymers (sulfobetaine methacrylate and sodium p-styrene sulfonate random copolymer and block copolymer) with sulfonic groups were covalently grafted from polysulfone (PSf) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) to improve blood compatibility. Field emission scanning electron microscopy (FE-SEM), attenuated total reflectance-Fourier transform infrared spectra (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and static water contact angle (WCA) were applied to characterize the morphologies, chemical compositions and hydrophilicity of the modified membranes. All the zwitterionic copolymer modified membranes showed improved blood compatibility, especially the anticoagulant property was obviously enhanced compared to the pristine PSf and simple zwitterionic polymer modified membranes. We also found that the random copolymer modified membranes showed better resistance to platelet adhesion than the block copolymer modified membranes. The zwitterionic copolymer modified membranes with integrated antifouling property and blood compatibility provided wide choice for specific applications such as hemodialysis, hemofiltration, and plasma separation. PMID:25072519

  7. Cholesterol Modifies Huntingtin Binding to, Disruption of, and Aggregation on Lipid Membranes.

    PubMed

    Gao, Xiang; Campbell, Warren A; Chaibva, Maxmore; Jain, Pranav; Leslie, Ashley E; Frey, Shelli L; Legleiter, Justin

    2016-01-12

    Huntington's disease (HD) is an inherited neurodegenerative disease caused by abnormally long CAG-repeats in the huntingtin gene that encode an expanded polyglutamine (polyQ) domain near the N-terminus of the huntingtin (htt) protein. Expanded polyQ domains are directly correlated to disease-related htt aggregation. Htt is found highly associated with a variety of cellular and subcellular membranes that are predominantly comprised of lipids. Since cholesterol homeostasis is altered in HD, we investigated how varying cholesterol content modifies the interactions between htt and lipid membranes. A combination of Langmuir trough monolayer techniques, vesicle permeability and binding assays, and in situ atomic force microscopy were used to directly monitor the interaction of a model, synthetic htt peptide and a full-length htt-exon1 recombinant protein with model membranes comprised of total brain lipid extract (TBLE) and varying amounts of exogenously added cholesterol. As the cholesterol content of the membrane increased, the extent of htt insertion decreased. Vesicles containing extra cholesterol were resistant to htt-induced permeabilization. Morphological and mechanical changes in the bilayer associated with exposure to htt were also drastically altered by the presence of cholesterol. Disrupted regions of pure TBLE bilayers were grainy in appearance and associated with a large number of globular aggregates. In contrast, morphological changes induced by htt in bilayers enriched in cholesterol were plateau-like with a smooth appearance. Collectively, these observations suggest that the presence and amount of cholesterol in lipid membranes play a critical role in htt binding and aggregation on lipid membranes.

  8. Cholesterol Modifies Huntingtin Binding to, Disruption of, and Aggregation on Lipid Membranes.

    PubMed

    Gao, Xiang; Campbell, Warren A; Chaibva, Maxmore; Jain, Pranav; Leslie, Ashley E; Frey, Shelli L; Legleiter, Justin

    2016-01-12

    Huntington's disease (HD) is an inherited neurodegenerative disease caused by abnormally long CAG-repeats in the huntingtin gene that encode an expanded polyglutamine (polyQ) domain near the N-terminus of the huntingtin (htt) protein. Expanded polyQ domains are directly correlated to disease-related htt aggregation. Htt is found highly associated with a variety of cellular and subcellular membranes that are predominantly comprised of lipids. Since cholesterol homeostasis is altered in HD, we investigated how varying cholesterol content modifies the interactions between htt and lipid membranes. A combination of Langmuir trough monolayer techniques, vesicle permeability and binding assays, and in situ atomic force microscopy were used to directly monitor the interaction of a model, synthetic htt peptide and a full-length htt-exon1 recombinant protein with model membranes comprised of total brain lipid extract (TBLE) and varying amounts of exogenously added cholesterol. As the cholesterol content of the membrane increased, the extent of htt insertion decreased. Vesicles containing extra cholesterol were resistant to htt-induced permeabilization. Morphological and mechanical changes in the bilayer associated with exposure to htt were also drastically altered by the presence of cholesterol. Disrupted regions of pure TBLE bilayers were grainy in appearance and associated with a large number of globular aggregates. In contrast, morphological changes induced by htt in bilayers enriched in cholesterol were plateau-like with a smooth appearance. Collectively, these observations suggest that the presence and amount of cholesterol in lipid membranes play a critical role in htt binding and aggregation on lipid membranes. PMID:26652744

  9. PVDF-HFP/ether-modified polysiloxane membranes obtained via airbrush spraying as active separators for application in lithium ion batteries.

    PubMed

    Seidel, S M; Jeschke, S; Vettikuzha, P; Wiemhöfer, H-D

    2015-08-01

    Improved hybrid polymer electrolyte membranes are introduced based on ether-modified polysiloxanes and poly(vinylidene fluoride-co-hexafluoropropylene) yielding a safe separator membrane, which is able to be sprayed directly onto lithium ion battery active materials, with an active role for enhanced ion transport.

  10. Reduction of thrombogenicity of PVC-based sodium selective membrane electrodes using heparin-modified chitosan.

    PubMed

    Badr, Ibrahim H A; Gouda, M; Abdel-Sattar, R; Sayour, Hossam E M

    2014-01-01

    Heparin-modified chitosan (H-chitosan) membrane was utilized to enhance biocompatibility of sodium selective membrane electrode based on the highly thrombogenic polyvinyl chloride (PVC). Sodium ion sensing film was prepared using PVC, sodium ionophore-X, potassium tetrakis(chlorophenyl)-borate, and o-nitrophenyloctylether. The PVC-based sensing film was sandwiched to chitosan or H-chitosan to prevent platelet adhesion on the surface of PVC. Potentiometric response characteristics of PVC-chitosan and PVC-H-chitosan membrane electrodes were found to be comparable to that of a control PVC based sodium-selective electrode. This indicates that chitosan and H-chitosan layers do not alter the response behaviour of the PVC-based sensing film. Biocompatibility of H-chitosan was confirmed by in vitro platelet adhesion study. The platelet adhesion investigations indicated that H-chitosan film is less thrombogenic compared to PVC, which could result in enhancement of biocompatibility of sodium selective membrane electrodes based on PVC, while maintaining the overall electrochemical performance of the PVC-based sensing film.

  11. Laminin modified infection-preventing collagen membrane containing silver sulfadiazine-hyaluronan microparticles.

    PubMed

    Lee, Jong-Eun; Park, Jong-Chul; Lee, Kwang Hoon; Oh, Sang Ho; Suh, Hwal

    2002-06-01

    The newly developed laminin modified infection-preventing collagen membrane consists of a 3 component laminate, comprising 2 outer collagen layers and a central laminin layer. The 2 outer collagen layers (dense and porous layers) were fabricated by air-drying and freeze drying, respectively, and the laminin layer was formed by a straightforward liquid coating method. In addition, hyaluronan based microparticles containing silver sulfadiazine (AgSD) were incorporated into the 2 collagen layers (AgSD content 50 microg/cm2). Laminin coated collagen surfaces did not promote fibroblast attachment but showed a retarded fibroblast proliferation rate and an increased rate of collagen synthesis versus pure collagen surfaces. In an animal study, a laminin coating on a nonmedicated collagen membrane significantly increased both wound size reduction and vessel proliferation 7 days after application versus polyurethane film. Interestingly, the laminin coated AgSD medicated collagen membrane demonstrated higher wound size reduction and vessel proliferation and lower inflammation than the polyurethane control, suggesting that the laminin AgSD medicated collagen membrane substantially improves dermal wound healing.

  12. Antibiofouling Polyvinylidene Fluoride Membrane Modified by Quaternary Ammonium Compound: Direct Contact-Killing versus Induced Indirect Contact-Killing.

    PubMed

    Zhang, Xingran; Ma, Jinxing; Tang, Chuyang Y; Wang, Zhiwei; Ng, How Yong; Wu, Zhichao

    2016-05-17

    Widespread applications of membrane technology call for the development of antibiofouling membranes. For the traditional contact-killing strategy, the antibacterial action is restricted to the surface: the membrane loses its antibiofouling efficacy once its surface is completely covered with a fouling layer. However, in this study, polyvinylidene fluoride (PVDF) microfiltration membranes blended with quaternary ammonium compound (QAC) exhibited a surprisingly lasting antimicrobial activity in the vicinity of the membrane surface. The results indicated that QAC was capable of driving surface segregation with a high structural stability, and the QAC modified membrane shows clear antibacterial effects against both Gram-positive and Gram-negative bacteria. Covering the modified membrane surface by an abiotic alginate layer resulted in a loss of antibacterial efficiency by 86.2%. In contrast, the antibacterial efficiency was maintained after developing a biofilm of Staphylococcus aureus of 30 μm in thickness. The current study may suggest that bacteria affected by contact-killing might interact with other bacteria in the vicinity, resulting in retarded biofilm growth. The antibiofouling effect and associated mechanism of the QAC modified membrane were further validated in a membrane bioreactor during long-term operation. PMID:27104660

  13. Square-wave stripping voltammetric determination of caffeic acid on electrochemically reduced graphene oxide-Nafion composite film.

    PubMed

    Filik, Hayati; Çetintaş, Gamze; Avan, Asiye Aslıhan; Aydar, Sevda; Koç, Serkan Naci; Boz, İsmail

    2013-11-15

    An electrochemical sensor composed of Nafion-graphene nanocomposite film for the voltammetric determination of caffeic acid (CA) was studied. A Nafion graphene oxide-modified glassy carbon electrode was fabricated by a simple drop-casting method and then graphene oxide was electrochemically reduced over the glassy carbon electrode. The electrochemical analysis method was based on the adsorption of caffeic acid on Nafion/ER-GO/GCE and then the oxidation of CA during the stripping step. The resulting electrode showed an excellent electrocatalytical response to the oxidation of caffeic acid (CA). The electrochemistry of caffeic acid on Nafion/ER-GO modified glassy carbon electrodes (GCEs) were studied by cyclic voltammetry and square-wave adsorption stripping voltammetry (SW-AdSV). At optimized test conditions, the calibration curve for CA showed two linear segments: the first linear segment increased from 0.1 to 1.5 and second linear segment increased up to 10 µM. The detection limit was determined as 9.1×10(-8) mol L(-1) using SW-AdSV. Finally, the proposed method was successfully used to determine CA in white wine samples.

  14. Photocurrent generation from thylakoid membranes on osmium-redox-polymer-modified electrodes.

    PubMed

    Hamidi, Hassan; Hasan, Kamrul; Emek, Sinan Cem; Dilgin, Yusuf; Åkerlund, Hans-Erik; Albertsson, Per-Åke; Leech, Dónal; Gorton, Lo

    2015-03-01

    Thylakoid membranes (TMs) are uniquely suited for photosynthesis owing to their distinctive structure and composition. Substantial efforts have been directed towards use of isolated photosynthetic reaction centers (PRCs) for solar energy harvesting, however, few studies investigate the communication between whole TMs and electrode surfaces, due to their complex structure. Here we report on a promising approach to generate photosynthesis-derived bioelectricity upon illumination of TMs wired with an osmium-redox-polymer modified graphite electrode, and generate a photocurrent density of 42.4 μA cm(-2).

  15. Poly(imide)/Organically-Modified Montmorillonite Nanocomposite as a Potential Membrane for Alkaline Fuel Cells

    PubMed Central

    Battirola, Liliane C.; Gasparotto, Luiz H. S.; Rodrigues-Filho, Ubirajara P.; Tremiliosi-Filho, Germano

    2012-01-01

    In this work we evaluated the potentiality of a poly(imide) (PI)/organically-modified montmorillonite (O-MMT) nanocomposite membrane for the use in alkaline fuel cells. Both X-ray diffraction and scanning electron microscopy revealed a good dispersion of O-MMT into the PI matrix and preservation of the O-MMT layered structure. When compared to the pure PI, the addition of O-MMT improved thermal stability and markedly increased the capability of absorbing electrolyte and ionic conductivity of the composite. The results show that the PI/O-MMT nanocomposite is a promising candidate for alkaline fuel cell applications. PMID:24958290

  16. Photocurrent generation from thylakoid membranes on osmium-redox-polymer-modified electrodes.

    PubMed

    Hamidi, Hassan; Hasan, Kamrul; Emek, Sinan Cem; Dilgin, Yusuf; Åkerlund, Hans-Erik; Albertsson, Per-Åke; Leech, Dónal; Gorton, Lo

    2015-03-01

    Thylakoid membranes (TMs) are uniquely suited for photosynthesis owing to their distinctive structure and composition. Substantial efforts have been directed towards use of isolated photosynthetic reaction centers (PRCs) for solar energy harvesting, however, few studies investigate the communication between whole TMs and electrode surfaces, due to their complex structure. Here we report on a promising approach to generate photosynthesis-derived bioelectricity upon illumination of TMs wired with an osmium-redox-polymer modified graphite electrode, and generate a photocurrent density of 42.4 μA cm(-2). PMID:25703722

  17. Exploiting lipopolysaccharide-induced deformation of lipid bilayers to modify membrane composition and generate two-dimensional geometric membrane array patterns

    PubMed Central

    Adams, Peter G.; Swingle, Kirstie L.; Paxton, Walter F.; Nogan, John J.; Stromberg, Loreen R.; Firestone, Millicent A.; Mukundan, Harshini; Montaño, Gabriel A.

    2015-01-01

    Supported lipid bilayers have proven effective as model membranes for investigating biophysical processes and in development of sensor and array technologies. The ability to modify lipid bilayers after their formation and in situ could greatly advance membrane technologies, but is difficult via current state-of-the-art technologies. Here we demonstrate a novel method that allows the controlled post-formation processing and modification of complex supported lipid bilayer arrangements, under aqueous conditions. We exploit the destabilization effect of lipopolysaccharide, an amphiphilic biomolecule, interacting with lipid bilayers to generate voids that can be backfilled to introduce desired membrane components. We further demonstrate that when used in combination with a single, traditional soft lithography process, it is possible to generate hierarchically-organized membrane domains and microscale 2-D array patterns of domains. Significantly, this technique can be used to repeatedly modify membranes allowing iterative control over membrane composition. This approach expands our toolkit for functional membrane design, with potential applications for enhanced materials templating, biosensing and investigating lipid-membrane processes. PMID:26015293

  18. Exploiting lipopolysaccharide-induced deformation of lipid bilayers to modify membrane composition and generate two-dimensional geometric membrane array patterns

    SciTech Connect

    Adams, Peter G.; Swingle, Kirstie L.; Paxton, Walter F.; Nogan, John J.; Stromberg, Loreen R.; Firestone, Millicent A.; Mukundan, Harshini; Montaño, Gabriel A.

    2015-05-27

    Supported lipid bilayers have proven effective as model membranes for investigating biophysical processes and in development of sensor and array technologies. The ability to modify lipid bilayers after their formation and in situ could greatly advance membrane technologies, but is difficult via current state-of-the-art technologies. Here we demonstrate a novel method that allows the controlled post-formation processing and modification of complex supported lipid bilayer arrangements, under aqueous conditions. We exploit the destabilization effect of lipopolysaccharide, an amphiphilic biomolecule, interacting with lipid bilayers to generate voids that can be backfilled to introduce desired membrane components. We further demonstrate that when used in combination with a single, traditional soft lithography process, it is possible to generate hierarchically-organized membrane domains and microscale 2-D array patterns of domains. Significantly, this technique can be used to repeatedly modify membranes allowing iterative control over membrane composition. This approach expands our toolkit for functional membrane design, with potential applications for enhanced materials templating, biosensing and investigating lipid-membrane processes.

  19. Exploiting lipopolysaccharide-induced deformation of lipid bilayers to modify membrane composition and generate two-dimensional geometric membrane array patterns

    DOE PAGES

    Adams, Peter G.; Swingle, Kirstie L.; Paxton, Walter F.; Nogan, John J.; Stromberg, Loreen R.; Firestone, Millicent A.; Mukundan, Harshini; Montaño, Gabriel A.

    2015-05-27

    Supported lipid bilayers have proven effective as model membranes for investigating biophysical processes and in development of sensor and array technologies. The ability to modify lipid bilayers after their formation and in situ could greatly advance membrane technologies, but is difficult via current state-of-the-art technologies. Here we demonstrate a novel method that allows the controlled post-formation processing and modification of complex supported lipid bilayer arrangements, under aqueous conditions. We exploit the destabilization effect of lipopolysaccharide, an amphiphilic biomolecule, interacting with lipid bilayers to generate voids that can be backfilled to introduce desired membrane components. We further demonstrate that when usedmore » in combination with a single, traditional soft lithography process, it is possible to generate hierarchically-organized membrane domains and microscale 2-D array patterns of domains. Significantly, this technique can be used to repeatedly modify membranes allowing iterative control over membrane composition. This approach expands our toolkit for functional membrane design, with potential applications for enhanced materials templating, biosensing and investigating lipid-membrane processes.« less

  20. Characterization of a heat-modifiable outer membrane protein of Haemophilus somnus.

    PubMed Central

    Tagawa, Y; Haritani, M; Ishikawa, H; Yuasa, N

    1993-01-01

    In immunoblot analysis, a murine monoclonal antibody (MAb), 27-1, which was produced to an outer membrane protein (OMP) of Haemophilus somnus, showed that a major OMP is heat modifiable, having a molecular mass of 28 kDa when the N-lauroylsarcosine-insoluble OMP preparation was solubilized at 60 degrees C and a mass of 37 kDa when the OMP preparation was solubilized at 100 degrees C. The heat-modifiable OMP reacted intensely with convalescent sera obtained from calves with experimental H. somnus pneumonia in immunoblot analysis. Immunoelectron microscopic and antibody absorption studies revealed that the MAb 27-1 epitope was not surface exposed on the intact bacterium. However, a decrease in antibody reactivity to the heat-modifiable OMP in immunoblot analysis after absorption of convalescent serum with intact bacterial cells of H. somnus suggests that a surface-exposed portion of the heat-modifiable OMP is expressed on the intact bacterium. MAb 27-1 reacted with 45 of 45 strains of H. somnus tested in immunoblot analysis. The apparent molecular mass of the antigen varied among strains, and five reactivity patterns demonstrated by MAb 27-1 were observed. MAb 27-1 also reacted with six species in the family Pasteurellaceae, Escherichia coli, and Salmonella dublin, but not with the other eight species of gram-negative bacteria. The heat-modifiable OMP of H. somnus showed immunological cross-reactivity with the OmpA protein of E. coli K-12 and significant N-terminal amino acid sequence homology with the OmpA proteins of gram-negative bacteria. We conclude that a major, 37-kDa heat-modifiable OMP of H. somnus, which elicits an antibody response in H. somnus-infected animals, is a common antigen among H. somnus strains tested and is structurally related to the OmpA protein of E. coli. Images PMID:8478064

  1. Enhanced antifouling behaviours of polyvinylidene fluoride membrane modified through blending with nano-TiO2/polyethylene glycol mixture

    NASA Astrophysics Data System (ADS)

    Zhang, Jie; Wang, Zhiwei; Zhang, Xingran; Zheng, Xiang; Wu, Zhichao

    2015-08-01

    Titanium dioxide (TiO2) nanoparticles/polyethylene glycol (PEG) mixture was used to modify polyvinylidene fluoride (PVDF) membranes aiming to improve their antifouling ability. The use of PEG could improve the dispersion of nanoparticles thanks to steric hindrance effects. Test results showed that compared to the original PVDF membrane, the modified membranes had higher hydrophilicity and lower negative Zeta potential, facilitating membrane fouling control. The extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) analysis indicated that the addition of TiO2 nanoparticles improved their electron donor monopolarity, i.e., enhanced electron-donating ability. The interaction energy barrier between soluble microbial products (SMP) and membrane surfaces was also improved, indicating that anti-fouling ability of the modified membrane was elevated. The optimal dosage of nano-TiO2 was found to be 0.15%, and further increase of dosage resulted in the aggregation of nanoparticles which consequently impaired the modification efficiency. Quartz crystal microbalance with dissipation (QCM-D) monitoring and SMP filtration tests confirmed the antifouling ability of the modified membrane.

  2. New modified polyetheretherketone membrane for liver cell culture in biohybrid systems: adhesion and specific functions of isolated hepatocytes.

    PubMed

    De Bartolo, L; Morelli, S; Rende, M; Gordano, A; Drioli, E

    2004-08-01

    There has been growing interest in innovative materials with physico-chemical properties that provide improved blood/cell compatibility. We propose new polymeric membranes made of modified polyetheretherketone (PEEK-WC) as materials with potential for use in biohybrid devices. PEEK-WC exhibits high chemical, thermal stability and mechanical resistance. Owing to its lack of crystallinity this polymer can be used for preparing membranes with cheap and flexible methods. We compared the properties of PEEK-WC membranes to polyurethane membranes prepared using the same phase inverse technique and commercial membranes. The physico-chemical properties of the membranes were characterised by contact angle measurements. The different parameters acid (gamma+), base (gamma-) and Lifshitz-van der Waals (gammaLW) of the surface free energy were calculated according to Good-van Oss's model. We evaluated the cytocompatibility of PEEK-WC membranes by culturing hepatocytes isolated from rat liver. Cell adhesion and metabolic behaviour in terms of ammonia elimination, urea synthesis and protein synthesis were evaluated during the first days of culture. Liver cells adhered and formed three-dimensional aggregates on the most tested membranes. PEEK-WC membranes promoted hepatocyte adhesion most effectively. Urea synthesis, ammonia elimination and protein synthesis improved significantly when cells adhered to PEEK-WC membrane. The considerable metabolic activities of cells cultured on this membrane confirmed the good structural and physico-chemical properties of the PEEK-WC membrane that could be a promising biomaterial for cell culture in biohybrid devices. PMID:15020136

  3. Colloidal crystal formation at the "Nafion-water" interface.

    PubMed

    Bunkin, Nikolay F; Gorelik, Vladimir S; Kozlov, Valeriy A; Shkirin, Alexey V; Suyazov, Nikolay V

    2014-03-27

    In our recent work [Bunkin et al. Water 2013, 4, 129-154] it was first obtained that the water layer, having a size of several tens of micrometers and being adjacent to the swollen Nafion interface, is characterized by enhanced optical density; the refractive index of water at the interface is 1.46. Furthermore, the birefringence effect was observed in this layer. To explain these results, it has been hypothesized that because of "disentangling" of charged polymer chains from the Nafion surface toward the bulk of water, a photonic crystal close to the surface is formed [Bunkin et al. Water 2013, 4, 129-154]. In this paper, we describe experiments with laser-stimulated luminescence from dry and swollen Nafion. It was shown in the experiment with dry Nafion that the apparatus function of our experimental setup (Green's function) is well-described by a Gaussian profile. It was obtained that a highly concentrated colloidal suspension of Nafion particles with a steep spatial boundary is formed in the water layer adjacent to the interface. The volume density of the Nafion particles as a function of the distance from the Nafion interface was found. These findings can be considered indirect confirmation of the previously formulated photonic crystal hypothesis [Bunkin et al. Water 2013, 4, 129-154]. PMID:24568638

  4. Colloidal crystal formation at the "Nafion-water" interface.

    PubMed

    Bunkin, Nikolay F; Gorelik, Vladimir S; Kozlov, Valeriy A; Shkirin, Alexey V; Suyazov, Nikolay V

    2014-03-27

    In our recent work [Bunkin et al. Water 2013, 4, 129-154] it was first obtained that the water layer, having a size of several tens of micrometers and being adjacent to the swollen Nafion interface, is characterized by enhanced optical density; the refractive index of water at the interface is 1.46. Furthermore, the birefringence effect was observed in this layer. To explain these results, it has been hypothesized that because of "disentangling" of charged polymer chains from the Nafion surface toward the bulk of water, a photonic crystal close to the surface is formed [Bunkin et al. Water 2013, 4, 129-154]. In this paper, we describe experiments with laser-stimulated luminescence from dry and swollen Nafion. It was shown in the experiment with dry Nafion that the apparatus function of our experimental setup (Green's function) is well-described by a Gaussian profile. It was obtained that a highly concentrated colloidal suspension of Nafion particles with a steep spatial boundary is formed in the water layer adjacent to the interface. The volume density of the Nafion particles as a function of the distance from the Nafion interface was found. These findings can be considered indirect confirmation of the previously formulated photonic crystal hypothesis [Bunkin et al. Water 2013, 4, 129-154].

  5. Microscopic Analysis of Current and Mechanical Properties of Nafion® Studied by Atomic Force Microscopy

    PubMed Central

    Hiesgen, Renate; Helmly, Stefan; Galm, Ines; Morawietz, Tobias; Handl, Michael; Friedrich, K. Andreas

    2012-01-01

    The conductivity of fuel cell membranes as well as their mechanical properties at the nanometer scale were characterized using advanced tapping mode atomic force microscopy (AFM) techniques. AFM produces high-resolution images under continuous current flow of the conductive structure at the membrane surface and provides some insight into the bulk conducting network in Nafion membranes. The correlation of conductivity with other mechanical properties, such as adhesion force, deformation and stiffness, were simultaneously measured with the current and provided an indication of subsurface phase separations and phase distribution at the surface of the membrane. The distribution of conductive pores at the surface was identified by the formation of water droplets. A comparison of nanostructure models with high-resolution current images is discussed in detail. PMID:24958429

  6. Polydimethysiloxane Modified Silica Nanochannel Membrane for Hydrophobicity-Based Molecular Filtration and Detection.

    PubMed

    Lin, Xingyu; Zhang, Bowen; Yang, Qian; Yan, Fei; Hua, Xin; Su, Bin

    2016-08-01

    We report in this work the fabrication of ultrathin silica nanochannel membranes inhomogeneously modified by polydimethysiloxane (PDMS), designated as PDMS-SNM, for hydrophobicity-based molecular filtration and detection. The modification was accomplished by spatially selective evaporation of hydrophobic PDMS oligomers onto the top surface of the membrane and orifice of silica nanochannels. Thanks to this hydrophobic ultrathin layer and beneath ultrasmall channels (2-3 nm in diameter), only small hydrophobic molecules are able to transport through the PDMS-SNM, whereas hydrophilic and large ones are remarkably inhibited. We first employed this PDMS-SNM as the molecular sieving matrix for selective electrochemical detection of hydrophobic organophosphates (OPs) in milk samples without pretreatment. The PDMS-SNM modified electrode displayed an excellent analytical performance and antifouling/anti-interference ability. We also prepared the free-standing PDMS-SNM consisting of perforated channels, which could filtrate molecules based on their hydrophobicity with an excellent selectivity. As demonstrated, 2,4,6-trinitrotoluene and dopamine could be separated with a selectivity coefficient as high as 335. Moreover, because of the inhomogeneous nanochannel structure and ultrasmall thickness, a remarkably high flux of hydrophobic molecules across the PDMS-SNM was obtained, which was 3-4 orders of magnitude higher than that reported previously. PMID:27414252

  7. Versatile antifouling polyethersulfone filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive.

    PubMed

    Zhao, Yi-Fan; Zhang, Pei-Bin; Sun, Jian; Liu, Cui-Jing; Yi, Zhuan; Zhu, Li-Ping; Xu, You-Yi

    2015-06-15

    Here we describe the development of versatile antifouling polyethersulfone (PES) filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive. Amphiphilic polyethersulfone-block-poly(2-hydroxyethyl methacrylate) (PES-b-PHEMA) was beforehand designed and used as the blending additive of PES membranes prepared by phase inversion technique. The surface enriched PHEMA blocks on membrane surface acted as an anchor to immobilize the initiating site. Poly(sulfobetaine methacrylate) (PSBMA) were subsequently grafted onto the PES blend membranes by surface-initiated atom transfer radical polymerization (SI-ATRP). The analysis of surface chemistry confirmed the successful grafting of zwitterionic PSBMA brushes on PES membrane surface. The resulted PES-g-PSBMA membranes were capable of separating proteins from protein solution and oil from oil/water emulsion efficiently. Furthermore, the modified membranes showed high hydrophilicity and strongly antifouling properties due to the incorporation of well-defined PSBMA layer. In addition, the PES-g-PSBMA membranes exhibited excellent blood compatibility and durability during the washing process. The developed antifouling PES membranes are versatile and can find their applications in protein filtration, blood purification and oil/water separation, etc. PMID:25752579

  8. {sup 1}H nuclear magnetic resonance study of hydrated water dynamics in perfluorosulfonic acid ionomer Nafion

    SciTech Connect

    Han, Jun Hee; Lee, Kyu Won; Jeon, G. W.; Lee, Cheol Eui; Park, W. K.; Choi, E. H.

    2015-01-12

    We have studied the dynamics of hydrated water molecules in the proton exchange membrane of Nafion by means of high-resolution {sup 1}H nuclear magnetic resonance (NMR) measurements. “Bound” and “free” states of hydrated water clusters as well as the exchange protons were identified from the NMR chemical shift measurements, and their activation energies were obtained from the temperature-dependent laboratory- and rotating-frame spin-lattice relaxation measurements. Besides, a peculiar motional transition in the ultralow frequency region was observed at 373 K for the “free” hydrated water from the rotating-frame NMR spin-lattice relaxation time measurements.

  9. DEVELOPMENT OF HIGH TEMPERATURE MEMBRANES AND IMPROVED CATHODE CATALYSTS; PROJECT PERIOD JANUARY 1, 2002 - DECEMBER 31, 2005

    SciTech Connect

    Lesia Protsailo

    2006-04-20

    Polymer Electrolyte Membranes (PEMs) currently available for fuel cell development work are limited to the temperature range of 60-80°C. For mass commercialization in the transportation arena, three important disadvantages that are linked with the relatively low operating temperature range need to be addressed. These three disadvantages are: (a) sluggish cathode kinetics, (b) CO poisoning at the anode and (c) inefficient thermal characteristics. All three of the above mentioned disadvantages could be solved by increasing the operating temperature range to 100-120°C. To understand the issues associated with high temperature PEMFCs operation, UTCFC has teamed with leading research groups that possess competencies in the field of polymer chemistry. The subcontractors on the program were investigating modified Nafion® and new non-Nafion® based, reinforced and non-reinforced membrane systems. Nafion® based PEMs rely on using high temperature inorganic solid conductor fillers like phosphotungstic acid. Hydrocarbon membrane systems are based on poly (arylene ether sulfone) polymers, PEEK, PAN, etc.

  10. A novel nitrite biosensor based on conductometric electrode modified with cytochrome c nitrite reductase composite membrane.

    PubMed

    Zhang, Zhiqiang; Xia, Siqing; Leonard, Didier; Jaffrezic-Renault, Nicole; Zhang, Jiao; Bessueille, François; Goepfert, Yves; Wang, Xuejiang; Chen, Ling; Zhu, Zhiliang; Zhao, Jianfu; Almeida, M Gabriela; Silveira, Célia M

    2009-02-15

    A conductometric biosensor for nitrite detection was developed using cytochrome c nitrite reductase (ccNiR) extracted from Desulfovibrio desulfuricans ATCC 27774 cells immobilized on a planar interdigitated electrode by cross-linking with saturated glutaraldehyde (GA) vapour in the presence of bovine serum albumin, methyl viologen (MV), Nafion, and glycerol. The configuration parameters for this biosensor, including the enzyme concentration, ccNiR/BSA ratio, MV concentration, and Nafion concentration, were optimized. Various experimental parameters, such as sodium dithionite added, working buffer solution, and temperature, were investigated with regard to their effect on the conductance response of the biosensor to nitrite. Under the optimum conditions at room temperature (about 25 degrees C), the conductometric biosensor showed a fast response to nitrite (about 10s) with a linear range of 0.2-120 microM, a sensitivity of 0.194 microS/microM [NO(2)(-)], and a detection limit of 0.05 microM. The biosensor also showed satisfactory reproducibility (relative standard deviation of 6%, n=5). The apparent Michaelis-Menten constant (K(M,app)) was 338 microM. When stored in potassium phosphate buffer (100mM, pH 7.6) at 4 degrees C, the biosensor showed good stability over 1 month. No obvious interference from other ionic species familiar in natural waters was detected. The application experiments show that the biosensor is suitable for use in real water samples. PMID:18804367

  11. Subsecond Morphological Changes in Nafion during Water Uptake Detected by Small-Angle X-ray Scattering

    SciTech Connect

    Kusoglu, Ahmet; Modestino, Miguel A.; Hexemer, Alexander; Segalman, Rachel A.; Weber, Adam Z.

    2011-11-09

    The ability of the Nafion membrane to absorb water rapidly and create a network of hydrated interconnected water domains provides this material with an unmatched ability to conduct ions through a chemically and mechanically robust membrane. The morphology and composition of these hydrated membranes significantly affects their transport properties and performance. This research demonstrates that differences in interfacial interactions between the membranes exposed to vapor or liquid water can cause significant changes in kinetics of water uptake. In situ small-angle X-ray scattering (SAXS) experiments captured the rapid swelling of the membrane in liquid water with a nanostructure rearrangement on the order of seconds. For membranes in contact with water vapor, morphological changes are four orders-of-magnitude slower than in liquid water, suggesting that interfacial resistance limits the penetration of water into the membrane. Furthermore, upon water absorption from liquid water, a structural rearrangement from a distribution of spherical and cylindrical domains to exclusively cylindrical-like domains is suggested. These differences in water-uptake kinetics and morphology provide a new perspective into Schroeder's paradox, which dictates a different water content for vapor- and liquid-equilibrated ionomers at unit activity. Lastly, the findings of this work provide critical insights into the fast kinetics of water absorption of the Nafion membrane, which can aid in the design of energy conversion devices that operate under frequent changes in environmental conditions.

  12. Comparing selected morphological models of hydrated Nafion using large scale molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Knox, Craig K.

    Experimental elucidation of the nanoscale structure of hydrated Nafion, the most popular polymer electrolyte or proton exchange membrane (PEM) to date, and its influence on macroscopic proton conductance is particularly challenging. While it is generally agreed that hydrated Nafion is organized into distinct hydrophilic domains or clusters within a hydrophobic matrix, the geometry and length scale of these domains continues to be debated. For example, at least half a dozen different domain shapes, ranging from spheres to cylinders, have been proposed based on experimental SAXS and SANS studies. Since the characteristic length scale of these domains is believed to be ˜2 to 5 nm, very large molecular dynamics (MD) simulations are needed to accurately probe the structure and morphology of these domains, especially their connectivity and percolation phenomena at varying water content. Using classical, all-atom MD with explicit hydronium ions, simulations have been performed to study the first-ever hydrated Nafion systems that are large enough (~2 million atoms in a ˜30 nm cell) to directly observe several hydrophilic domains at the molecular level. These systems consisted of six of the most significant and relevant morphological models of Nafion to-date: (1) the cluster-channel model of Gierke, (2) the parallel cylinder model of Schmidt-Rohr, (3) the local-order model of Dreyfus, (4) the lamellar model of Litt, (5) the rod network model of Kreuer, and (6) a 'random' model, commonly used in previous simulations, that does not directly assume any particular geometry, distribution, or morphology. These simulations revealed fast intercluster bridge formation and network percolation in all of the models. Sulfonates were found inside these bridges and played a significant role in percolation. Sulfonates also strongly aggregated around and inside clusters. Cluster surfaces were analyzed to study the hydrophilic-hydrophobic interface. Interfacial area and cluster volume

  13. Multifunctional Graphene/Platinum/Nafion Hybrids via Ice Templating

    SciTech Connect

    Estevez, Luis; Kelarakis, Antonios; Gong, Qianming; Da’as, Eman Husni; Giannelis, Emmanuel P.

    2011-04-27

    We report the synthesis of multifunctional hybrids in both films and bulk form, combining electrical and ionic conductivity with porosity and catalytic activity. The hybrids are synthesized by a two-step process: (a) ice templation of an aqueous suspension comprised of Nafion, graphite oxide, and chloroplatinic acid to form a microcellular porous network and (b) mild reduction in hydrazine or monosodium citrate which leads to graphene-supported Pt nanoparticles on a Nafion scaffold

  14. Adsorption kinetic character of copper ions onto a modified chitosan transparent thin membrane from aqueous solution.

    PubMed

    Cheng, Zihong; Liu, Xiaoshuai; Han, Mei; Ma, Wei

    2010-10-15

    A modified chitosan transparent thin membrane (MCTTM) was prepared and used as the adsorbent to investigate the adsorption kinetics due to excellent capacity of removing copper ions in water solution. The structure and morphology of MCTTM were characterized by SEM analysis and FTIR analysis. External mass transfer, intra particle diffusion, and pseudo-first and pseudo-second order models were used to describe the adsorption process. The results obtained from the study illustrated that the adsorption process could be described by the pseudo-second order model, which indicated adsorption process was a chemical adsorption behavior of chelation ion exchange proved by the FTIR and adsorption free energy analysis. External mass transfer and intra particle diffusion processes were the rate-controlling steps.

  15. Adsorption kinetic character of copper ions onto a modified chitosan transparent thin membrane from aqueous solution.

    PubMed

    Cheng, Zihong; Liu, Xiaoshuai; Han, Mei; Ma, Wei

    2010-10-15

    A modified chitosan transparent thin membrane (MCTTM) was prepared and used as the adsorbent to investigate the adsorption kinetics due to excellent capacity of removing copper ions in water solution. The structure and morphology of MCTTM were characterized by SEM analysis and FTIR analysis. External mass transfer, intra particle diffusion, and pseudo-first and pseudo-second order models were used to describe the adsorption process. The results obtained from the study illustrated that the adsorption process could be described by the pseudo-second order model, which indicated adsorption process was a chemical adsorption behavior of chelation ion exchange proved by the FTIR and adsorption free energy analysis. External mass transfer and intra particle diffusion processes were the rate-controlling steps. PMID:20634000

  16. Three-Step Water Sorption of Thin Nafion Films

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Daisuke; Ogata, Yudai; Yamada, Norifumi; Tanaka, Keiji

    2015-03-01

    Nafion has been widely used as a proton exchange film in polymer electrolyte fuel cell (PEFC). Although downsizing PEFC is one of the interesting developments in the near future, it appears that most studies conducted so far are limited to bulk systems. Here we examined water sorption behavior in thin Nafion films based on optical and neutron reflectivity measurements. Nafion films were prepared on silver and silicon oxide substrates. It was found that the thicknesses of Nafion thin films increased with time after contacting water in three steps. The asymptotic swelling ratios in regimes I, II and III were 1.05, 1.26 and 1.41, respectively. These values were in-dependent of the substrate species, and were coincident with the transition points of different hydration states in the bulk Nafion; water binding to sulfonic acid groups, the formation of sphere-like ionic clusters, and bridge formation between clusters. The swelling was much slower in thin films than in the bulk due to the mobility restriction of Nafion near the substrate.

  17. Transport rectification in nanopores with outer membranes modified with surface charges and polyelectrolytes.

    PubMed

    Tagliazucchi, Mario; Rabin, Yitzhak; Szleifer, Igal

    2013-10-22

    This work reports a comprehensive theoretical study of the transport-rectification properties of cylindrical nanopores with neutral inner walls and chemically modified outer membrane. The chemical species on the two outer sides of the membrane have charges of opposite sign and can be either surface-confined species (i.e., surface charges) or polyelectrolyte brushes. The advantage of this design over other types of rectifying nanopores is that it requires controlling the composition of the outer walls of the pore (which are easy to access) rather than the inner walls, thus simplifying the fabrication process. Ion-current rectification in nanopores with charged outer walls is ascribed to applied-potential-induced changes in the ionic concentration within the pore. The rectification efficiency is studied as a function of pore length, radius, surface charge and bulk electrolyte concentration. An analytical model is derived for the case of surface-confined charges that predicts the current-potential curves in very good agreement with the numerical calculations. Neutral nanopores with polyelectrolyte-modified outer walls have two distinct advantages compared to surface-charged systems: (i) they exhibit higher rectification factors due to the large charge density immobilized by the polyelectrolyte brushes, and (ii) the applied potential deforms the polyelectrolyte chains toward the oppositely charged electrode. This deformation brings the polyelectrolyte brushes into the pore in the low conductivity state and expels them from the pore in the high conductivity regime. Calculations of the potentials of mean-force suggest that the applied-field-induced conformational changes can be used to control the translocation of cargoes larger than ions, such as proteins and nanoparticles.

  18. Development of structured polymer electrolyte membranes for fuel cell applications

    NASA Astrophysics Data System (ADS)

    Gasa, Jeffrey

    The objective of this research was to explore structure-property relationships to develop the understanding needed for introduction of superior PEM materials. Polymer electrolyte membranes based on sulfonated poly(ether ketone ketone) (SPEKK) were fabricated using N-methyl pyrrolidone as casting solvent. The membranes were characterized in terms of properties that were relevant to fuel cell applications, such as proton conductivity, methanol permeability, and swelling properties, among others. It was found in this study that the proton conductivity of neat SPEKK membranes could reach the conductivity of commercial membranes such as NafionRTM. However, when the conductivity of SPEKK was comparable to NafionRTM, the swelling of SPEKK in water was quite excessive. The swelling problem was remedied by modifying the microstructure of SPEKK using different techniques. One of them involved blending of lightly sulfonated PEKK with highly acidic particles (sulfonated crosslinked polystyrene-SXLPS). Low sulfonation level of SPEKK was used to reduce the swelling of the membrane in water and the role of the highly acidic particles was to enhance the proton conductivity of the membrane. Because of the residual crystallinity in SPEKK with low sulfonation levels (IEC < 1 meq/g), the composite membranes exhibited excellent dimensional stability in water at elevated temperatures (30-90 °C). Also, the resistance to swelling of these composite membranes in methanol-water mixtures was far better than NafionRTM, and so was the methanol permeability. Another technique explored was blending with non-conductive polymers (poly(ether imide) and poly(ether sulfone)) to act as mechanical reinforcement. It was found that miscibility behavior of the blends had a significant impact on the transport and swelling properties of these blends, which could be explained by the blend microstructure. The miscibility behavior was found to be strongly dependent on the sulfonation level of SPEKK. The

  19. An oxalate selective electrode based on modified PVC-membrane with tetra-butylammonium--Clinoptilolite nanoparticles.

    PubMed

    Hoseini, Zohre; Nezamzadeh-Ejhieh, Alireza

    2016-03-01

    A modified PVC-membrane electrode with tetra-butylammonium bromide - Clinoptilolite nano-particles (TBA-NCP) showed good Nernstian slope (29.9±0.6 mV per decade of oxalate concentration) in concentration range of 3.1×10(-7)-8.3×10(-1) mol L(-1) with a detection limit of 1.5×10(-7) mol L(-1). The best performance was obtained with a membrane composition of 31.5% PVC, 62.5% DOP and 6% TBA-NCP in the temperature range of 20-35 °C and the pH range of 4-9. The fast response time and good reproducibility over a period of 3 months are other characteristics of the sensor. The proposed electrode was successfully used as an indicator electrode in titration of oxalate ions with CaCl2 solution. The proposed electrode was also used in direct potentiometric determination of oxalate in many real samples such as: mushroom, black and green tea, spinach and beet.

  20. Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

    PubMed

    Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

    2012-07-30

    In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane.

  1. Plasma Membranes Modified by Plasma Treatment or Deposition as Solid Electrolytes for Potential Application in Solid Alkaline Fuel Cells

    PubMed Central

    Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

    2012-01-01

    In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane. PMID:24958295

  2. Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

    PubMed

    Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

    2012-01-01

    In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane. PMID:24958295

  3. New process for alleviation of membrane fouling of modified hybrid MBR system for advanced domestic wastewater treatment.

    PubMed

    Shuo, Liu; Baozhen, Wang; Hongjun, Han; Yanping, Liu

    2008-01-01

    A pilot-scale hybrid membrane bioreactor using a submerged flat panel membrane was designed and applied for advanced treatment of domestic wastewater. The new process adapted to the hybrid membrane bioreactor exhibits substantial decrease in membrane fouling and much easier cleaning. In this study, the new process configurations including the addition of anoxic/anaerobic zones, the package of synthetic fibrous fabric carrier for biofilm attached growth, activated sludge recycling and modified dosage of polished diatomite with high activity and multi-functions were investigated to select the optimal operational parameters for the hybrid membrane bioreactor system. The carrier package in the aerobic zone contributed 3.65 g/L (maximum) of fixed biomass to the system, thus reducing the suspended biomass, and has decreased the membrane cleaning cycle remarkably. The operation performance at the sludge recycle rate 0, 100%, 200% and 300% showed that, the trans-membrane pressure of flat panel membrane declined sharply with the increase of sludge recycling rate within a certain range, and 200% was decided to be optimal for in the membrane bioreactor system. EPS concentration in each sludge recycling rate was 135 mg/L, 92 mg/L, 68 mg/L and 55 mg/L respectively. The addition of anoxic and anaerobic zones degraded some large molecular organic compounds, which facilitated the biodegradation and removal of organic substances in aerobic zone. The modified dosage of polished diatomite has played a major important role for both preventing of membrane from fouling and its much easier cleaning when it formed.

  4. Hyperbranched poly(benzimidazole-co-benzene) with honeycomb structure as a membrane for high-temperature proton-exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Bhadra, Sambhu; Kim, Nam Hoon; Choi, Ji Sun; Rhee, Kyong Yop; Lee, Joong Hee

    Hyperbranched poly(benzimidazole-co-benzene) (PBIB) with a honeycomb structure is synthesized by condensation polymerization of trimesic acid (TMA) and 3,3‧-diaminobenzidine (DAB) for use as a membrane high-temperature proton-exchange membrane fuel cells (HT-PEMFCs). The hyperbranched honeycomb structure of polybenzimidazole (PBI) has been introduced to impart higher mechanical strength to doped PBI membranes. The stress at break of the phosphoric acid doped PBIB (DPBIB) membrane (29 ± 3 MPa) is comparable with that of Nafion (28 ± 2 MPa) and much superior to doped PBI membranes. The DPBIB membrane exhibits lower proton conductivity than Nafion 115. On the other hand, the proton conductivity of Nafion 115 is enhanced with increase in relative humidity, whereas humidity has only a moderate effect on the proton conductivity of the DPBIB membrane. Consequently, the Nafion 115 membrane in a fuel cell cannot operate in the absence of humidity, whereas the DPBIB membrane can perform well. The power output of the DPBIB membrane in a fuel cell is superior under humid conditions than under dry conditions. The maximum power output from the DPBIB and Nafion 115 membranes is comparable under humid conditions. It is concluded that the DPBIB membrane, but not Nafion, is suitable for application in HT-PEMFCs.

  5. Improved manufacturing technology for producing porous Nafion for high-performance ionic polymer–metal composite actuators

    NASA Astrophysics Data System (ADS)

    Zhao, Dongxu; Li, Dichen; Wang, Yanjie; Chen, Hualing

    2016-07-01

    The current actuation performance of ionic polymer–metal composites (IPMCs) limits their further application in the aerospace, energy, and optics fields, among others. To overcome this issue, we developed a freeze-drying process to generate Nafion membranes with a porous structure, the characteristics of which were investigated using thermogravimetric analysis, Fourier transform infrared spectrometry, field-emission scanning electron microscopy, and water uptake tests. The pores fabricated using the developed freeze-drying process had a diameter of approximately 270 nm, and a porosity of nearly 40.45%. The displacement and the central angle were introduced as variables to evaluate the bending deformation of an IPMC actuator based on the porous Nafion membrane. Compared with conventional actuators, this IPMC actuator showed an increase in displacement of 4963.6% at 2 V, and an increase in central angle of 73.35% at 3 V. Although the blocking forces of this IPMC actuator decreased to some extent, it was confirmed that the integrated actuation performance, which was evaluated using the strain energy density increment, was improved. The performance of the IPMC actuator was enhanced as a result of the porous Nafion structure manufactured using the developed freeze-drying process.

  6. Improved manufacturing technology for producing porous Nafion for high-performance ionic polymer-metal composite actuators

    NASA Astrophysics Data System (ADS)

    Zhao, Dongxu; Li, Dichen; Wang, Yanjie; Chen, Hualing

    2016-07-01

    The current actuation performance of ionic polymer-metal composites (IPMCs) limits their further application in the aerospace, energy, and optics fields, among others. To overcome this issue, we developed a freeze-drying process to generate Nafion membranes with a porous structure, the characteristics of which were investigated using thermogravimetric analysis, Fourier transform infrared spectrometry, field-emission scanning electron microscopy, and water uptake tests. The pores fabricated using the developed freeze-drying process had a diameter of approximately 270 nm, and a porosity of nearly 40.45%. The displacement and the central angle were introduced as variables to evaluate the bending deformation of an IPMC actuator based on the porous Nafion membrane. Compared with conventional actuators, this IPMC actuator showed an increase in displacement of 4963.6% at 2 V, and an increase in central angle of 73.35% at 3 V. Although the blocking forces of this IPMC actuator decreased to some extent, it was confirmed that the integrated actuation performance, which was evaluated using the strain energy density increment, was improved. The performance of the IPMC actuator was enhanced as a result of the porous Nafion structure manufactured using the developed freeze-drying process.

  7. Optimum ionic conductivity and diffusion coefficient of ion-exchange membranes at high methanol feed concentrations in a direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Lee, K.; Nam, J.-D.

    In direct methanol fuel cells (DMFCs), the optimum characteristics of ion-exchange membranes are investigated at high concentrations of methanol feed up to 7 M by modifying the diffusion coefficient and the ionic conductivity of the polyelectrolyte material. A Nafion membrane is modified by the incorporation of layered double hydroxide (LDH) nanoplatelets with different Mg 2+:Al 3+ ratios. When the feed concentration of methanol is lower than 3 M, the DMFC is controlled by the ionic conductivity of the polyelectrolyte membrane because methanol cross-over is not relatively significant. When the feed concentration is high, however, the diffusion coefficient of methanol is the key factor that determines the performance of the fuel cell. This is due to a high concentration gradient of methanol across the polyelectrolyte membrane. The open-circuit voltage is increased by the decreased diffusion coefficient in LDH/Nafion nanocomposite membranes at methanol feed concentrations up to 7 M; apparently because methanol cross-over is suppressed by the incorporation of LDH. The maximum power density of the DMFC is determined by the two competing transport processes of ion conduction and methanol diffusion, especially at a relatively high methanol concentration, that can provide optimum operating conditions in the membrane.

  8. High-Flux Positively Charged Nanocomposite Nanofiltration Membranes Filled with Poly(dopamine) Modified Multiwall Carbon Nanotubes.

    PubMed

    Zhao, Feng-Yang; Ji, Yan-Li; Weng, Xiao-Dan; Mi, Yi-Fang; Ye, Chun-Chun; An, Quan-Fu; Gao, Cong-Jie

    2016-03-01

    The poor dispensability of pristine carbon nanotubes in water impedes their implications in thin-film nanocomposite membranes for crucial utilities such as water purification. In this work, high-flux positively charged nanocomposite nanofiltration membranes were exploited by uniformly embedding poly(dopamine) modified multiwall carbon nanotubes (PDA-MWCNTs) in polyamide thin-film composite membranes. With poly(dopamine) modification, fine dispersion of MWCNTs in polyethyleneimine (PEI) aqueous solutions was achieved, which was interracially polymerized with trimesoyl chloride (TMC) n-hexane solutions to prepare nanocomposite membranes. The compatibility and interactions between modified MWCNTs and polyamide matrix were enhanced, attributed to the poly(dopamine) coatings on MWCNT surfaces, leading to significantly improved water permeability. At optimized conditions, pure water permeability of the PEI/PDA-MWCNTs/TMC nanofiltration membrane (M-4) was 15.32 L m(-2) h(-1) bar(-1), which was ∼1.6 times increased compared with that of pristine PEI/TMC membranes. Salt rejection of M-4 to different multivalent cations decreased in the sequence ZnCl2 (93.0%) > MgCl2 (91.5%) > CuCl2 (90.5%) ≈ CaCl2, which is well-suited for water softening and heavy metal ion removal. PMID:26901491

  9. [Anti-tumor activity of folate receptor targeting docetaxel-loaded membrane-modified liposomes].

    PubMed

    Li, Xiang; Zhang, Jing; Wang, Dong-Kai; Pan, Wei-San

    2013-07-01

    The anti-tumor activity of folate receptor targeting docetaxel-loaded membrane-modified liposomes (FA-PDCT-L) was investigated in vitro and in vivo. FA-PDCT-L was prepared by organic solvent injection method. Transmission electron microscope, dynamic light scattering and electrophoretic light scattering were employed to study the physicochemical parameters of FA-PDCT-L. The inhibitory effects of docetaxel injection (DCT-I), non-modified DCT liposomes (DCT-L) and FA-PDCT-L on the growth of MCF-7 and A-549 cells at different incubation times were detected by CCK-8 assay; and the hemolytic test was employed in vitro. Tumor mice were randomized into 4 groups: DCT-I, DCT-L, FA-PDCT-L and control group (normal saline), and given drugs at 10 mg x kg(-1) x d(-1) through tail vein. The tumor volume, mice weight, inhibition rate of tumor and life span were measured at the end of experiments. The IC50 of the FA-PDCT-L for MCF-7 and A549 cell lines were significantly lower than that of DCT-I and DCT-L, without hemolysis reaction observed. Compared with control group, the weights of tumor in DCT-I, DCT-L and FA-PDCT-L were decreased, especially for FA-PDCT-L, with inhibitory rates at 79.03 % (P < 0.05). The life span and median survival time of FA-PDCT-L treated mice were significantly higher than that of DCT-I and DCT-L. In conclusion, FA-PDCT-L shows a good anti-tumor activity, indicating that it is potential carriers for DCT in the treatment of tumor.

  10. Pyruvate modifies metabolic flux and nutrient sensing during extracorporeal membrane oxygenation in an immature swine model

    SciTech Connect

    Ledee, Dolena R.; Kajimoto, Masaki; O'Kelly-Priddy, Colleen M.; Olson, Aaron; Isern, Nancy G.; Robillard Frayne, Isabelle; Des Rosiers, Christine; Portman, Michael A.

    2015-07-01

    Extracorporeal membrane oxygenation (ECMO) provides mechanical circulatory support for infants and children with postoperative cardiopulmonary failure. Nutritional support is mandatory during ECMO, although specific actions for substrates on the heart have not been delineated. Prior work shows that enhancing pyruvate oxidation promotes successful weaning from ECMO. Accordingly, we closely examined the role of prolonged systemic pyruvate supplementation in modifying metabolic parameters during the unique conditions of ventricular unloading provided by ECMO. Twelve male mixed breed Yorkshire piglets (age 30-49 days) received systemic infusion of either normal saline (Group C) or pyruvate (Group P) during ECMO for 8 hours. Over the final hour piglets received [2-13C] pyruvate, and [13C6]-L-leucine, as an indicator for oxidation and protein synthesis. A significant increase in lactate and pyruvate concentrations occurred, along with an increase in the absolute concentration of all measured CAC intermediates. Group P showed greater anaplerotic flux through pyruvate carboxylation although pyruvate oxidation relative to citrate synthase flux was similar to Group C. The groups demonstrated similar leucine fractional contributions to acetyl-CoA and fractional protein synthesis rates. Pyruvate also promoted an increase in the phosphorylation state of several nutrient sensitive enzymes, such as AMPK and ACC, and promoted O-GlcNAcylation through the hexosamine biosynthetic pathway (HBP). In conclusion, prolonged pyruvate supplementation during ECMO modified anaplerotic pyruvate flux and elicited changes in important nutrient and energy sensitive pathways, while preserving protein synthesis. Therefore, the observed results support the further study of nutritional supplementation and its downstream effects on cardiac adaptation during ventricular unloading.

  11. Enhanced proton conductivity by the influence of modified montmorillonite on poly (vinyl alcohol) based blend composite membranes

    NASA Astrophysics Data System (ADS)

    Palani, P. Bahavan; Abidin, K. Sainul; Kannan, R.; Rajashabala, S.; Sivakumar, M.

    2016-05-01

    The highest proton conductivity value of 0.0802 Scm-1 is obtained at 6wt% of protonated MMT added to the PVA/PEG blends. The polymer blend composite membranes are prepared with varied concentration of Poly vinyl alcohol (PVA), Poly ethylene glycol (PEG) and Montmorillonite (MMT) by solution casting method. The Na+ MMT was modified (protonated) to H+ MMT with ion exchange process. The prepared membranes were characterized by using TGA, FTIR, XRD, Ion Exchange Capacity, Water/Methanol uptake, swelling ratio and proton conductivity. The significant improvements in the hydrolytic stability were observed. In addition, thermal stability of the composite membranes were improved and controlled by the addition of MMT. All the prepared membranes are shown appreciable values of proton conductivity at room temperature with 100% relative humidity.

  12. Kv1.5 Association Modifies Kv1.3 Traffic and Membrane Localization*S⃞

    PubMed Central

    Vicente, Rubén; Villalonga, Núria; Calvo, Maria; Escalada, Artur; Solsona, Carles; Soler, Concepció; Tamkun, Michael M.; Felipe, Antonio

    2008-01-01

    Kv1.3 activity is determined by raft association. In addition to Kv1.3, leukocytes also express Kv1.5, and both channels control physiological responses. Because the oligomeric composition may modify the channel targeting to the membrane, we investigated heterotetrameric Kv1.3/Kv1.5 channel traffic and targeting in HEK cells. Kv1.3 and Kv1.5 generate multiple heterotetramers with differential surface expression according to the subunit composition. FRET analysis and pharmacology confirm the presence of functional hybrid channels. Raft association was evaluated by cholesterol depletion, caveolae colocalization, and lateral diffusion at the cell surface. Immunoprecipitation showed that both Kv1.3 and heteromeric channels associate with caveolar raft domains. However, homomeric Kv1.3 channels showed higher association with caveolin traffic. Moreover, FRAP analysis revealed higher mobility for hybrid Kv1.3/Kv1.5 than Kv1.3 homotetramers, suggesting that heteromers target to distinct surface microdomains. Studies with lipopolysaccharide-activated macrophages further supported that different physiological mechanisms govern Kv1.3 and Kv1.5 targeting to rafts. Our results implicate the traffic and localization of Kv1.3/Kv1.5 heteromers in the complex regulation of immune system cells. PMID:18218624

  13. Determination of labile trace metals with screen-printed electrode modified by a crown-ether based membrane.

    PubMed

    Parat, Corinne; Betelu, Stéphanie; Authier, Laurent; Potin-Gautier, Martine

    2006-07-28

    In this work, we have undertaken the construction of a screen-printed electrode modified by a specific membrane to protect the working surface from interferences during the analysis of trace metals by anodic stripping voltammetry. Different crown-ethers selected for their metals affinity have been incorporated into a membrane then deposed on the working surface of the electrode. Each modified electrode has been first tested in an acidified KNO3 10(-1) mol L(-1) solution (pH 2) doped by free Cd2+ and Pb2+ ions. The response and selectivity of the modified electrodes have been investigated according to different parameters: (i) the substrates (commercial ink or carbon based homemade ink), (ii) the electrode support (polystyrene or transparency film) and (iii) crown-ethers nature (dibenzo-24-crown-8 and tetrathiacyclododecane 12-crown-4). The influence of the substrate on the response of the electrode is clearly demonstrated. Homemade ink appears as the most appropriate substrate to modify the working surface of the screen-printed electrode by a crown-ether based membrane. The effect of the composition of the membrane has been shown too. The best membrane developed showed a detection limit of 0.6 x 10(-8) mol L(-1) for Cd and 0.8 x 10(-8) mol L(-1) for Pb and a quantification limit of 10(-8) mol L(-1) for Cd and 2 x 10(-8) mol L(-1) for Pb. This method, which integrates the extraction, preconcentration and measurement, was successfully applied to environmental samples without pretreatment.

  14. Effects of surface roughening of Nafion 117 on the mechanical and physicochemical properties of ionic polymer–metal composite (IPMC) actuators

    NASA Astrophysics Data System (ADS)

    Wang, Yanjie; Zhu, Zicai; Liu, Jiayu; Chang, Longfei; Chen, Hualing

    2016-08-01

    In this paper, the surface of a Nafion membrane was roughened by the sandblasting method, mainly considering the change of sandblasting time and powder size. The roughened surfaces were characterized in terms of their topography from the confocal laser scanning microscope (CLSM) and SEM. The key surface parameters, such as Sa (the arithmetical mean deviation of the specified surface profile), SSA (the surface area ratio before and after roughening) and the area measurement on the histogram from the CLSM images, were extracted and evaluated from the roughened membranes. Also, the detailed change in surface and interfacial electrodes were measured and discussed together with the surface resistance, equivalent modulus, capacitance and performances of IPMC actuators based on the roughened membranes. The results show that a suitable sandblasting condition, resulting in the decrease in the bending stiffness and the increase in the interface area closely related to the capacitance, can effectively increase the electromechanical responses of IPMCs. Although the surface roughening by sandblasting caused a considerable lowering of mechanical strength, it was very effective for enlarging the interfacial area between Nafion membrane and the electrode layers, and for forming a penetrated electrode structure, which facilitated improvement of the surface resistance and capacitance characteristics of IPMCs. In this work, a quantitative relationship was built between the topography of Nafion membrane surface and electromechanical performance of IPMCs by means of sandblasting.

  15. Effects of surface roughening of Nafion 117 on the mechanical and physicochemical properties of ionic polymer-metal composite (IPMC) actuators

    NASA Astrophysics Data System (ADS)

    Wang, Yanjie; Zhu, Zicai; Liu, Jiayu; Chang, Longfei; Chen, Hualing

    2016-08-01

    In this paper, the surface of a Nafion membrane was roughened by the sandblasting method, mainly considering the change of sandblasting time and powder size. The roughened surfaces were characterized in terms of their topography from the confocal laser scanning microscope (CLSM) and SEM. The key surface parameters, such as Sa (the arithmetical mean deviation of the specified surface profile), SSA (the surface area ratio before and after roughening) and the area measurement on the histogram from the CLSM images, were extracted and evaluated from the roughened membranes. Also, the detailed change in surface and interfacial electrodes were measured and discussed together with the surface resistance, equivalent modulus, capacitance and performances of IPMC actuators based on the roughened membranes. The results show that a suitable sandblasting condition, resulting in the decrease in the bending stiffness and the increase in the interface area closely related to the capacitance, can effectively increase the electromechanical responses of IPMCs. Although the surface roughening by sandblasting caused a considerable lowering of mechanical strength, it was very effective for enlarging the interfacial area between Nafion membrane and the electrode layers, and for forming a penetrated electrode structure, which facilitated improvement of the surface resistance and capacitance characteristics of IPMCs. In this work, a quantitative relationship was built between the topography of Nafion membrane surface and electromechanical performance of IPMCs by means of sandblasting.

  16. Biodegradation of a biochar-modified waterborne polyacrylate membrane coating for controlled-release fertilizer and its effects on soil bacterial community profiles.

    PubMed

    Zhou, Zijun; Du, Changwen; Li, Ting; Shen, Yazhen; Zeng, Yin; Du, Jie; Zhou, Jianmin

    2015-06-01

    Biochar-modified polyacrylate-like polymers are promising waterborne polymer-based membrane coatings for controlled-release fertilizers. However, the effect of these membrane polymers on paddy soil is unknown. A soil incubation experiment was conducted using Fourier transform infrared photoacoustic spectroscopy to monitor the changes in the polymer-coated membranes in paddy soil, and Biolog EcoPlates and polymerase chain reaction-denaturing gradient gel electrophoresis were used to detect the effects of the membranes on soil bacterial community profiles. Compared to unmodified membranes, the biodegradation rate of the biochar-modified membrane was slower, and the membrane was more intact, which improved and guaranteed the controlled release of nutrients. Compared to the soil without membranes, the biochar-modified membranes, as well as unmodified ones, showed no significant impacts on the composition diversity of soil dominant bacterial community. The activity and functional diversity of soil culturable microbial community during the early stage of incubation were reduced by biochar-modified membranes due to the release of small amount of soluble organic materials but were both recovered in the 12(th) month of the incubation period. Therefore, the biochar-modified waterborne polyacrylate was environmentally friendly, demonstrating its potential both in the development of coated controlled-release fertilizers and in the utilization of crop residue. PMID:25567059

  17. Biodegradation of a biochar-modified waterborne polyacrylate membrane coating for controlled-release fertilizer and its effects on soil bacterial community profiles.

    PubMed

    Zhou, Zijun; Du, Changwen; Li, Ting; Shen, Yazhen; Zeng, Yin; Du, Jie; Zhou, Jianmin

    2015-06-01

    Biochar-modified polyacrylate-like polymers are promising waterborne polymer-based membrane coatings for controlled-release fertilizers. However, the effect of these membrane polymers on paddy soil is unknown. A soil incubation experiment was conducted using Fourier transform infrared photoacoustic spectroscopy to monitor the changes in the polymer-coated membranes in paddy soil, and Biolog EcoPlates and polymerase chain reaction-denaturing gradient gel electrophoresis were used to detect the effects of the membranes on soil bacterial community profiles. Compared to unmodified membranes, the biodegradation rate of the biochar-modified membrane was slower, and the membrane was more intact, which improved and guaranteed the controlled release of nutrients. Compared to the soil without membranes, the biochar-modified membranes, as well as unmodified ones, showed no significant impacts on the composition diversity of soil dominant bacterial community. The activity and functional diversity of soil culturable microbial community during the early stage of incubation were reduced by biochar-modified membranes due to the release of small amount of soluble organic materials but were both recovered in the 12(th) month of the incubation period. Therefore, the biochar-modified waterborne polyacrylate was environmentally friendly, demonstrating its potential both in the development of coated controlled-release fertilizers and in the utilization of crop residue.

  18. Preparation and characterization of thin-film composite membrane with nanowire-modified support for forward osmosis process.

    PubMed

    Low, Ze-Xian; Liu, Qi; Shamsaei, Ezzatollah; Zhang, Xiwang; Wang, Huanting

    2015-01-01

    Internal concentration polarization (ICP) in forward osmosis (FO) process is a characteristic problem for asymmetric thin-film composite (TFC) FO membrane which leads to lower water flux. To mitigate the ICP effect, modification of the substrates' properties has been one of the most effective methods. A new polyethersulfone-based ultrafiltration membrane with increased surface porosity and high water flux was recently produced by incorporating Zn2GeO4 nanowires. The composite membrane was used as a substrate for the fabrication of TFC FO membrane, by coating a thin layer of polyamide on top of the substrate. The substrate and the nanowires were characterized by a range of techniques such as SEM, XRD, and contact angle goniometry. The water permeability and molecular weight cut-offs (MWCO) of the substrate; and the FO performance of the TFC membrane were also determined. The Zn2GeO4-modified membrane showed ~45% increase in water permeability and NaCl salt rejection of 80% under RO mode. In FO mode, the ratio of water flux to reverse solute flux was also improved. However, lower FO flux was obtained which could be due to ICP. The result shows that Zn2GO4 nanowire may be used as a modifier to the substrate to improve the quality of the polyamide layer on the substrate to improve the flux and selectivity, but not as effective in reducing ICP. This work demonstrates that the incorporation of nanomaterials to the membrane substrate may be an alternative approach to improve the formation of polyamide skin layer to achieve better FO performance. PMID:25803239

  19. Preparation and Characterization of Thin-Film Composite Membrane with Nanowire-Modified Support for Forward Osmosis Process

    PubMed Central

    Low, Ze-Xian; Liu, Qi; Shamsaei, Ezzatollah; Zhang, Xiwang; Wang, Huanting

    2015-01-01

    Internal concentration polarization (ICP) in forward osmosis (FO) process is a characteristic problem for asymmetric thin-film composite (TFC) FO membrane which leads to lower water flux. To mitigate the ICP effect, modification of the substrates’ properties has been one of the most effective methods. A new polyethersulfone-based ultrafiltration membrane with increased surface porosity and high water flux was recently produced by incorporating Zn2GeO4 nanowires. The composite membrane was used as a substrate for the fabrication of TFC FO membrane, by coating a thin layer of polyamide on top of the substrate. The substrate and the nanowires were characterized by a range of techniques such as SEM, XRD, and contact angle goniometry. The water permeability and molecular weight cut-offs (MWCO) of the substrate; and the FO performance of the TFC membrane were also determined. The Zn2GeO4-modified membrane showed ~45% increase in water permeability and NaCl salt rejection of 80% under RO mode. In FO mode, the ratio of water flux to reverse solute flux was also improved. However, lower FO flux was obtained which could be due to ICP. The result shows that Zn2GO4 nanowire may be used as a modifier to the substrate to improve the quality of the polyamide layer on the substrate to improve the flux and selectivity, but not as effective in reducing ICP. This work demonstrates that the incorporation of nanomaterials to the membrane substrate may be an alternative approach to improve the formation of polyamide skin layer to achieve better FO performance. PMID:25803239

  20. Improved oxygen reduction reaction catalyzed by Pt/Clay/Nafion nanocomposite for PEM fuel cells.

    PubMed

    Narayanamoorthy, B; Datta, K K R; Eswaramoorthy, M; Balaji, S

    2012-07-25

    A novel Pt nanoparticle (Pt NP) embedded aminoclay/Nafion (Pt/AC/N) nanocomposite catalyst film was prepared for oxygen reduction reaction by sol-gel method. The prepared nanocomposite films were surface characterized using XRD and TEM and thermal stability was studied by TGA. The prepared film has firmly bound Pt NP and could exhibit an improved electro-reduction activity compared to vulcan carbon/Nafion supported Pt NP (Pt/VC/N). Moreover, the Pt/AC/N film possessed good stability in the acidic environment. The limiting current density of the Pt/AC/N film with 35.4 μg/cm(2) of Pt loading was found to be 4.2 mA/cm(2), which is 30% higher than that of the Pt/VC/N. The maximum H2O2 intermediate formation was found to be ∼1.6% and the reaction found to follow a four electron transfer mechanism. Accelerated durability test for 2000 potential cycles showed that ca. 78% of initial limiting current was retained. The results are encouraging for possible use of the Pt/AC/N as the free-standing electrocatalyst layer for polymer electrolyte membrane fuel cells.

  1. Electrodialysis heterogeneous ion exchange membranes modified by SiO2 nanoparticles: fabrication and electrochemical characterization.

    PubMed

    Hosseini, S M; Ahmadi, Z; Nemati, M; Parvizian, F; Madaeni, S S

    2016-01-01

    In the current study mixed matrix heterogeneous cation exchange membranes were prepared by solution casting technique. The effect of SiO(2) nanoparticles in the polymeric solution on the physicochemical properties of prepared membranes was studied. Scanning optical microscope images showed uniform particle distribution and relatively uniform surfaces for the prepared membranes. The membrane water content was reduced by silica nanoparticles in the membranes' matrix. The membrane ion exchange capacity, membrane potential, transport number and selectivity were improved initially by an increase of SiO(2) nanoparticles concentration up to 1%wt in prepared membranes and then showed a decreasing trend with a further increase in additive ratio from 1 to 4%wt. The ionic permeability and flux were also decreased initially by an increase of silica nanoparticles concentration up to 0.5%wt in the membrane matrix and then increased again with a further increase in nanoparticles concentration from 0.5 to 4%wt. Moreover, the results exhibited that using silica nanoparticles in the membrane matrix caused an obvious decrease in areal electrical resistance. The opposite trend was found for membrane mechanical strength using SiO(2) nanoparticles. PMID:27148708

  2. Electrodialysis heterogeneous ion exchange membranes modified by SiO2 nanoparticles: fabrication and electrochemical characterization.

    PubMed

    Hosseini, S M; Ahmadi, Z; Nemati, M; Parvizian, F; Madaeni, S S

    2016-01-01

    In the current study mixed matrix heterogeneous cation exchange membranes were prepared by solution casting technique. The effect of SiO(2) nanoparticles in the polymeric solution on the physicochemical properties of prepared membranes was studied. Scanning optical microscope images showed uniform particle distribution and relatively uniform surfaces for the prepared membranes. The membrane water content was reduced by silica nanoparticles in the membranes' matrix. The membrane ion exchange capacity, membrane potential, transport number and selectivity were improved initially by an increase of SiO(2) nanoparticles concentration up to 1%wt in prepared membranes and then showed a decreasing trend with a further increase in additive ratio from 1 to 4%wt. The ionic permeability and flux were also decreased initially by an increase of silica nanoparticles concentration up to 0.5%wt in the membrane matrix and then increased again with a further increase in nanoparticles concentration from 0.5 to 4%wt. Moreover, the results exhibited that using silica nanoparticles in the membrane matrix caused an obvious decrease in areal electrical resistance. The opposite trend was found for membrane mechanical strength using SiO(2) nanoparticles.

  3. Constructing proton-conductive highways within an ionomer membrane by embedding sulfonated polymer brush modified graphene oxide

    NASA Astrophysics Data System (ADS)

    Zhao, Liping; Li, Yifan; Zhang, Haoqin; Wu, Wenjia; Liu, Jindun; Wang, Jingtao

    2015-07-01

    Sulfonated polymer brush modified graphene oxide (SP-GO) fillers with controllable brush length are synthesized via the facile distillation-precipitation polymerization, and then incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix to fabricate composite membranes. The influences of SP-GO upon the microstructures, including thermal and mechanical properties, water uptake/swelling, proton conduction, H2 permeability and single PEMFC performances of composite membranes are intensively investigated. It is found that the SP-GO fillers are uniformly dispersed and tend to lie perpendicularly to the cross-section surface of the whole membrane, which allow SP-GO fillers creating inter-connected and broad ionic pathways through the sulfonic acid groups in polymer brushes. Meanwhile, the SP-GO fillers connect the ionic clusters in SPEEK matrix via interfacial interactions. In such a way, proton-transfer highways are constructed along the SPEEK/SP-GO interface, which lower the proton transfer activation energy and enhance the proton conductivities of the composite membranes under both hydrated and anhydrous conditions. Furthermore, elevating the brush length on SP-GO could further enhance the proton conductivity. Compared to SPEEK control membrane, a 95.5% increase in hydrated conductivity, an 178% increase in anhydrous conductivity and a 37% increase in maximum power density are obtained for the optimal composite membrane.

  4. Application of pervaporation and vapor permeation processes to separate aqueous ethanol solution through chemically modified Nylon 4 membranes

    SciTech Connect

    Wang, Y.H.; Teng, M.Y.; Lee, K.R.; Wang, D.M.; Lai, J.Y.

    1998-08-01

    The pervaporation performance of a Nylon 4 membrane, chemically grafted by N,N-dimethylaminoethyl methacrylate (DMAEM), DMAEM-g-N4, was studied by measurement of the permeation ratio and the pervaporation separation index. It was found that the water permselectivity and permeation rate for the chemically modified Nylon 4 membrane were higher than those of the unmodified Nylon 4 membrane. Optimum pervaporation results, a separation factor of 28.3, and a permeation rate of 439 g/m{sup 2}{center_dot}h, were obtained when the degree of grafting was 12.7%. It was also found that all the permeation ratios at low temperature were less than unity. In addition, compared with pervaporation, vapor permeation effectively increases the permselectivity of water.

  5. Electrochemistry and electrocatalysis of myoglobin immobilized in sulfonated graphene oxide and Nafion films.

    PubMed

    Chen, Guiying; Sun, Hong; Hou, Shifeng

    2016-06-01

    In this study, sulfonated graphene oxide (SGO) was synthesized and characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was used to make Mb-SGO-Nafion composite films by coating myoglobin (Mb) on the glassy carbon electrodes (GCE). Positions of the Soret absorption bands suggested that Mb retained its native conformation in the films. Mb-SGO-Nafion film modified electrode showed a pair of well-defined and nearly reversible cyclic voltammetry peaks at around -0.39 V versus saturated calomel electrode (SCE) in pH 7.0 buffers, characteristic of heme Fe(III)/Fe(II) redox couples. Electrochemical parameters such as electron transfer rate constant (ks) and formal potential (E(o')) were estimated by fitting the data of square-wave voltammetry with nonlinear regression analysis. Experimental data demonstrated that the electron transfer between Mb and electrode was greatly facilitated and showed good electrocatalytic properties toward various substrates, such as H2O2 and NaNO2, with significant lowering of reduction overpotential.

  6. Electrochemistry and electrocatalysis of myoglobin immobilized in sulfonated graphene oxide and Nafion films.

    PubMed

    Chen, Guiying; Sun, Hong; Hou, Shifeng

    2016-06-01

    In this study, sulfonated graphene oxide (SGO) was synthesized and characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was used to make Mb-SGO-Nafion composite films by coating myoglobin (Mb) on the glassy carbon electrodes (GCE). Positions of the Soret absorption bands suggested that Mb retained its native conformation in the films. Mb-SGO-Nafion film modified electrode showed a pair of well-defined and nearly reversible cyclic voltammetry peaks at around -0.39 V versus saturated calomel electrode (SCE) in pH 7.0 buffers, characteristic of heme Fe(III)/Fe(II) redox couples. Electrochemical parameters such as electron transfer rate constant (ks) and formal potential (E(o')) were estimated by fitting the data of square-wave voltammetry with nonlinear regression analysis. Experimental data demonstrated that the electron transfer between Mb and electrode was greatly facilitated and showed good electrocatalytic properties toward various substrates, such as H2O2 and NaNO2, with significant lowering of reduction overpotential. PMID:27019153

  7. 125I-labeled peptide mapping of some heat-modifiable proteins of the gonococcal outer membrane.

    PubMed Central

    Swanson, J

    1980-01-01

    Gonococci from opaque colonies have cell wall outer membrane proteins that are lacking from organisms which form transparent colonies. These "colony opacity-associated" proteins are among a group of "minor" proteins that exhibit heat modification of their apparent subunit molecular sizes, are easily extracted by deoxycholate, have apparent subunit molecular weights varying from 24,000 to 29,000 and are exposed on the surfaces of gonococci. Other minor proteins found on gonococci are the "leukocyte association proteins," whose presence correlates with reactivities of gonococci with human neutrophils. Several of the colony opacity-associated proteins and leukocyte association proteins were subjected to 125I-peptide mapping of protein bands separated by polyacrylamide electrophoresis in the presence of sodium dodecyl sulfate. The structural similarities and differences among these heat-modifiable surface proteins were studied, as well as their similarities with the major protein of the gonococcal outer membrane. A relatively high apparent degree of structural homology is found among the heat-modifiable proteins from different strains of opaque colony gonococcal forms. There is also some apparent structural homology for 125I-peptides of heat-modifiable versus major proteins of the gonococcal outer membrane. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6 Fig. 7 Fig. 8 PMID:6769820

  8. Treatment of lead contaminated water by a PVDF membrane that is modified by zirconium, phosphate and PVA.

    PubMed

    Zhao, Dandan; Yu, Yang; Chen, J Paul

    2016-09-15

    Lead contamination is one of the most serious problems in drinking water facing humans. In this study, a novel zirconium phosphate modified polyvinyl alcohol (PVA)-PVDF membrane was developed for lead removal. The zirconium ions and PVA were firstly coated onto a PVDF membrane through crosslinking reactions with glutaraldehyde, which was then modified by phosphate. The adsorption kinetics study showed that most of ultimate uptake occurred in 5 h. The adsorption increased with an increase in pH; the optimal adsorption was achieved at pH 5.5. The experimental data were better described by Langmuir equation than Freundlich equation; the maximum adsorption capacity was 121.2 mg-Pb/g at pH 5.5, much higher than other reported adsorptive membranes. The membrane exhibited a higher selectivity for lead over zinc with a relative selectivity coefficient (Pb(2+)/Zn(2+)) of 9.92. The filtration study showed that the membrane with an area of 12.56 cm(2) could treat 13.9 L (equivalent to 73,000 bed volumes) of lead containing wastewater with an influent concentration of 224.5 μ g/L to meet the maximum contaminant level of 15 μ g/L. It was demonstrated that the membrane did well in the removal of lead in both simulated wastewater and lead-spiked reservoir water and had a good reusability in its applications. The XPS studies revealed that the lead uptake was mainly due to cation exchange between hydrogen ions and lead ions.

  9. Treatment of lead contaminated water by a PVDF membrane that is modified by zirconium, phosphate and PVA.

    PubMed

    Zhao, Dandan; Yu, Yang; Chen, J Paul

    2016-09-15

    Lead contamination is one of the most serious problems in drinking water facing humans. In this study, a novel zirconium phosphate modified polyvinyl alcohol (PVA)-PVDF membrane was developed for lead removal. The zirconium ions and PVA were firstly coated onto a PVDF membrane through crosslinking reactions with glutaraldehyde, which was then modified by phosphate. The adsorption kinetics study showed that most of ultimate uptake occurred in 5 h. The adsorption increased with an increase in pH; the optimal adsorption was achieved at pH 5.5. The experimental data were better described by Langmuir equation than Freundlich equation; the maximum adsorption capacity was 121.2 mg-Pb/g at pH 5.5, much higher than other reported adsorptive membranes. The membrane exhibited a higher selectivity for lead over zinc with a relative selectivity coefficient (Pb(2+)/Zn(2+)) of 9.92. The filtration study showed that the membrane with an area of 12.56 cm(2) could treat 13.9 L (equivalent to 73,000 bed volumes) of lead containing wastewater with an influent concentration of 224.5 μ g/L to meet the maximum contaminant level of 15 μ g/L. It was demonstrated that the membrane did well in the removal of lead in both simulated wastewater and lead-spiked reservoir water and had a good reusability in its applications. The XPS studies revealed that the lead uptake was mainly due to cation exchange between hydrogen ions and lead ions. PMID:27311109

  10. Surface Modified Biodegradable Electrospun Membranes as a Carrier for Human Embryonic Stem Cell-Derived Retinal Pigment Epithelial Cells.

    PubMed

    Sorkio, Anni; Porter, Patrick J; Juuti-Uusitalo, Kati; Meenan, Brian J; Skottman, Heli; Burke, George A

    2015-09-01

    Human embryonic stem cell-derived retinal pigment epithelial (hESC-RPE) cells are currently undergoing clinical trials to treat retinal degenerative diseases. Transplantation of hESC-RPE cells in conjuction with a supportive biomaterial carrier holds great potential as a future treatment for retinal degeneration. However, there has been no such biodegradable material that could support the growth and maturation of hESC-RPE cells so far. The primary aim of this work was to create a thin porous poly (L-lactide-co-caprolactone) (PLCL) membrane that could promote attachment, proliferation, and maturation of the hESC-RPE cells in serum-free culture conditions. The PLCL membranes were modified by atmospheric pressure plasma processing and coated with collagen IV to enhance cell growth and maturation. Permeability of the membranes was analyzed with an Ussing chamber system. Analysis with scanning electron microscopy, contact angle measurement, atomic force microscopy, and X-ray photoelectron spectroscopy demonstrated that plasma surface treatment augments the surface properties of the membrane, which enhances the binding and conformation of the protein. Cell proliferation assays, reverse transcription-polymerase chain reaction, indirect immunofluoresence staining, trans-epithelial electrical resistance measurements, and in vitro phagocytosis assay clearly demonstrated that the plasma treated PLCL membranes supported the adherence, proliferation, maturation and functionality of hESC-RPE cells in serum-free culture conditions. Here, we report for the first time, how PLCL membranes can be modified with atmospheric pressure plasma processing to enable the formation of a functional hESC-RPE monolayer on a porous biodegradable substrate, which have a potential as a tissue-engineered construct for regenerative retinal repair applications.

  11. Determination of As in tobacco by using electrochemical hydride generation at a Nafion® solid polymer electrolyte cell hyphenated with atomic fluorescence spectrometry

    NASA Astrophysics Data System (ADS)

    Yang, Qinghua; Gan, Wuer; Deng, Yun; Sun, Huihui

    2011-11-01

    In the present work, a novel solid polymer electrolyte hydride generation (SPE-HG) cell was developed. The home-made SPE-HG cell, mainly composed of three components (Nafion®117 membrane for separating and H + exchanging, a soft graphite felt cathode and a Ti mesh modified by Ir anode), was employed for detecting As by coupling to atomic fluorescence spectrometry (AFS). The H + generated by electrolysis of pure water in anode chamber transferred to cathode chamber through SPE, and immediately reacted with As 3 + to generate AsH 3. The relative mechanisms and operation conditions for hydride generation of As were investigated in detail. The developed cell employed water as an alternative of acid anolyte, with virtues of low-cost, more than 6 months lifetime and environment friendly compared with the conventional cell. Under the optimized conditions, the limit of determination of As 3 + for sample blank solution was 0.12 μg L - 1 , the RSD was 2.9% for 10 consecutive measurements of 5 μg L - 1 As 3 + standard solution. The accuracy of the method was verified by the determination of As in the reference Tea (GBW07605) and the developed method was successfully applied to determine trace amounts of As in tobacco samples with recovery from 97% to 103%.

  12. Structural and transport properties of Nafion in hydrobromic-acid solutions

    SciTech Connect

    Kusoglu, A; Cho, KT; Prato, RA; Weber, AZ

    2013-12-01

    Proton-exchange membranes are key solid-state ion carriers in many relevant energy technologies including flow batteries, fuel cells, and solar-fuel generators. In many of these systems, the membranes are in contact with electrolyte solutions. In this paper, we focus on the impact of different HBr, a flow-battery and exemplary acid electrolyte, external concentrations on the conductivity of Nafion, a perfluorosulfonic acid membrane that is commonly used in many energy-related applications. The peak and then decrease in conductivity is correlated with measured changes in the water and HBr content within the membrane. In addition, small-angle x-ray scattering is used to probe the nanostructure to correlate how the interactions of the bromide ion with the fixed sulfonic-acid sites impact conductivity and hydrophilic domain distance. It is also shown that membrane pretreatment has a large impact on the underlying structure/function relationship. The obtained data and results are useful for delineation of optimal operating regimes for flow batteries and similar technologies as well as in understanding underlying structure/function relationships of ionomers in electrolyte solutions. (C) 2013 Elsevier B.V. All rights reserved.

  13. Effect of gating modifier toxins on membrane thickness: implications for toxin effect on gramicidin and mechanosensitive channels.

    PubMed

    Chen, Rong; Chung, Shin-Ho

    2013-02-22

    Various gating modifier toxins partition into membranes and interfere with the gating mechanisms of biological ion channels. For example, GsMTx4 potentiates gramicidin and several bacterial mechanosensitive channels whose gating kinetics are sensitive to mechanical properties of the membrane, whereas binding of HpTx2 shifts the voltage-activity curve of the voltage-gated potassium channel Kv4.2 to the right. The detailed process by which the toxin partitions into membranes has been difficult to probe using molecular dynamics due to the limited time scale accessible. Here we develop a protocol that allows the spontaneous assembly of a polypeptide toxin into membranes in atomistic molecular dynamics simulations of tens of nanoseconds. The protocol is applied to GsMTx4 and HpTx2. Both toxins, released in water at the start of the simulation, spontaneously bind into the lipid bilayer within 50 ns, with their hydrophobic patch penetrated into the bilayer beyond the phosphate groups of the lipids. It is found that the bilayer is about 2 Å thinner upon the binding of a GsMTx4 monomer. Such a thinning effect of GsMTx4 on membranes may explain its potentiation effect on gramicidin and mechanosensitive channels.

  14. Staphylococcal Phenotypes Induced by Naturally Occurring and Synthetic Membrane-Interactive Polyphenolic β-Lactam Resistance Modifiers

    PubMed Central

    Palacios, Lucia; Rosado, Helena; Micol, Vicente; Rosato, Adriana E.; Bernal, Patricia; Arroyo, Raquel; Grounds, Helen; Anderson, James C.; Stabler, Richard A.; Taylor, Peter W.

    2014-01-01

    Galloyl catechins, in particular (-)-epicatechin gallate (ECg), have the capacity to abrogate β-lactam resistance in methicillin-resistant strains of Staphylococcus aureus (MRSA); they also prevent biofilm formation, reduce the secretion of a large proportion of the exoproteome and induce profound changes to cell morphology. Current evidence suggests that these reversible phenotypic traits result from their intercalation into the bacterial cytoplasmic membrane. We have endeavoured to potentiate the capacity of ECg to modify the MRSA phenotype by stepwise removal of hydroxyl groups from the B-ring pharmacophore and the A:C fused ring system of the naturally occurring molecule. ECg binds rapidly to the membrane, inducing up-regulation of genes responsible for protection against cell wall stress and maintenance of membrane integrity and function. Studies with artificial membranes modelled on the lipid composition of the staphylococcal bilayer indicated that ECg adopts a position deep within the lipid palisade, eliciting major alterations in the thermotropic behaviour of the bilayer. The non-galloylated homolog (-)-epicatechin enhanced ECg-mediated effects by facilitating entry of ECg molecules into the membrane. ECg analogs with unnatural B-ring hydroxylation patterns induced higher levels of gene expression and more profound changes to MRSA membrane fluidity than ECg but adopted a more superficial location within the bilayer. ECg possessed a high affinity for the positively charged staphylococcal membrane and induced changes to the biophysical properties of the bilayer that are likely to account for its capacity to disperse the cell wall biosynthetic machinery responsible for β-lactam resistance. The ability to enhance these properties by chemical modification of ECg raises the possibility that more potent analogs could be developed for clinical evaluation. PMID:24699700

  15. Preparation of antifouling polyvinylpyrrolidone (PVP 40K) modified polyethersulfone (PES) ultrafiltration (UF) membrane for water purification

    NASA Astrophysics Data System (ADS)

    Vatsha, Banele; Ngila, Jane Catherine; Moutloali, Richard M.

    This study reports the fabrication of polyethersulfone (PES) membrane using the phase inversion method in the presence of polyvinylpyrrolidone (PVP, 40K) as pore-forming agent. The membranes were made from two PES concentration types, i.e. 16 and 18 wt.%. The effect of high molecular weight PVP concentration (2-10%) was examined in order to obtain a membrane with good performance, i.e. high water flux and reasonable Bovine Serum Albumin (BSA, protein model solution) rejection. The optimised membranes were characterised by ATR-FTIR, AFM, SEM, contact angle and dead-end membrane filtration tests. It was found that PVP moieties have positive influence in the prepared PES membranes. SEM surface and cross-sectional images were used to observed morphological changes as PVP content was varied. The pore sizes increased with PVP content for membranes prepared from 16 wt.% PES polymer, whereas at the higher PVP content in 18 wt.% PES membrane, pore sizes tend to decrease or completely disappear. The CA decreased gradually for the 16 wt.% PES with increasing PVP content whereas in the 18 wt.% PES the CA decreased initially before tapering off or increasing slightly. The rejection of BSA solution by both neat PES and PVP-containing PES membrane was above 85%. AFM surface topography exhibited increase in roughness value with PVP content. FTIR/ATR spectra corroborated the functional composition of neat PES and PVP molecule dispersed on PES membrane backbone. The results attained confirmed the potential industrial application of PVP molecule to minimise fouling tendencies.

  16. Improved antibacterial activity of nanofiltration polysulfone membranes modified with silver nanoparticles.

    PubMed

    Andrade, Patricia Fernanda; de Faria, Andreia Fonseca; Oliveira, Silvana Ruella; Arruda, Marco Aurélio Zezzi; Gonçalves, Maria do Carmo

    2015-09-15

    Polysulfone membranes (PSf) containing silver nanoparticles were prepared by the wet phase-inversion process. Silver nanoparticles (AgNP) were dispersed into the polymer matrix using two different methodologies. In the first one, the AgNP were synthesized and further dispersed into the polymer solution (ex situ process). In the second method, the formation of the AgNP was performed in situ. The AgNP crystalline structure in the PSf membranes was confirmed by X-ray diffraction. Field emission scanning electron microscopy images showed that the addition of AgNP in PSf membranes caused no significant changes to the finger-like morphology. When the ex situ methodology was applied, 45 nm average size AgNP were uniformly distributed in the internal pores of the membranes. However, when the AgNP were formed through the in situ process, the AgNP were uniformly and preferentially distributed on the top and bottom surfaces of the membrane. In the last case, the AgNP showed cubic morphology when present in the bottom and top surfaces, however, when inside the membrane their morphology was spherical. The cubic-like nanoparticles displayed a 38 nm average edge length. The silver ion released from the membrane during water filtration was measured using inductively coupled plasma mass spectrometry, which showed a silver leaching of approximately 2 μg L(-1). The nanocomposite membranes prepared by the in situ method exhibited a better antibacterial activity, in comparison to those prepared by ex situ, and also a decrease in 90% Escherichia coli adhered cells compared to the pristine PSf membranes. In conclusion, the in situ procedure can be considered a feasible, simple, and reproducible methodology to prepare anti-biofouling polysulfone membranes containing AgNP.

  17. Study and development of sulfated zirconia based proton exchange fuel cell membranes

    NASA Astrophysics Data System (ADS)

    Kemp, Brittany Wilson

    With the increasing consumption of energy, fuel cells are among the most promising alternatives to fossil fuels, provided some technical challenges are overcome. Proton exchange membrane fuel cells (PEMFCs) have been investigated and improvements have been made, but the problem with NafionRTM, the main membrane for PEMFCs, has not been solved. NafionRTM restricts the membranes from operating at higher temperatures, thus preventing them from working in small electronics. The problem is to develop a novel fuel cell membrane that performs comparably to NafionRTM in PEMFCs. The membranes were fabricated by applying sulfated zirconia, via template wetting, to porous alumina membranes. The fabricated membranes showed a proton conductivity of 0.016 S/cm in comparison to the proton conductivity of Nafion RTM (0.05 S/cm). Both formic acid and methanol had a lower crossover flux through the sulfated zirconia membranes (formic acid- 2.89x10 -7 mols/cm2s and methanol-1.78x10-9 mols/cm2s) than through NafionRTM (formic acid-2.03x10 -8 mols/cm2s methanol-2.42x10-6 mols/cm 2s), indicating that a sulfated zirconia PEMFC may serve as a replacement for NafionRTM.

  18. An Improvement Delivery of siRNA by IRQ Ligand-Modified Double Membranous Nano-Carrier

    NASA Astrophysics Data System (ADS)

    Mudhakir, Diky; Tan, Erdal; Akita, Hidetaka; Harashima, Hideyoshi

    2010-10-01

    In the present study, the enhancement of siRNA delivery into cytosol from the IRQ-modified multi-envelope type nano-device (IRQ-MEND) was investigated. It is known that IRQ-MEND efficiently enters cells by clathrin-mediated endocytosis and caveolar endocytosis pathways, resulting in gene silencing. In the present study, we controlled the number of layers of IRQ-MEND encapsulating siRNA by using double membranous nano-device strategy. This vector design overcomes intracellular barriers such as endosomal membrane, resulting drastically enhance transgene expression. In addition, the contribution of uptake mechanism of IRQ-modified nano-carrier to transgene expression was studied. The use of hypertonic treatment inhibited gene silencing, but it was not suppressed by the addition of filipin. These results indicate that low pH is important to induce the transgene expression. In conclusion, delivery of cytosolic siRNA can be enhanced by the use of double-membranous nano-carrier system which utilizes a clathrin-mediated endocytosis pathway to induce gene silencing.

  19. Hierarchical Nafion enhanced carbon aerogels for sensing applications

    NASA Astrophysics Data System (ADS)

    Weng, Bo; Ding, Ailing; Liu, Yuqing; Diao, Jianglin; Razal, Joselito; Lau, King Tong; Shepherd, Roderick; Li, Changming; Chen, Jun

    2016-02-01

    This work describes the fabrication of hierarchical 3D Nafion enhanced carbon aerogels (NECAGs) for sensing applications via a fast freeze drying method. Graphene oxide, multiwalled carbon nanotubes and Nafion were mixed and extruded into liquid nitrogen followed by the removal of ice crystals by freeze drying. The addition of Nafion enhanced the mechanical strength of NECAGs and effective control of the cellular morphology and pore size was achieved. The resultant NECAGs demonstrated high strength, low density, and high specific surface area and can achieve a modulus of 20 kPa, an electrical conductivity of 140 S m-1, and a specific capacity of 136.8 F g-1 after reduction. Therefore, NECAG monoliths performed well as a gas sensor and as a biosensor with high sensitivity and selectivity. The remarkable sensitivity of 8.52 × 103 μA mM-1 cm-2 was obtained in dopamine (DA) detection, which is two orders of magnitude better than the literature reported values using graphene aerogel electrodes made from a porous Ni template. These outstanding properties make the NECAG a promising electrode candidate for a wide range of applications. Further in-depth investigations are being undertaken to probe the structure-property relationship of NECAG monoliths prepared under various conditions.This work describes the fabrication of hierarchical 3D Nafion enhanced carbon aerogels (NECAGs) for sensing applications via a fast freeze drying method. Graphene oxide, multiwalled carbon nanotubes and Nafion were mixed and extruded into liquid nitrogen followed by the removal of ice crystals by freeze drying. The addition of Nafion enhanced the mechanical strength of NECAGs and effective control of the cellular morphology and pore size was achieved. The resultant NECAGs demonstrated high strength, low density, and high specific surface area and can achieve a modulus of 20 kPa, an electrical conductivity of 140 S m-1, and a specific capacity of 136.8 F g-1 after reduction. Therefore, NECAG

  20. Low Crossover Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

    NASA Technical Reports Server (NTRS)

    Prakash, G. K. Surya; Smart, Marshall; Atti, Anthony R.; Olah, George A.; Narayanan, S. R.; Valdez, T.; Surampudi, S.

    1996-01-01

    Direct Methanol Fuel Cells (DMFC's) using polymer electrolyte membranes are promising power sources for portable and vehicular applications. State of the art technology using Nafion(R) 117 membranes (Dupont) are limited by high methanol permeability and cost, resulting in reduced fuel cell efficiencies and impractical commercialization. Therefore, much research in the fuel cell field is focused on the preparation and testing of low crossover and cost efficient polymer electrolyte membranes. The University of Southern California in cooperation with the Jet Propulsion Laboratory is focused on development of such materials. Interpenetrating polymer networks are an effective method used to blend polymer systems without forming chemical links. They provide the ability to modify physical and chemical properties of polymers by optimizing blend compositions. We have developed a novel interpenetrating polymer network based on poly (vinyl - difluoride)/cross-linked polystyrenesulfonic acid polymer composites (PVDF PSSA). Sulfonation of polystyrene accounts for protonic conductivity while the non-polar, PVDF backbone provides structural integrity in addition to methanol rejection. Precursor materials were prepared and analyzed to characterize membrane crystallinity, stability and degree of interpenetration. USC JPL PVDF-PSSA membranes were also characterized to determine methanol permeability, protonic conductivity and sulfur distribution. Membranes were fabricated into membrane electrode assemblies (MEA) and tested for single cell performance. Tests include cell performance over a wide range of temperatures (20 C - 90 C) and cathode conditions (ambient Air/O2). Methanol crossover values are measured in situ using an in-line CO2 analyzer.

  1. Electrochemical Properties of a Thiol Monolayers Coated Gold Electrode Modified with Osmium Gel Membrane as Enzyme Sensor

    NASA Astrophysics Data System (ADS)

    Yabutani, Tomoki; Okada, Nobuyuki; Maruyama, Kenichi; Motonaka, Junko

    The electrochemical behavior of an enzyme sensor for glucose using a gold electrode modified with thiol self-assembled membrane and osmium complex gel as an electron transferring mediator has further been investigated by electrochemical analysis. The gold electrode was initially coated with aminomethanethiol self assembling mono layer membrane(thiol-SAM) and then immobilized with glucose oxidase using poly(vinylpyridine-co-allylamine) (PVP-co-AA), gel coordinated with osmium bipyridine complexes (GOD/Os-PVP-co-AA gel). The cleaning condition of the surface of the Au electrode prior to coating thiol SAM was optimized for reduction of interference caused by concomitant compounds. It was found that interfering influence was most efficiently reduced in the case of use of the Au electrode immersed into nitric acid. The current ratio with a thiol coated gold electrode modified with Os-PVP-co-AA gel in glucose solution in the presence to absence of ascorbic acid, acetaminophen, and uric acid (ID+I/II) was 1.006, 1.014, and 1.018, respectively. The peak current response of glucose in the electrode modified with thiol SAM was dropped to 60 98% as compared with that without thiol SAM.

  2. Modifier role of internal H+ in activating the Na+-H+ exchanger in renal microvillus membrane vesicles.

    PubMed

    Aronson, P S; Nee, J; Suhm, M A

    1982-09-01

    The intracellular pH in animal cells in generally maintained at a higher level than would be expected if H+ were passively distributed across the plasma membrane. In a wide variety of cells including sea urchin eggs, skeletal muscle, renal and intestinal epithelial cells, and neuroblastoma cells, plasma membrane Na+-H+ exchangers mediate the uphill extrusion of H+ coupled to, and thus energized by, the downhill entry of Na+. Plasma membrane vesicles isolated from the luminal (microvillus, brush border) surface of renal proximal tubular cells possess a Na+-H+ exchanger that seems to be representative of the Na+-H+ exchangers found in other tissues. For example, the renal microvillus membrane Na+-H+ exchanger, like other Na+-H+ exchangers, mediates electroneutral cation exchange, is sensitive to inhibition by the diuretic drug amiloride, and has affinity for Li+ in addition to Na+ and H+ (refs 5, 9). Here we have examined the effect of internal H+ on the activity of the Na+-H+ exchanger in renal microvillus membrane vesicles. Our results suggest that internal H+, independent of its role as a substrate for exchange with external independent of its role as a substrate for exchange with external independent of its role as a substrate for exchange with external Na+, has an important modifier role as an allosteric activator of the Na+-H+ exchanger. Allosteric behaviour with respect to internal H+ is a property that would enhance the ability of plasma membrane Na+-H+ exchangers to extrude intracellular acid loads and thereby contribute to the regulation of intracellular pH.

  3. Autofocus fluid lens device construction and implementation of modified ionic polymer metal composite (IPMC) membrane actuators

    NASA Astrophysics Data System (ADS)

    Kiefer, Rudolf; Kiveste, Harti; Punning, Andres; Kesküla, Arko; Lulla, Tõnis; Aabloo, Alvo

    2014-03-01

    The autofocus fluid lens device, as developed by Philips, is based on water/oil interfaces forming a spherical lens where the meniscus of the liquid can be switched by applying a high voltage to change from a convex to a concave divergent lens. In this work we construct a device to evaluate the performance of membrane actuators based on electro active polymers, in a design applicable for autofocus fluid lens applications. The membrane with a hole in the middle separates the oil phase from the electrolyte phase, forming a meniscus in the middle of the membrane between the oil and electrolyte. If the membrane actuator shows a certain force and displacement, the meniscus between oil and electrolyte changes form between concave and convex, applicable as a fluid lens. Ionic polymer metal composites (IPMCs) are applied in this work to investigate how the performance of the membrane actuator takes place in Milli-Q, certain electrolytes and in combination with an electrochemically deposited conducting polymer. The goal of this work is to investigate the extent of membrane displacement of IPMC actuators operating at a low voltage (+/-0.7 V), and the back relaxation phenomena of IPMC actuators.

  4. BASELINE MEMBRANE SELECTION AND CHARACTERIZATION FOR AN SDE

    SciTech Connect

    Colon-Mercado, H; David Hobbs, D

    2007-04-03

    Thermochemical processes are being developed to provide global-scale quantities of hydrogen. A variant on sulfur-based thermochemical cycles is the Hybrid Sulfur (HyS) Process which uses a sulfur dioxide depolarized electrolyzer (SDE) to produce the hydrogen. In FY05 and FY06, testing at the Savannah River National Laboratory (SRNL) explored a low temperature fuel cell design concept for the SDE. The advantages of this design concept include high electrochemical efficiency and small footprint that are crucial for successful implementation on a commercial scale. A key component of the SDE is the ion conductive membrane through which protons produced at anode migrate to the cathode and react to produce hydrogen. An ideal membrane for the SDE should have both low ionic resistivity and low sulfur dioxide transport. These features allow the electrolyzer to perform at high currents with low potentials, along with preventing contamination of both the hydrogen output and poisoning of the catalysts involved. Another key component is the electrocatalyst material used for the anode and cathode. Good electrocatalysts should be chemically stable and have a low overpotential for the desired electrochemical reactions. This report summarizes results from activities to evaluate commercial and experimental membranes for the SDE. Several different types of commercially-available membranes were analyzed for sulfur dioxide transport as a function of acid strength including perfluorinated sulfonic acid (PFSA), sulfonated poly-etherketone-ketone, and poly-benzimidazole (PBI) membranes. Experimental membranes from the sulfonated diels-alder polyphenylenes (SDAPP) and modified Nafion{reg_sign} 117 were evaluated for SO{sub 2} transport as well. These membranes exhibited reduced transport coefficient for SO{sub 2} transport without the loss in ionic conductivity. The use of Nafion{reg_sign} with EW 1100 is recommended for the present SDE testing due to the limited data regarding chemical

  5. Sialidase NEU3 Dynamically Associates to Different Membrane Domains Specifically Modifying Their Ganglioside Pattern and Triggering Akt Phosphorylation

    PubMed Central

    Pasini, Mario; Dileo, Loredana; Orizio, Flavia; Monti, Eugenio; Caimi, Luigi; Venerando, Bruno; Bresciani, Roberto

    2014-01-01

    Lipid rafts are known to regulate several membrane functions such as signaling, trafficking and cellular adhesion. The local enrichment in sphingolipids and cholesterol together with the low protein content allows their separation by density gradient flotation after extraction with non-ionic detergent at low temperature. These structures are also referred to as detergent resistant membranes (DRM). Among sphingolipids, gangliosides play important roles in different biological events, including signal transduction and tumorigenesis. Sialidase NEU3 shows high enzymatic specificity toward gangliosides. Moreover, the enzyme is present both at the cell surface and in endosomal structures and cofractionates with caveolin. Although changes in the expression level of NEU3 have been correlated to different tumors, little is known about the precise distribution of the protein and its ability in modifying the ganglioside composition of DRM and non-DRM, thus regulating intracellular events. By means of inducible expression cell system we found that i) newly synthesized NEU3 is initially associated to non-DRM; ii) at steady state the protein is equally distributed between the two membrane subcompartments, i.e., DRM and non-DRM; iii) NEU3 is degraded via the proteasomal pathway; iv) the enzyme specifically modifies the ganglioside composition of the membrane areas where it resides; and v) NEU3 triggers phosphorylation of Akt, even in absence of exogenously administered EGF. Taken together our data demonstrate that NEU3 regulates the DRM ganglioside content and it can be considered as a modulator of Akt phosphorylation, further supporting the role of this enzyme in cancer and tumorigenesis. PMID:24925219

  6. Pure and Modified Co-Poly(amide-12-b-ethylene oxide) Membranes for Gas Separation Studied by Molecular Investigations

    PubMed Central

    De Lorenzo, Luana; Tocci, Elena; Gugliuzza, Annarosa; Drioli, Enrico

    2012-01-01

    This paper deals with a theoretical investigation of gas transport properties in a pure and modified PEBAX block copolymer membrane with N-ethyl-o/p-toluene sulfonamide (KET) as additive molecules. Molecular dynamics simulations using COMPASS force field, Gusev-Suter Transition State Theory (TST) and Monte Carlo methods were used. Bulk models of PEBAX and PEBAX/KET in different copolymer/additive compositions were assembled and analyzed to evaluate gas permeability and morphology to characterize structure-performance relationships. PMID:24958285

  7. Membrane lipid raft organization is uniquely modified by n-3 polyunsaturated fatty acids

    PubMed Central

    Turk, Harmony F.; Chapkin, Robert S.

    2012-01-01

    Fish oil, enriched in bioactive n-3 polyunsaturated fatty acids (PUFA), has been shown to play a role in prevention of colon cancer. The effects of n-3 PUFA are pleiotropic and multifaceted, resulting in an incomplete understanding of their molecular mechanisms of action. Here, we focus on a highly conserved mechanism of n-3 PUFA, which is the alteration of the organization of the plasma membrane. We highlight recent work demonstrating that enrichment of n-3 PUFA in the plasma membrane alters the lateral organization of membrane signaling assemblies (i.e. lipid rafts). This mechanism is central for n-3 PUFA regulation of downstream signaling, T-cell activation, transcriptional activation, and cytokine secretion. We conclude that these studies provide strong evidence for a predominant mechanism by which n-3 PUFA function in colon cancer prevention. PMID:22515942

  8. Hierarchical Nafion enhanced carbon aerogels for sensing applications.

    PubMed

    Weng, Bo; Ding, Ailing; Liu, Yuqing; Diao, Jianglin; Razal, Joselito; Lau, King Tong; Shepherd, Roderick; Li, Changming; Chen, Jun

    2016-02-14

    This work describes the fabrication of hierarchical 3D Nafion enhanced carbon aerogels (NECAGs) for sensing applications via a fast freeze drying method. Graphene oxide, multiwalled carbon nanotubes and Nafion were mixed and extruded into liquid nitrogen followed by the removal of ice crystals by freeze drying. The addition of Nafion enhanced the mechanical strength of NECAGs and effective control of the cellular morphology and pore size was achieved. The resultant NECAGs demonstrated high strength, low density, and high specific surface area and can achieve a modulus of 20 kPa, an electrical conductivity of 140 S m(-1), and a specific capacity of 136.8 F g(-1) after reduction. Therefore, NECAG monoliths performed well as a gas sensor and as a biosensor with high sensitivity and selectivity. The remarkable sensitivity of 8.52 × 10(3)μA mM(-1) cm(-2) was obtained in dopamine (DA) detection, which is two orders of magnitude better than the literature reported values using graphene aerogel electrodes made from a porous Ni template. These outstanding properties make the NECAG a promising electrode candidate for a wide range of applications. Further in-depth investigations are being undertaken to probe the structure-property relationship of NECAG monoliths prepared under various conditions. PMID:26791962

  9. Mechanical Properties of Composite SPEEK Polymer Membranes Modified with Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Sprugis, E.; Reinholds, I.; Vaivars, G.

    2015-03-01

    In this work, the mechanical properties of sulphonated polyetheretherketone (SPEEK) membranes impregnated with 3 different ionic liquids (1-butyl-2,3-dimethyl- imidazolium dimethylphosphate ([BMMIM][Me2PO4])), 1,2,3-trimethylimidazolium dimethylphosphate ([MMMIM][Me2PO4])), 1,3-dimethylimidazolium dimethylphosphate ([MMIM][Me2PO4])) have been investigated. Prepared SPEEK/ionic liquid composite membranes are characterized by mechanical testing both in room and elevated temperatures. It was found that the stiffness and tensile strength of composites decreased by increasing the content of ionic liquid and the length of alkyl radical in ionic liquid as well as by increasing the temperature.

  10. Dietary fat modifies mitochondrial and plasma membrane apoptotic signaling in skeletal muscle of calorie-restricted mice.

    PubMed

    López-Domínguez, José Alberto; Khraiwesh, Husam; González-Reyes, José Antonio; López-Lluch, Guillermo; Navas, Plácido; Ramsey, Jon Jay; de Cabo, Rafael; Burón, María Isabel; Villalba, José M

    2013-12-01

    Calorie restriction decreases skeletal muscle apoptosis, and this phenomenon has been mechanistically linked to its protective action against sarcopenia of aging. Alterations in lipid composition of membranes have been related with the beneficial effects of calorie restriction. However, no study has been designed to date to elucidate if different dietary fat sources with calorie restriction modify apoptotic signaling in skeletal muscle. We show that a 6-month calorie restriction decreased the activity of the plasma membrane neutral sphingomyelinase, although caspase-8/10 activity was not altered, in young adult mice. Lipid hydroperoxides, Bax levels, and cytochrome c and AIF release/accumulation into the cytosol were also decreased, although caspase-9 activity was unchanged. No alterations in caspase-3 and apoptotic index (DNA fragmentation) were observed, but calorie restriction improved structural features of gastrocnemius fibers by increasing cross-sectional area and decreasing circularity of fibers in cross sections. Changing dietary fat with calorie restriction produced substantial alterations of apoptotic signaling. Fish oil augmented the protective effect of calorie restriction decreasing plasma membrane neutral sphingomyelinase, Bax levels, caspase-8/10, and -9 activities, while increasing levels of the antioxidant coenzyme Q at the plasma membrane, and potentiating the increase of cross-sectional area and the decrease of fiber circularity in cross sections. Many of these changes were not found when we used lard. Our data support that dietary fish oil with calorie restriction produces a cellular anti-apoptotic environment in skeletal muscle with a downregulation of components involved in the initial stages of apoptosis engagement, both at the plasma membrane and the mitochondria.

  11. High resolution neutron imaging of water in the polymer electrolyte fuel cell membrane

    SciTech Connect

    Mukherjee, Partha P; Makundan, Rangachary; Spendelow, Jacob S; Borup, Rodney L; Hussey, D S; Jacobson, D L; Arif, M

    2009-01-01

    Water transport in the ionomeric membrane, typically Nafion{reg_sign}, has profound influence on the performance of the polymer electrolyte fuel cell, in terms of internal resistance and overall water balance. In this work, high resolution neutron imaging of the Nafion{reg_sign} membrane is presented in order to measure water content and through-plane gradients in situ under disparate temperature and humidification conditions.

  12. Amperometric biosensors based on nafion coated screen-printed electrodes for the determination of cholinesterase inhibitors.

    PubMed

    Gogol, E V; Evtugyn, G A; Marty, J L; Budnikov, H C; Winter, V G

    2000-11-01

    Screen-printed electrodes coated with the nafion layer have been investigated for cholinesterase biosensor design. The butyrylcholinesterase (ChE) from horse serum was immobilised onto the nafion layer by cross-linking with glutaraldehyde vapours. The biosensors obtained showed better long-term stability and lower working potential in comparison to those obtained with no nafion coating. The sensitivity of a biosensor toward organophosphate pesticides is not affected by the nafion coating. The detection limits were found to be 3.5x10(-7) M for trichlorfon and 1.5x10(-7) M for coumaphos. PMID:18968123

  13. Impedance Spectroscopic Investigation of Proton Conductivity in Nafion Using Transient Electrochemical Atomic Force Microscopy (AFM)

    PubMed Central

    Hink, Steffen; Wagner, Norbert; Bessler, Wolfgang G.; Roduner, Emil

    2012-01-01

    Spatially resolved impedance spectroscopy of a Nafion polyelectrolyte membrane is performed employing a conductive and Pt-coated tip of an atomic force microscope as a point-like contact and electrode. The experiment is conducted by perturbing the system by a rectangular voltage step and measuring the incurred current, followed by Fourier transformation and plotting the impedance against the frequency in a conventional Bode diagram. To test the potential and limitations of this novel method, we present a feasibility study using an identical hydrogen atmosphere at a well-defined relative humidity on both sides of the membrane. It is demonstrated that good quality impedance spectra are obtained in a frequency range of 0.2–1000 Hz. The extracted polarization curves exhibit a maximum current which cannot be explained by typical diffusion effects. Simulation based on equivalent circuits requires a Nernst element for restricted diffusion in the membrane which suggests that this effect is based on the potential dependence of the electrolyte resistance in the high overpotential region. PMID:24958175

  14. A modified cable formalism for modeling neuronal membranes at high frequencies.

    PubMed

    Bédard, Claude; Destexhe, Alain

    2008-02-15

    Intracellular recordings of cortical neurons in vivo display intense subthreshold membrane potential (V(m)) activity. The power spectral density of the V(m) displays a power-law structure at high frequencies (>50 Hz) with a slope of approximately -2.5. This type of frequency scaling cannot be accounted for by traditional models, as either single-compartment models or models based on reconstructed cell morphologies display a frequency scaling with a slope close to -4. This slope is due to the fact that the membrane resistance is short-circuited by the capacitance for high frequencies, a situation which may not be realistic. Here, we integrate nonideal capacitors in cable equations to reflect the fact that the capacitance cannot be charged instantaneously. We show that the resulting nonideal cable model can be solved analytically using Fourier transforms. Numerical simulations using a ball-and-stick model yield membrane potential activity with similar frequency scaling as in the experiments. We also discuss the consequences of using nonideal capacitors on other cellular properties such as the transmission of high frequencies, which is boosted in nonideal cables, or voltage attenuation in dendrites. These results suggest that cable equations based on nonideal capacitors should be used to capture the behavior of neuronal membranes at high frequencies. PMID:17921220

  15. A Modified Cable Formalism for Modeling Neuronal Membranes at High Frequencies

    PubMed Central

    Bédard, Claude; Destexhe, Alain

    2008-01-01

    Intracellular recordings of cortical neurons in vivo display intense subthreshold membrane potential (Vm) activity. The power spectral density of the Vm displays a power-law structure at high frequencies (>50 Hz) with a slope of ∼−2.5. This type of frequency scaling cannot be accounted for by traditional models, as either single-compartment models or models based on reconstructed cell morphologies display a frequency scaling with a slope close to −4. This slope is due to the fact that the membrane resistance is short-circuited by the capacitance for high frequencies, a situation which may not be realistic. Here, we integrate nonideal capacitors in cable equations to reflect the fact that the capacitance cannot be charged instantaneously. We show that the resulting nonideal cable model can be solved analytically using Fourier transforms. Numerical simulations using a ball-and-stick model yield membrane potential activity with similar frequency scaling as in the experiments. We also discuss the consequences of using nonideal capacitors on other cellular properties such as the transmission of high frequencies, which is boosted in nonideal cables, or voltage attenuation in dendrites. These results suggest that cable equations based on nonideal capacitors should be used to capture the behavior of neuronal membranes at high frequencies. PMID:17921220

  16. Synthesis, antimicrobial activity, and membrane permeabilizing properties of C-terminally modified nisin conjugates accessed by CuAAC.

    PubMed

    Slootweg, Jack C; van der Wal, Steffen; Quarles van Ufford, H C; Breukink, Eefjan; Liskamp, Rob M J; Rijkers, Dirk T S

    2013-12-18

    Functionalization of the lantibiotic nisin with fluorescent reporter molecules is highly important for the understanding of its mode of action as a potent antimicrobial peptide. In addition to this, multimerization of nisin to obtain multivalent peptide constructs and conjugation of nisin to bioactive molecules or grafting it on surfaces can be attractive methods for interference with bacterial growth. Here, we report a convenient method for the synthesis of such nisin conjugates and show that these nisin derivatives retain both their antimicrobial activity and their membrane permeabilizing properties. The synthesis is based on the Cu(I)-catalyzed alkyne-azide cycloaddition reaction (CuAAC) as a bioorthogonal ligation method for large and unprotected peptides in which nisin was C-terminally modified with propargylamine and subsequently efficiently conjugated to a series of functionalized azides. Two fluorescently labeled nisin conjugates together with a dimeric nisin construct were prepared while membrane insertion as well as antimicrobial activity were unaffected by these modifications. This study shows that C-terminal modification of nisin does not deteriorate biological activity in sharp contrast to N-terminal modification and therefore C-terminally modified nisin analogues are valuable tools to study the antibacterial mode of action of nisin. Furthermore, the ability to use stoichiometric amounts of the azide containing molecule opens up possibilities for surface tethering and more complex multivalent structures.

  17. Synthesis, antimicrobial activity, and membrane permeabilizing properties of C-terminally modified nisin conjugates accessed by CuAAC.

    PubMed

    Slootweg, Jack C; van der Wal, Steffen; Quarles van Ufford, H C; Breukink, Eefjan; Liskamp, Rob M J; Rijkers, Dirk T S

    2013-12-18

    Functionalization of the lantibiotic nisin with fluorescent reporter molecules is highly important for the understanding of its mode of action as a potent antimicrobial peptide. In addition to this, multimerization of nisin to obtain multivalent peptide constructs and conjugation of nisin to bioactive molecules or grafting it on surfaces can be attractive methods for interference with bacterial growth. Here, we report a convenient method for the synthesis of such nisin conjugates and show that these nisin derivatives retain both their antimicrobial activity and their membrane permeabilizing properties. The synthesis is based on the Cu(I)-catalyzed alkyne-azide cycloaddition reaction (CuAAC) as a bioorthogonal ligation method for large and unprotected peptides in which nisin was C-terminally modified with propargylamine and subsequently efficiently conjugated to a series of functionalized azides. Two fluorescently labeled nisin conjugates together with a dimeric nisin construct were prepared while membrane insertion as well as antimicrobial activity were unaffected by these modifications. This study shows that C-terminal modification of nisin does not deteriorate biological activity in sharp contrast to N-terminal modification and therefore C-terminally modified nisin analogues are valuable tools to study the antibacterial mode of action of nisin. Furthermore, the ability to use stoichiometric amounts of the azide containing molecule opens up possibilities for surface tethering and more complex multivalent structures. PMID:24266643

  18. Ti3C2Tx Filler Effect on the Proton Conduction Property of Polymer Electrolyte Membrane.

    PubMed

    Liu, Yahua; Zhang, Jiakui; Zhang, Xiang; Li, Yifan; Wang, Jingtao

    2016-08-10

    Conductive polymer electrolyte membranes are increasingly attractive for a wide range of applications in hydrogen-relevant devices, for instance hydrogen fuel cells. In this study, two-dimensional Ti3C2Tx, a typical representative of the recently developed MXene family, is synthesized and employed as a universal filler for its features of large specific surface area, high aspect ratio, and sufficient terminated -OH groups. The Ti3C2Tx is incorporated into polymer matrix to explore its function on membrane microstructure and proton conduction property. Both phase-separated (acidic Nafion and sulfonated poly(ether ether ketone)) and non-phase-separated (basic chitosan) polymers are utilized as membrane matrixes. The microstructures, physicochemical properties, and proton conduction properties of the membranes are extensively investigated. It is demonstrated that Ti3C2Tx generates significant promotion effect on proton conduction of the composite membrane by facilitating both vehicle-type and Grotthuss-type proton transfer, yielding several times increased proton conductivity for every polymer-based composite membrane under various conditions, and the composite membrane achieves elevated hydrogen fuel cell performance. The stable Ti3C2Tx also reinforces the thermal and mechanical stabilities of these composite membranes. Since the MXene family includes more than 70 members, this exploration is expected to open up new perspectives for expanding their applications, especially as membrane modifiers and proton conductors. PMID:27430190

  19. Ti3C2Tx Filler Effect on the Proton Conduction Property of Polymer Electrolyte Membrane.

    PubMed

    Liu, Yahua; Zhang, Jiakui; Zhang, Xiang; Li, Yifan; Wang, Jingtao

    2016-08-10

    Conductive polymer electrolyte membranes are increasingly attractive for a wide range of applications in hydrogen-relevant devices, for instance hydrogen fuel cells. In this study, two-dimensional Ti3C2Tx, a typical representative of the recently developed MXene family, is synthesized and employed as a universal filler for its features of large specific surface area, high aspect ratio, and sufficient terminated -OH groups. The Ti3C2Tx is incorporated into polymer matrix to explore its function on membrane microstructure and proton conduction property. Both phase-separated (acidic Nafion and sulfonated poly(ether ether ketone)) and non-phase-separated (basic chitosan) polymers are utilized as membrane matrixes. The microstructures, physicochemical properties, and proton conduction properties of the membranes are extensively investigated. It is demonstrated that Ti3C2Tx generates significant promotion effect on proton conduction of the composite membrane by facilitating both vehicle-type and Grotthuss-type proton transfer, yielding several times increased proton conductivity for every polymer-based composite membrane under various conditions, and the composite membrane achieves elevated hydrogen fuel cell performance. The stable Ti3C2Tx also reinforces the thermal and mechanical stabilities of these composite membranes. Since the MXene family includes more than 70 members, this exploration is expected to open up new perspectives for expanding their applications, especially as membrane modifiers and proton conductors.

  20. Reducing the thrombogenicity of ion-selective electrode membranes through the use of a silicone-modified segmented polyurethane.

    PubMed

    Berrocal, M J; Badr, I H; Gao, D; Bachas, L G

    2001-11-01

    The susceptibility of segmented polyurethanes (SPUs) to in vivo oxidative cleavage and hydrolysis constitutes a drawback in the use of these materials in the fabrication of implantable devices. The introduction of poly(dimethylsiloxane) (PDMS) groups into the polymer main chain has been previously reported to enhance the stability of SPUs. Herein, we evaluated the use of BioSpan-S, a silicone-modified SPU, in the design of membranes for cation-selective electrodes. The resulting electrodes exhibited good potentiometric response with all of the tested ionophores (valinomycin, sodium ionophore X, and nonactin). The obtained selectivity coefficients meet the selectivity requirements for the determination of sodium and potassium in blood. Moreover, as reflected by SEM studies, membranes prepared with BioSpan-S showed less adhesion of platelets than membranes prepared with conventional poly(vinyl chloride) (PVC). These results lead to the conclusion that BioSpan-S would be an appropriate candidate for the fabrication of implantable ion-selective electrodes. PMID:11721937

  1. 'Should I stay or should I go?' Bacterial attachment vs biofilm formation on surface-modified membranes.

    PubMed

    Bernstein, Roy; Freger, Viatcheslav; Lee, Jin-Hyung; Kim, Yong-Guy; Lee, Jintae; Herzberg, Moshe

    2014-01-01

    A number of techniques are used for testing the anti-biofouling activity of surfaces, yet the correlation between different results is often questionable. In this report, the correlation between initial bacterial deposition (fast tests, reported previously) and biofilm growth (much slower tests) was analyzed on a pristine and a surface-modified reverse osmosis membrane ESPA-1. The membrane was modified with grafted hydrophilic polymers bearing negatively charged, positively charged and zwitter-ionic moieties. Using three different bacterial strains it was found that there was no general correlation between the initial bacterial deposition rates and biofilm growth on surfaces, the reasons being different for each modified surface. For the negatively charged surface the slowest deposition due to the charge repulsion was eventually succeeded by the largest biofilm growth, probably due to secretion of extracellular polymeric substances (EPS) that mediated a strong attachment. For the positively charged surface, short-term charge attraction by quaternary amine groups led to the fastest deposition, but could be eventually overridden by their antimicrobial activity, resulting in non-consistent results where in some cases a lower biofilm formation rate was observed. The results indicate that initial deposition rates have to be used and interpreted with great care, when used for assessing the anti-biofouling activity of surfaces. However, for a weakly interacting 'low-fouling' zwitter-ionic surface, the positive correlation between initial cell deposition and biofilm growth, especially under flow, suggests that for this type of coating initial deposition tests may be fairly indicative of anti-biofouling potential.

  2. Pt/C-Electrocatalyst Painting on Polymer Electrolyte Membrane by Electrostatic Spray Deposition

    NASA Astrophysics Data System (ADS)

    Umeda, Minoru; Kawaguchi, Syunsuke; Yamada, Akifumi; Uchida, Isamu

    2005-02-01

    An electrocatalyst painting technique for use in a limited surface area of a polymer electrolyte membrane has been developed by employing electrostatic spray deposition (ESD). ESD is a process in which an aerosol of a solution is ejected from a metal syringe nozzle with a high applied voltage under atmosphere to obtain a thin film on the counter electrode. First, a dispersion containing Pt-loading carbon (Pt/C) powder and Nafion solution was sprayed by using the ESD technique. As a result, the dispersion was deposited over the entire surface area of a polymer electrolyte membrane of Nafion that was placed on the counter Au electrode, whereas, the dispersion was neither deposited on an electric-insulating poly(ethylene telephthalete) (PET) nor on the Nafion membrane on the PET. For the experiment, the Nafion membrane was pretreated to give it ionic conductivity. Next, a dye solution containing Rhodamine B was sprayed in the same manner, with the same result. In the case where the sizes of Nafion membrane and Au electrode were the same, the deposition only occurred on the Nafion/Au layered structure. According to these results, the aerosol generated at the syringe nozzle is introduced to the conductive area and kept away from the insulating area. Finally, for the untreated Nafion membrane on which a water droplet was placed, ESD of the Pt/C dispersion was conducted. Consequently, an electrocatalyst layer was successfully formed only at the wetted point of the Nafion membrane. This technique enables the painting of an electrocatalyst layer over a limited area without the use of any surface mask.

  3. Promotion of initial anti-tumor effect via polydopamine modified doxorubicin-loaded electrospun fibrous membranes

    PubMed Central

    Yuan, Ziming; Zhao, Xin; Wang, Xiaohu; Qiu, Wangwang; Chen, Xinliang; Zheng, Qi; Cui, Wenguo

    2014-01-01

    Drug-loaded electrospun PLLA membranes are not conducive to adhesion between materials and tissues due to the strong hydrophobicity of PLLA, which possibly attenuate the drugs’ effect loaded on the materials. In the present work, we developed a facile method to improve the hydrophilicity of doxorubicin (DOX)-loaded electrospun PLLA fibrous membranes, which could enhance the anti-tumor effect at the early stage after implantation. A mussel protein, polydopamine (PDA), could be easily grafted on the surface of hydrophobic DOX-loaded electrospun PLLA membranes (PLLA-DOX/pDA) in water solution. The morphology analysis of PLLA-DOX/pDA fibers displayed that though the fiber diameter was slightly swollen, they still maintained a 3D fibrous structure, and the XPS analysis certified that pDA had successfully been grafted onto the surface of the fibers. The results of surface wettability analysis showed that the contact angle decreased from 136.7° to 0° after grafting. In vitro MTT assay showed that the cytotoxicity of PLLA-DOX/pDA fibers was the strongest, and the stereologic cell counting assay demonstrated that the adhesiveness of PLLA/pDA fiber was significantly better than PLLA fiber. In vivo tumor-bearing mice displayed that, after one week of implantation, the tumor apoptosis and necrosis of PLLA-DOX/pDA fibers were the most obvious from histopathology and TUNEL assay. The caspase-3 activity of PLLA-DOX/pDA group was the highest using biochemical techniques, and the Bax: Bcl-2 ratio increased significantly in PLLA-DOX/pDA group through qRT-PCR analysis. All the results demonstrated that pDA can improve the affinity of the electrospun PLLA membranes and enhance the drug effect on tumors. PMID:25337186

  4. Regulation of Epithelial Cell Morphology and Functions Approaching To More In Vivo-Like by Modifying Polyethylene Glycol on Polysulfone Membranes

    PubMed Central

    Shen, Chong; Zhang, Guoliang; Meng, Qin

    2012-01-01

    Cytocompatibility is critically important in design of biomaterials for application in tissue engineering. However, the currently well-accepted “cytocompatible" biomaterials are those which promote cells to sustain good attachment/spreading. The cells on such materials usually lack the self-assembled cell morphology and high cell functions as in vivo. In our view, biomaterials that can promote the ability of cells to self-assemble and demonstrate cell-specific functions would be cytocompatible. This paper examined the interaction of polyethylene glycol (PEG) modified polysulfone (PSf) membranes with four epithelial cell types (primary liver cells, a liver tumor cell line, and two renal tubular cell lines). Our results show that PSf membranes modified with proper PEG promoted the aggregation of both liver and renal cells, but the liver cells more easily formed aggregates than the renal tubular cells. The culture on PEG-modified PSf membranes also enhanced cell-specific functions. In particular, the cells cultured on F127 membranes with the proper PEG content mimicked the in vivo ultrastructure of liver cells or renal tubules cells and displayed the highest cell functions. Gene expression data for adhesion proteins suggest that the PEG modification impaired cell-membrane interactions and increased cell-cell interactions, thus facilitating cell self-assembly. In conclusion, PEG-modified membrane could be a cytocompatible material which regulates the morphology and functions of epithelial cells in mimicking cell performance in vivo. PMID:22558349

  5. Detection of SEB gene by bilayer lipid membranes nucleic acid biosensor supported by modified patch-clamp pipette electrode.

    PubMed

    Liu, Nan; Gao, Zhixian; Zhou, HuanYing; Yue, Mingxiang

    2007-04-15

    This work reports a kind of novel bilayer lipid membranes (BLMs) nucleic acid biosensor supported by modified patch-clamp pipette electrode was developed to detect staphylococcus enterotoxins B (SEB) gene. BLMs were formed within 15 min and able to be operated at least 24 h. Hydrophobic dodecane tail (C12) modified 18 bp single-stranded DNA (ssDNA) probe was immobilized on BLMs. The electrochemical currents versus the different concentration of ssDNA probe immobilized on BLMs indicated linearly correlation. The BLMs nucleic acid biosensor was fabricated by selecting the ssDNA probe as the signal sensing element with the concentration of 273.65 ng/mL. The electrochemical performance of the biosensor for the detection of SEB was investigated. The result showed that linear relationship was found between the current and ln(concentration) from 20 to 5000 ng/mL and the detection limit was 20 ng/mL. In addition, the biosensor was specific response to SEB gene and showed no significant current alteration in electrolyte which containing no SEB gene. Finally, Atom Force Microscope (AFM) images could be observed and used to evaluate the superficial microstructure of BLMs, ssDNA immobilized on BLMs and BLMs after hybridization. The BLMs nucleic acid biosensor supported by modified patch-clamp pipette electrode will become a highly sensitive, rapid, selective analytical tool for detection of Staphylococcus aureus, which produce SEB. PMID:17092700

  6. Molecular dynamics simulation of hydrated Nafion with a reactive force field for water.

    PubMed

    Hofmann, Detlef W M; Kuleshova, Liudmila; D'Aguanno, Bruno

    2008-03-01

    We apply a newly parameterized central force field to highlight the problem of proton transport in fuel cell membranes and show that central force fields are potential candidates to describe chemical reactions on a classical level. After a short sketch of the parameterization of the force field, we validate the obtained force field for several properties of water. The experimental and simulated radial distribution functions are reproduced very accurately as a consequence of the applied parameterization procedure. Further properties, geometry, coordination, diffusion coefficient and density, are simulated adequately for our purposes. Afterwards we use the new force field for the molecular dynamics simulation of a swollen polyelectrolyte membrane similar to the widespread Nafion 117. We investigate the equilibrated structures, proton transfer, lifetimes of hydronium ions, the diffusion coefficients, and the conductivity in dependence of water content. In a short movie we demonstrate the ability of the obtained force field to describe the bond breaking/formation, and conclude that this force field can be considered as a kind of a reactive force field. The investigations of the lifetimes of hydronium ions give us the information about the kinetics of the proton transfer in a membrane with low water content. We found the evidence for the second order reaction. Finally, we demonstrate that the model is simple enough to handle the large systems sufficient to calculate the conductivity from molecular dynamics simulations. The detailed analysis of the conductivity reveals the importance of the collective moving of hydronium ions in membrane, which might give an interesting encouragement for further development of membranes.

  7. Cycling performance and efficiency of sulfonated poly(sulfone) membranes in vanadium redox flow batteries

    SciTech Connect

    Kim, Soowhan; Yan, Jingling; Schwenzer, Birgit; Zhang, Jianlu; Li, Liyu; Liu, Jun; Yang, Zhenguo; Hickner, Michael A.

    2010-11-30

    As an alternative to the expensive Nafion® ion exchange membrane, an inexpensive commercially-available Radel® polymer was sulfonated, fabricated into a thin membrane, and evaluated for its performance in a vanadium redox flow battery (VRFB). The sulfonated Radel (S-Radel) membrane showed almost an order of magnitude lower permeability of V (IV) ions (2.07×10-7 cm2/min), compared to Nafion 117 (1.29×10-6 cm2/min), resulting in better coulombic efficiency (~98% vs. 95% at 50 mA/cm2) and lower capacity loss per cycle. Even though the S-Radel membrane had slightly higher membrane resistance, the energy efficiency of the VRFB with the S-Radel membrane was comparable to that of Nafion due to its better coulombic efficiency. The S-Radel membrane exhibited good performance up to 40 cycles, but a decay in performance at later cycles was observed.

  8. Synthesis of indium sulphide quantum dots in perfluoronated ionomer membrane

    SciTech Connect

    Sumi, R.; Warrier, Anita R.; Vijayan, C.

    2014-01-28

    In this paper, we demonstrate a simple and efficient method for synthesis of β-indium sulphide (In{sub 2}S{sub 3}) nanoparticles embedded in an ionomer matrix (nafion membrane). The influence of reaction temperature on structural, compositional and optical properties of these films were analysed using X-Ray Diffraction, EDAX, UV-Vis absorption spectroscopy and photoluminescence studies. Average particle diameter was estimated using modified effective mass approximation method. Absorption spectra of In{sub 2}S{sub 3} nanoparticles show blue shift compared to bulk In{sub 2}S{sub 3}, indicating strong quantum size confinement effects. PL emission in the wavelength range 530–600 nm was recorded using a 488 nm line from an Ar{sup +} laser as the excitation source.

  9. A novel electrochemical sensor for the analysis of β-agonists: the poly(acid chrome blue K)/graphene oxide-nafion/glassy carbon electrode.

    PubMed

    Lin, Xiaoyun; Ni, Yongnian; Kokot, Serge

    2013-09-15

    A novel modified electrode was constructed by the electro-polymerization of 4,5-dihydroxy-3-[(2-hydroxy-5-sulfophenyl)azo]-2,7-naphthalenedisulfonic acid trisodium salt (acid chrome blue K (ACBK)) at a graphene oxide (GO)-nafion modified glassy carbon electrode (GCE). The characterization of an electrochemically synthesized poly-ACBK/GO-nafion film was investigated by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques, and the results were interpreted and compared at each stage of the electrode construction. Electrochemical oxidation of eight β-agonists - clenbuterol, salbutamol, terbutaline, ractopamine, dopamine, dobutamine, adrenaline, and isoprenaline, was investigated by CV at the different electrodes. At the poly-ACBK/GO-nafion/GCE, the linear sweep voltammetry peak currents of the eight β-agonists increased linearly with their concentrations in the range of 1.0-36.0 ng mL(-1), respectively, and their corresponding limits of detection (LODs) were within the 0.58-1.46 ng mL(-1) range. This electrode showed satisfactory reproducibility and stability, and was used successfully for the quantitative analysis of clenbuterol in pork samples.

  10. Superacid-doped polybenzimidazole-decorated carbon nanotubes: a novel high-performance proton exchange nanocomposite membrane.

    PubMed

    Hasani-Sadrabadi, Mohammad Mahdi; Dashtimoghadam, Erfan; Majedi, Fatemeh Sadat; Moaddel, Homayoun; Bertsch, Arnaud; Renaud, Philippe

    2013-12-01

    Here we demonstrate design and electrochemical characterization of novel proton exchange membranes based on Nafion and superacid-doped polymer coated carbon nanotubes (CNTs). Polybenzimidazole-decorated CNT (PBI-CNT), a high-performance proton exchange nanostructure, was doped using phosphotungstic acid (PWA) as a super proton conductor. The engineered nanohybrid structure was shown to retain water molecules and provide high proton conduction at low humidity and elevated temperatures. The developed complex nanomaterial was then incorporated into the Nafion matrix to fabricate nanocomposite membranes. The acid-base interactions between imidazole groups of PBI and sulfonate groups of Nafion facilitate proton conductivity, especially at elevated temperatures. The improved characteristics of the membranes at the nanoscale result in enhanced fuel cell power generation capacity (386 mW cm(-2)) at elevated temperatures and low humidity (40% R.H.), which was found to be considerably higher than the commercial Nafion®117 membrane (73 mW cm(-2)). PMID:24108383

  11. Understanding the Effects of Compression and Constraints on Water Uptake of Fuel-Cell Membranes

    SciTech Connect

    Kusoglu, Ahmet; Kienitz, Brian L.; Weber, Adam Z.

    2011-01-01

    Accurate characterization of polymer-electrolyte fuel cells (PEFCs) requires understanding the impact of mechanical and electrochemical loads on cell components. An essential aspect of this relationship is the effect of compression on the polymer membrane?s water-uptake behavior and transport properties. However, there is limited information on the impact of physical constraints on membrane properties. In this paper, we investigate both theoretically and experimentally how the water uptake of Nafion membrane changes under external compression loads. The swelling of a compressed membrane is modeled by modifying the swelling pressure in the polymer backbone which relies on the changes in the microscopic volume of the polymer. The model successfully predicts the water content of the compressed membrane measured through in-situ swelling-compression tests and neutron imaging. The results show that external mechanical loads could reduce the water content and conductivity of the membrane, especially at lower temperatures, higher humidities, and in liquid water. The modeling framework and experimental data provide valuable insight for the swelling and conductivity of constrained and compressed membranes, which are of interest in electrochemical devices such as batteries and fuel cells.

  12. Electrochemical redox properties of polypyrrole/Nafion composite film in a solid polymer electrolyte battery

    SciTech Connect

    Momma, Toshiyuki; Kakuda, Satoko; Yarimizu, Hideki; Osaka, Tetsuya

    1995-06-01

    Nafion{reg_sign} was introduced into a polypyrrole (PPy) matrix, and the redox performance of the PPy/Nafion electrode was investigated in a polyethylene oxide (PEO)-LiClO{sub 4} electrolyte. A rougher interface between polymer cathode and polymer electrolyte is usually needed for an all-solid battery, however, the PPy/Nafion cathode works well regardless of the flat surface of the PPy/Nafion film. When compared to a PPy film doped with ClO{sub 4}{sup {minus}} anions with a similar morphology, the PPy/Nafion film showed better redox performance. The results of the impedance spectroscopy and potential-step chronoamperometry confirmed that the improvement in the redox reaction of the PPy/Nafion film was due to the enhancement of the ion diffusion rate in the film. Thus, the PPy/Nafion film showed good charging-discharging properties in a rechargeable Li/PEO-LiClO{sub 4}/(PPy/Nafion) battery.

  13. Electrotransportation of aniline through a perfluorosulfonate ion-exchange membrane

    SciTech Connect

    Katakura, Katsumi . Dept. of Chemical Engineering); Inaba, Minoru; Toyama, Koji; Ogumi, Zempachi; Takehara, Zenichiro . Division of Energy and Hydrocarbon Chemistry)

    1994-07-01

    Transport phenomena of aniline through Na[sup +]-, K[sup +]-, and Cs[sup +]-form of a perfluorosulfonate ion-exchange membrane, Nafion 117, under a flow of dc current, electrotransportation, were investigated. In each form, an increase in transport number of anilinium cation was observed in the current density range from 0.3 to 1.3 mA cm[sup [minus]2]. The transport number of the anilinium cation in Cs[sup +]-form was larger than that expected from the concentration and diffusion coefficient of the anilinium cation in Cs[sup +]-form Nafion. These aniline transport phenomena may be attributable to a structural change of Nafion or a decrease in hydrophobic interaction between the anilinium cation and Nafion caused by the flow of dc current.

  14. Porous silicon membrane-modified electrodes for label-free voltammetric detection of MS2 bacteriophage.

    PubMed

    Reta, Nekane; Michelmore, Andrew; Saint, Christopher; Prieto-Simón, Beatriz; Voelcker, Nicolas H

    2016-06-15

    A proof of concept for the label-free detection of bacteriophage MS2, a model indicator of microbiological contamination, is validated in this work as a porous silicon (pSi) membrane-based electrochemical biosensor. PSi membranes were used to afford nanochannel architectures. The sensing mechanism was based on the nanochannel blockage caused by MS2 binding to immobilized capture antibodies. This blockage was quantified by measuring the oxidation current of the electroactive species reaching the electrode surface, by means of differential pulse voltammetry (DPV). The immunosensor showed a limit of detection of 6 pfu/mL in buffer, allowing the detection of MS2 to levels commonly found in real-world applications, and proved to be unaffected by matrix effects when analyzing MS2 in reservoir water. This platform enables the straightforward, direct and sensitive detection of a broad range of target analytes and constitutes a promising approach towards the development of portable electronic point of sample analysis devices.

  15. Plasma Modified Polypropylene Membranes as the Lithium-Ion Battery Separators

    NASA Astrophysics Data System (ADS)

    Wang, Zhengduo; Zhu, Huiqin; Yang, Lizhen; Wang, Xinwei; Liu, Zhongwei; Chen, Qiang

    2016-04-01

    To reduce the thermal shrinkage of the polymeric separators and improve the safety of the Li-ion batteries, plasma treatment and plasma enhanced vapor chemical deposition (PECVD) of SiOx-like are carried out on polypropylene (PP) separators, respectively. Critical parameters for separator properties, such as the thermal shrinkage rate, porosity, wettability, and mechanical strength, are evaluated on the plasma treated PP membranes. O2 plasma treatment is found to remarkably improve the wettability, porosity and electrolyte uptake. PECVD SiOx-like coatings are found to be able to effectively reduce the thermal shrinkage rate of the membranes and increase the ionic conductivity. The electrolyte-philicity of the SiOx-like coating surface can be tuned by the varying O2 content in the gas mixture during the deposition. Though still acceptable, the mechanical strength is reduced after PECVD, which is due to the plasma etching. supported by National Natural Science Foundation of China (Nos. 11175024, 11375031), the Beijing Institute of Graphic and Communication Key Project of China (No. 23190113051), the Shenzhen Science and Technology Innovation Committee of China (No. JCYJ20130329181509637), BJNSFC (No. KZ201510015014), and the State Key Laboratory of Electrical Insulation and Power Equipment of China (No. EIPE15208)

  16. Nonhumidified High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

    NASA Technical Reports Server (NTRS)

    Kinder, James D.

    2005-01-01

    Fuel cells are being considered for a wide variety of aerospace applications. One of the most versatile types of fuel cells is the proton-exchange-membrane (PEM) fuel cell. PEM fuel cells can be easily scaled to meet the power and space requirements of a specific application. For example, small 100-W PEM fuel cells are being considered for personal power for extravehicular activity suit applications, whereas larger PEM fuel cells are being designed for primary power in airplanes and in uninhabited air vehicles. Typically, PEM fuel cells operate at temperatures up to 80 C. To increase the efficiency and power density of the fuel cell system, researchers are pursuing methods to extend the operating temperature of the PEM fuel cell to 180 C. The most widely used membranes in PEM fuel cells are Nafion 112 and Nafion 117--sulfonated perfluorinated polyethers that were developed by DuPont. In addition to their relatively high cost, the properties of these membranes limit their use in a PEM fuel cell to around 80 C. The proton conductivity of Nafion membranes significantly decreases above 80 C because the membrane dehydrates. The useful operating range of Nafion-based PEM fuel cells can be extended to over 100 C if ancillary equipment, such as compressors and humidifiers, is added to maintain moisture levels within the membrane. However, the addition of these components reduces the power density and increases the complexity of the fuel cell system.

  17. Preparation, characterization and performance of poly(m-phenylene isophthalamide)/organically modified montmorillonite nanocomposite membranes in removal of perfluorooctane sulfonate.

    PubMed

    Luo, Qin; Liu, Yanxia; Liu, Guixia; Zhao, Changwei

    2016-08-01

    Nanocomposite membranes containing poly(m-phenylene isophthalamide) (PMIA) and organically modified montmorillonite (OMMT) were prepared by a combination of solution dispersion and wet-phase inversion methods, and the effects of OMMT addition on the properties and performance of fabricated nanofiltration membranes were investigated. The membranes were characterized by contact angle measurements, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis, and zeta potential. The performance of the membranes was elucidated by the removal of perfluorooctane sulfonate (PFOS) at neutral pH. Increasing OMMT concentration improved the thermal stability and hydrophilicity of the membranes. The permeation and rejection of PFOS were significantly improved. The performance of fabricated nanofiltration membranes in removal of PFOS varied depending on the solute and membrane properties as well as solution conditions. Finally, a comparison between fabricated membranes and a commercial NF membrane (ESNA1-K1, Hydecanme) proved that the OMMT addition is a convenient procedure for producing nanocomposite membranes with superior properties and performance. PMID:27521944

  18. PVDF-Nafion nanomembranes coated microneedles for in vivo transcutaneous implantable glucose sensing.

    PubMed

    Chen, Dajing; Wang, Cang; Chen, Wei; Chen, Yuquan; Zhang, John X J

    2015-12-15

    We demonstrate that microporous PVDF membranes sandwiched between multiple layers of nanomaterials can be used for continuous monitoring of glucose level in vivo. This is achieved by coating needle electrodes with Polyaniline nanofiber, Platinum nanoparticles, glucose oxidase enzyme and porous layers, successfully fabricated with layer-by-layer deposition. Nanoparticles incorporated into conductive Polyaniline nanofibers resulted in high surface to volume ratio and electrocatalytic activity for glucose enzyme. A composite coating membrane of porous PVDF and nano-sphere Nafion limited the glucose transportation and increased the lifetime of in vivo measurements. The glucose biosensor exhibited a sub-microamperometric output current, fast response time of less than 30s and a sensitivity of 0.23 μA/mM. The linear sensing range in terms of glucose concentration was from 0 to 20mM. Implantable experiments using mice models showed excellent response to the variation of blood glucose concentration while maintaining biocompatibility with the surrounding tissues. The sensitivity was shown to remain within 10% close to initial sensitivity within the 7 days of continuous monitoring, and maintain at 70% of the initial sensitivity within 21 days. PMID:26276540

  19. Concentration Dependence of VO2+ Crossover of Nafion for Vanadium Redox Flow Batteries

    SciTech Connect

    Lawton, Jamie; Jones, Amanda; Zawodzinski, Thomas A

    2013-01-01

    The VO2+ crossover, or permeability, through Nafion in a vanadium redox flow battery (VRFB) was monitored as a function of sulfuric acid concentration and VO2+ concentration. A vanadium rich solution was flowed on one side of the membrane through a flow field while symmetrically on the other side a blank or vanadium deficit solution was flowed. The blank solution was flowed through an electron paramagnetic resonance (EPR) cavity and the VO2+ concentration was determined from the intensity of the EPR signal. Concentration values were fit using a solution of Fick s law that allows for the effect of concentration change on the vanadium rich side. The fits resulted in permeability values of VO2+ ions across the membrane. Viscosity measurements of many VO2+ and H2SO4 solutions were made at 30 60 C. These viscosity values were then used to determine the effect of the viscosity of the flowing solution on the permeability of the ion. 2013 The Electrochemical Society. [DOI: 10.1149/2.004306jes] All rights reserved.

  20. Role of interfacial protein membrane in oxidative stability of vegetable oil substitution emulsions applicable to nutritionally modified sausage.

    PubMed

    Jiang, Jiang; Xiong, Youling L

    2015-11-01

    The potential health risk associated with excessive dietary intake of fat and cholesterol has led to a renewed interest in replacing animal fat with nutritionally-balanced unsaturated oil in processed meats. However, as oils are more fluid and unsaturated than fats, one must overcome the challenge of maintaining both physical and chemical (oxidative) stabilities of prepared emulsions. Apart from physical entrapments, an emulsion droplet to be incorporated into a meat protein gel matrix (batter) should be equipped with an interactive protein membrane rather than a small surfactant, and the classical DLVO stabilization theory becomes less applicable. This review paper describes the steric effects along with chemical roles (radical scavenging and metal ion chelation) of proteins and their structurally modified derivatives as potential interface-building materials for oxidatively stable meat emulsions.

  1. Role of interfacial protein membrane in oxidative stability of vegetable oil substitution emulsions applicable to nutritionally modified sausage.

    PubMed

    Jiang, Jiang; Xiong, Youling L

    2015-11-01

    The potential health risk associated with excessive dietary intake of fat and cholesterol has led to a renewed interest in replacing animal fat with nutritionally-balanced unsaturated oil in processed meats. However, as oils are more fluid and unsaturated than fats, one must overcome the challenge of maintaining both physical and chemical (oxidative) stabilities of prepared emulsions. Apart from physical entrapments, an emulsion droplet to be incorporated into a meat protein gel matrix (batter) should be equipped with an interactive protein membrane rather than a small surfactant, and the classical DLVO stabilization theory becomes less applicable. This review paper describes the steric effects along with chemical roles (radical scavenging and metal ion chelation) of proteins and their structurally modified derivatives as potential interface-building materials for oxidatively stable meat emulsions. PMID:26008711

  2. Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis Cells: Evaluation of Key Membrane Properties.

    PubMed

    Albert, Albert; Barnett, Alejandro O; Thomassen, Magnus S; Schmidt, Thomas J; Gubler, Lorenz

    2015-10-14

    Radiation-grafted membranes can be considered an alternative to perfluorosulfonic acid (PFSA) membranes, such as Nafion, in a solid polymer electrolyte electrolyzer. Styrene, acrylonitrile, and 1,3-diisopropenylbenzene monomers are cografted into preirradiated 50 μm ethylene tetrafluoroethylene (ETFE) base film, followed by sulfonation to introduce proton exchange sites to the obtained grafted films. The incorporation of grafts throughout the thickness is demonstrated by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis of the membrane cross-sections. The membranes are analyzed in terms of grafting kinetics, ion-exchange capacity (IEC), and water uptake. The key properties of radiation-grafted membranes and Nafion, such as gas crossover, area resistance, and mechanical properties, are evaluated and compared. The plot of hydrogen crossover versus area resistance of the membranes results in a property map that indicates the target areas for membrane development for electrolyzer applications. Tensile tests are performed to assess the mechanical properties of the membranes. Finally, these three properties are combined to establish a figure of merit, which indicates that radiation-grafted membranes obtained in the present study are promising candidates with properties superior to those of Nafion membranes. A water electrolysis cell test is performed as proof of principle, including a comparison to a commercial membrane electrode assembly (MEA).

  3. Preparation and High Permeance of SiO₂-Modified Substrate Supported ZSM-5 Membrane by Pre-Seeding and Secondary Nucleation.

    PubMed

    Cheng, Zhi-Lin; Liu, Zan; Wang, Sheng

    2016-01-01

    SiO₂-modified substrate supported compact ZSM-5 membranes with high permeance were prepared using the secondary nucleation method. The synthesis mixture had a molar composition of 10Na₂O:84SiO₂: 100NaCI:5TPABr:3500H₂O. In order to obtain high permeance, a SiO₂ meso- porous top layer was added to the macroporous substrate in this study. The SEM images of the seed layer indicate that about 400-500 nm round shaped seeds consisting of 60 nm zeolites fully covered the modifying substrate. The XRD patterns of the zeolite membranes show the purity of the ZSM-5 crystal phase, and reveal the formation of a random orientation on the SiO₂-modified substrate. The SEM images of the zeolite membranes indicate that the membranes consist of highly intergrown crystals, with a maximum thickness of about 30 µm. The results of gas permeability studies indicate that the SiO₂-modified substrate supported ZSM-5 membranes show good permeance, with the maximum H₂permeance achieved being 12.5 x 10⁻⁷ mol s⁻¹ m⁻² Pa⁻¹. The maximum H₂/N₂ and H₂/CO permselectivities were 4.01 and 4.37 respectively, which are higher than those of the corresponding Knudsen diffusion. The method used resulted in high permeance, while keeping the sustainable permselectivity, and is therefore desirable for practical applications. PMID:27398579

  4. In vitro investigation of antioxidant, anti-Inflammatory, and antiplatelet adhesion properties of genistein-modified poly(ethersulfone)/poly(vinylpyrrolidone) hemodialysis membranes.

    PubMed

    Chang, Teng; DeFine, Linda; Alexander, Thomas; Kyu, Thein

    2015-04-01

    Hemocompatibility of genistein-modified poly(ethersulfone)/poly(vinylpyrrolidone) (PES/PVP) hemodialysis (HD) membranes has been investigated in vitro with emphasis on evaluation of cell viability, antioxidant, anti-inflammatory, and antiplatelet adhesion properties. Genistein modified PES/PVP membranes reveal significant reduction of the reactive oxygen species and also considerable suppression of interleukin-1β and tumor necrosis factor-α levels in whole blood, but to a lesser extent ininterleukin-6. The incorporation of PVP into the HD membrane reduces platelet adhesion by virtue of its hydrophilicity. Of particular importance is that platelet adhesion of the genistein modified membranes declines noticeably at low concentrations of genistein for about 5-10%, beyond which it raises the number of adhered platelets. The initial decline in the platelet adhesion is attributable to genistein's ability to inhibit intercellular and/or vascular cell adhesion, whereas the reversal of this adhesion trend with further increase of genistein loading is ascribed to the inherent hydrophobicity of the genistein modified HD membrane.

  5. Wettability modified nanoporous ceramic membrane for simultaneous residual heat and condensate recovery

    PubMed Central

    Hu, H. W.; Tang, G. H.; Niu, D.

    2016-01-01

    Recovery of both latent heat and condensate from boiler flue gas is significant for improving boiler efficiency and water conservation. The condensation experiments are carried out to investigate the simultaneous heat and mass transfer across the nanoporous ceramic membranes (NPCMs) which are treated to be hydrophilic and hydrophobic surfaces using the semicontinuous supercritical reactions. The effects of typical parameters including coolant flow rate, vapor/nitrogen gas mixture temperature, water vapor volume fraction and transmembrane pressure on heat and mass transfer performance are studied. The experimental results show that the hydrophilic NPCM exhibits higher performances of condensation heat transfer and condensate recovery. However, the hydrophobic modification results in remarkable degradation of heat and condensate recovery from the mixture. Molecular dynamics simulations are conducted to establish a hydrophilic/hydrophobic nanopore/water liquid system, and the infiltration characteristics of the single hydrophilic/hydrophobic nanopore is revealed. PMID:27270997

  6. Wettability modified nanoporous ceramic membrane for simultaneous residual heat and condensate recovery

    NASA Astrophysics Data System (ADS)

    Hu, H. W.; Tang, G. H.; Niu, D.

    2016-06-01

    Recovery of both latent heat and condensate from boiler flue gas is significant for improving boiler efficiency and water conservation. The condensation experiments are carried out to investigate the simultaneous heat and mass transfer across the nanoporous ceramic membranes (NPCMs) which are treated to be hydrophilic and hydrophobic surfaces using the semicontinuous supercritical reactions. The effects of typical parameters including coolant flow rate, vapor/nitrogen gas mixture temperature, water vapor volume fraction and transmembrane pressure on heat and mass transfer performance are studied. The experimental results show that the hydrophilic NPCM exhibits higher performances of condensation heat transfer and condensate recovery. However, the hydrophobic modification results in remarkable degradation of heat and condensate recovery from the mixture. Molecular dynamics simulations are conducted to establish a hydrophilic/hydrophobic nanopore/water liquid system, and the infiltration characteristics of the single hydrophilic/hydrophobic nanopore is revealed.

  7. Wettability modified nanoporous ceramic membrane for simultaneous residual heat and condensate recovery.

    PubMed

    Hu, H W; Tang, G H; Niu, D

    2016-01-01

    Recovery of both latent heat and condensate from boiler flue gas is significant for improving boiler efficiency and water conservation. The condensation experiments are carried out to investigate the simultaneous heat and mass transfer across the nanoporous ceramic membranes (NPCMs) which are treated to be hydrophilic and hydrophobic surfaces using the semicontinuous supercritical reactions. The effects of typical parameters including coolant flow rate, vapor/nitrogen gas mixture temperature, water vapor volume fraction and transmembrane pressure on heat and mass transfer performance are studied. The experimental results show that the hydrophilic NPCM exhibits higher performances of condensation heat transfer and condensate recovery. However, the hydrophobic modification results in remarkable degradation of heat and condensate recovery from the mixture. Molecular dynamics simulations are conducted to establish a hydrophilic/hydrophobic nanopore/water liquid system, and the infiltration characteristics of the single hydrophilic/hydrophobic nanopore is revealed. PMID:27270997

  8. Wettability modified nanoporous ceramic membrane for simultaneous residual heat and condensate recovery.

    PubMed

    Hu, H W; Tang, G H; Niu, D

    2016-06-07

    Recovery of both latent heat and condensate from boiler flue gas is significant for improving boiler efficiency and water conservation. The condensation experiments are carried out to investigate the simultaneous heat and mass transfer across the nanoporous ceramic membranes (NPCMs) which are treated to be hydrophilic and hydrophobic surfaces using the semicontinuous supercritical reactions. The effects of typical parameters including coolant flow rate, vapor/nitrogen gas mixture temperature, water vapor volume fraction and transmembrane pressure on heat and mass transfer performance are studied. The experimental results show that the hydrophilic NPCM exhibits higher performances of condensation heat transfer and condensate recovery. However, the hydrophobic modification results in remarkable degradation of heat and condensate recovery from the mixture. Molecular dynamics simulations are conducted to establish a hydrophilic/hydrophobic nanopore/water liquid system, and the infiltration characteristics of the single hydrophilic/hydrophobic nanopore is revealed.

  9. A simple method to prepare modified polyethersulfone membrane with improved hydrophilic surface by one-pot: The effect of hydrophobic segment length and molecular weight of copolymers.

    PubMed

    Ran, Fen; Li, Jie; Lu, Yi; Wang, Lingren; Nie, Shengqiang; Song, Haiming; Zhao, Lei; Sun, Shudong; Zhao, Changsheng

    2014-04-01

    A simple method to prepare modified polyethersulfone (PES) membrane by one-pot is provided, and the method includes three steps: polymerization of vinyl pyrrolidone (VP), copolymerization of methyl methacrylate (MMA) and blending with PES. The effect of the PMMA segment length and molecular weight of the copolymer (PVP-b-PMMA-b-PVP, as an additive) on the structures and properties of the modified membranes was investigated. Activated partial thromboplastin time (APTT) tests indicated that with the increase of the poly(methyl methacrylate) (PMMA) segment length in the chains of the copolymers and with the increase of the molecular weight of the copolymers, the APTTs of the modified membranes increased to some extent, since less of the additives were lost during liquid-liquid phase separation process. Therefore, the copolymer was designed and prepared with appropriate ratio of poly(vinyl pyrrolidone) (PVP) to MMA and with appropriate molecular weight for better membrane performance. When the copolymer was blended in the membrane, the water permeance, protein anti-fouling property and sieving coefficients for PEG-12000 increased obviously. The simple, credible and feasible method had the potential to be used for the modification of membranes with improved blood compatibility, ultrafiltration and antifouling properties of biomaterials and for practical production.

  10. Alternate Fuel Cell Membranes for Energy Independence

    SciTech Connect

    Storey, Robson, F.; Mauritz, Kenneth, A.; Patton, Derek, L.; Savin, Daniel, A.

    2012-12-18

    properties of experimental membranes, 9) fabrication and FC performance testing of membrane electrode assemblies (MEA) from experimental membranes, and 10) measurement of ex situ and in situ membrane durability of experimental membranes. Although none of the experimental hydrocarbon membranes that issued from the project displayed proton conductivities that met DOE requirements, the project contributed to our basic understanding of membrane structure-property relationships in a number of key respects. An important finding of the benchmark studies is that physical degradation associated with humidity and temperature variations in the FC tend to open new fuel crossover pathways and act synergistically with chemical degradation to accelerate overall membrane degradation. Thus, for long term membrane survival and efficient fuel utilization, membranes must withstand internal stresses due to humidity and temperature changes. In this respect, rigid aromatic hydrocarbon fuel cell membranes, e.g. PAES, offer an advantage over un-modified Nafion membranes. The benchmark studies also showed that broadband dielectric spectroscopy is a potentially powerful tool in assessing shifts in the fundamental macromolecular dynamics caused by Nafion chemical degradation, and thus, this technique is of relevance in interrogating proton exchange membrane durability in fuel cells and macromolecular dynamics as coupled to proton migration, which is of fundamental relevance in proton exchange membranes in fuel cells. A key finding from the hydrocarbon membrane synthesis effort was that rigid aromatic polymers containing isolated ion exchange groups tethered tightly to the backbone (short tether), such as HPPS, provide excellent mechanical and durability properties but do not provide sufficient conductivity, in either random or block configuration, when used as the sole ion exchange monomer. However, we continue to hypothesize that longer tethers, and tethered groups spaced more closely within the

  11. New High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

    NASA Technical Reports Server (NTRS)

    Kinder, James D.

    2004-01-01

    Fuel cells are receiving a considerable amount of attention for potential use in a variety of areas, including the automotive industry, commercial power generation, and personal electronics. Research at the NASA Glenn Research Center has focused on the development of fuel cells for use in aerospace power systems for aircraft, unmanned air vehicles, and space transportation systems. These applications require fuel cells with higher power densities and better durability than what is required for nonaerospace uses. In addition, membrane cost is a concern for any fuel cell application. The most widely used membrane materials for proton exchange membrane (PEM) fuel cells are based on sulfonated perfluorinated polyethers, typically Nafion 117, Flemion, or Aciplex. However, these polymers are costly and do not function well at temperatures above 80 C. At higher temperatures, conventional membrane materials dry out and lose their ability to conduct protons, essential for the operation of the fuel cell. Increasing the operating temperature of PEM fuel cells from 80 to 120 C would significantly increase their power densities and enhance their durability by reducing the susceptibility of the electrode catalysts to carbon monoxide poisoning. Glenn's Polymers Branch has focused on developing new, low-cost membranes that can operate at these higher temperatures. A new series of organically modified siloxane (ORMOSIL) polymers were synthesized for use as membrane materials in a high-temperature PEM fuel cell. These polymers have an organic portion that can allow protons to transport through the polymer film and a cross-linked silica network that gives the polymers dimensional stability. These flexible xerogel polymer films are thermally stable, with decomposition onset as high as 380 C. Two types of proton-conducting ORMOSIL films have been produced: (1) NASA-A, which can coordinate many highly acid inorganic salts that facilitate proton conduction and (2) NASA-B, which has been

  12. Preparation of graphene oxide doped eggshell membrane bioplatform modified Prussian blue nanoparticles as a sensitive hydrogen peroxide sensor.

    PubMed

    Mohammad-Rezaei, Rahim; Razmi, Habib; Dehgan-Reyhan, Sajjad

    2014-06-01

    This study describes the preparation and characterization of graphene oxide doped eggshell membrane (GO-ESM) as a novel electrochemical bioplatform for electroanalytical purposes. The GO-ESM bioplatform was prepared by incorporation of GO nano-sheets into the ESM via a facile sonication procedure. Field emission scanning electron microscopy and X-ray diffraction powder techniques were used to characterize the developed bioplatform. The electrochemistry of GO-ESM was investigated by decorating it on the surface of carbon ceramic electrode (CCE) by an O-ring. The GO-ESM platform was modified with Prussian blue (PB) via a facile dip-coating method. Then the resulted modified electrode (PB|GO-ESM|CCE) was used as a novel hydrogen peroxide electrochemical sensor. The fabricated electrode responds efficiently to H2O2 over the concentration range 125nM-195μM with a detection limit of 31nM (S/N=3) and sensitivity 8.8μAμM(-1)cm(-2). The PB|GO-ESM|CCE has been successfully applied to determination of H2O2 content in spiked milk samples. Due to good stability, environmental friendly, cheapness, nontoxic, well behaved electrochemical properties, and biocompatibility, the fabricated bioplatform has the promising future for practical applications. PMID:24742966

  13. Characterization of vanadium ion uptake in sulfonated diels alder poly(phenylene) membranes

    SciTech Connect

    Lawton, Jamie; Jones, Amanda; Tang, Zhijiang; Lindsey, Melanie; Zawodzinski, Thomas A

    2015-11-28

    Sulfonated diels alder poly(phenylene) (SDAPP), alternative aromatic hydrocarbon membranes for vanadium redox flow batteries (VRFBs) are characterized using electron paramagnetic resonance (EPR). Membranes soaked in sulfuric acid and vanadyl sulfate are analyzed to determine the membrane environment in which the vanadyl ion (VO2+) diffuses in the membranes. These results are compared to Nafion 117 membranes. In contrast to Nafion, the VO2+ in SDAPP membranes exists in two different environments. The results of analysis of rotational diffusion determined from fits the EPR spectral lineshapes in comparison with previously reported permeation studies and measurements of partitioning functions reported here suggest that the diffusion pathways in SDAPP are very different than in Nafion.

  14. Characterization of vanadium ion uptake in sulfonated diels alder poly(phenylene) membranes

    DOE PAGES

    Lawton, Jamie; Jones, Amanda; Tang, Zhijiang; Lindsey, Melanie; Zawodzinski, Thomas A

    2015-11-28

    Sulfonated diels alder poly(phenylene) (SDAPP), alternative aromatic hydrocarbon membranes for vanadium redox flow batteries (VRFBs) are characterized using electron paramagnetic resonance (EPR). Membranes soaked in sulfuric acid and vanadyl sulfate are analyzed to determine the membrane environment in which the vanadyl ion (VO2+) diffuses in the membranes. These results are compared to Nafion 117 membranes. In contrast to Nafion, the VO2+ in SDAPP membranes exists in two different environments. The results of analysis of rotational diffusion determined from fits the EPR spectral lineshapes in comparison with previously reported permeation studies and measurements of partitioning functions reported here suggest that themore » diffusion pathways in SDAPP are very different than in Nafion.« less

  15. Surface modified electrospun poly(vinyl alcohol) membranes for extracting nanoparticles from water

    NASA Astrophysics Data System (ADS)

    Mahanta, Narahari; Valiyaveettil, Suresh

    2011-11-01

    Contamination of water from nanomaterials will be an emerging problem in the future due to incorporation of nanomaterials in many commercial products and improper disposal of waste materials. In this report, electrospun polyvinyl alcohol nanofibers (PVA NFs) with diameters ranging between 300 and 500 nm were used for the extraction of nanosized contaminants from the aqueous environment. To obtain the best extraction efficiency, surface hydroxyl groups of PVA NFs were chemically modified with functional groups, such as thiols and amines. Two model nanoparticles (silver and gold) dissolved in water were used for adsorption studies. Depending on the nature of the surface functionalities, the fibers showed unique ability to adsorb nanoparticles. The extraction studies revealed that the amine and thiol modified PVA NFs showed 90% extraction efficiency for both silver and gold nanoparticles. The thiol and amine functionalized PVA NFs showed maximum adsorption capacities (Qt) towards Au NPs, which were around 79-84 mg g-1. Similarly for Ag NP extraction, amine functionalized PVA NFs showed a value for Qt at 56 mg g-1. Our results highlight that functionalized nanofibers have high extraction efficiency for dissolved nanoparticles in water and can be used for removal of the nanocontaminants from the aqueous environment.Contamination of water from nanomaterials will be an emerging problem in the future due to incorporation of nanomaterials in many commercial products and improper disposal of waste materials. In this report, electrospun polyvinyl alcohol nanofibers (PVA NFs) with diameters ranging between 300 and 500 nm were used for the extraction of nanosized contaminants from the aqueous environment. To obtain the best extraction efficiency, surface hydroxyl groups of PVA NFs were chemically modified with functional groups, such as thiols and amines. Two model nanoparticles (silver and gold) dissolved in water were used for adsorption studies. Depending on the nature of

  16. Vibrational spectroscopy of ion exchange membranes

    NASA Astrophysics Data System (ADS)

    Kumari, Dunesh

    Infrared Spectroscopy (IR) and density functional theory (DFT) calculations were used to study Nafion, a sulfonated tetrafluoroethylene ionomer used as the electrolyte material of choice for polymer electrolyte membrane fuel cells (PEMFCs). A methodology is described for assignment of infrared peaks in terms of mechanically coupled internal coordinates of near neighbor functional groups. This work demonstrates (chapter 2--4) the use of ionomer functional group internal coordinate coupling analysis to assign two key Nafion peaks formerly assigned as the sulfonate symmetric stretch (1056 cm -1) and a COC (A) vibrational mode (971 cm-1). The experiments and theory complement each other to show that the dominate motions of the 1056 cm-1 and 971 cm-1 modes are attributed to the COC (A) and the sulfonate stretch respectively, exactly reverse of the convention used for decades. The salient point is that both peaks result from mechanically coupled internal coordinates of both functional groups. This explains why the 1056 cm-1 and 971 cm -1 peaks shift together with changes in the sulfonate group environment (i.e., ion exchange or membrane dehydration). The assignments, correlated with extensive literature data, and new data showing both peaks vanishing upon rigorous dehydration (i.e. conversion of a C3V deprotonated -SO3- to a C1 -SO3H) of the membrane, were based on the correlation of observed IR peaks with animations of mechanically coupled internal coordinates obtained by DFT calculations. Further, the above methodology was augmented with polarization modulated infrared reflection-adsorption spectroscopy (PM-IRRAS) to elucidate the Nafion ionomers functional groups that participate in self-assembly of Nafion onto Pt surfaces. A model for Nafion adsorption onto Pt shows that the Nafion side-chain sulfonate and CF3 co-adsorbates are structural components of the Nafion-Pt interface. The DFT-spectroscopy method of assigning peaks in terms of mechanically coupled internal

  17. Kinetic studies of ligand substitution rates for the Ru(NH/sub 3/)/sub 5/(H/sub 2/O)/sup 2 +/ ion in Nafion films

    SciTech Connect

    Lieber, C.M.; Schmidt, M.H.; Lewis, N.S.

    1986-10-01

    Substitution rates have been measured for reaction of a number of pyridines with the Nafion-bound Ru(NH/sub 3/)/sub 5/(H/sub 2/O)/sup 2 +/ complex. Reaction activities have been determined by electrochemical techniques, which also allow for determination of site thermodynamics and heterogeneity during the course of the reaction. Diffusion-coefficient effects are investigated by variation in polymer film thickness, and partition coefficients have been determined under equilibrium conditions by optical absorbance techniques. The partition-coefficient corrected rate law is found to be first order in Nafion-bound (Ru/sup II/) and first order in ligand concentration in the polymer phase. The partition-coefficient corrected bimolecular rate constants for a variety of pyridine ligands are found to vary by a factor of 5, which contrasts with the relatively constant substitution rates observed in aqueous solution. Also, sterically hindered ligands, such as 2-propylpyridine, exhibit surprisingly high substitution rate constants on the Nafion-bound Ru/sup II/ ion. These rate data indicate that pronounced molecular reactivity changes can occur upon electrode modification and have implications with respect to the design of chemically modified electrodes for use in electrocatalysis.

  18. Time-dependent mechanical behavior of proton exchange membrane fuel cell electrodes

    NASA Astrophysics Data System (ADS)

    Lu, Zongwen; Santare, Michael H.; Karlsson, Anette M.; Busby, F. Colin; Walsh, Peter

    2014-01-01

    The electrodes used for Proton Exchange Membrane Fuel Cells (PEMFCs) are typically painted or sprayed onto the membrane during manufacturing, making it difficult to directly characterize their mechanical behavior as a stand-alone material. An experimental-numerical hybrid technique is devised to extract the electrode properties from the experimentally measured properties of Nafion® 211 membrane

  19. SPEEK/PVDF/PES Composite as Alternative Proton Exchange Membrane for Vanadium Redox Flow Batteries

    NASA Astrophysics Data System (ADS)

    Fu, Zhimin; Liu, Jinying; Liu, Qifeng

    2016-01-01

    A membrane consisting of a blend of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and poly(ether sulfone) (PES) has been fabricated and used as an ion exchange membrane for application in vanadium redox flow batteries (VRBs). The vanadium ion permeability of the SPEEK/PVDF/PES membrane was one order of magnitude lower than that of Nafion 117 membrane. The low-cost composite membrane exhibited better performance than Nafion 117 membrane at the same operating condition. A VRB single cell with SPEEK/PVDF/PES membrane showed significantly lower capacity loss, higher coulombic efficiency (>95%), and higher energy efficiency (>82%) compared with Nafion 117 membrane. In the self-discharge test, the duration of the cell with the SPEEK/PVDF/PES membrane was nearly two times longer than that with Nafion 117 membrane. Considering these good properties and its low cost, SPEEK/PVDF/PES membrane is expected to have excellent commercial prospects as an ion exchange membrane for VRB systems.

  20. Cellular compatibility of a gamma-irradiated modified siloxane-poly(lactic acid)-calcium carbonate hybrid membrane for guided bone regeneration.

    PubMed

    Takeuchi, Naoshi; Machigashira, Miho; Yamashita, Daisuke; Shirakata, Yoshinori; Kasuga, Toshihiro; Noguchi, Kazuyuki; Ban, Seiji

    2011-01-01

    A bi-layered silicon-releasable membrane consisting of a siloxane-poly(lactic acid) (PLA)-vaterite hybrid material (Si-PVH) microfiber mesh and a PLA microfiber mesh has been developed by an electrospinning method for guided bone regeneration (GBR) application. The bi-layered membrane was modified to a three-laminar structure by sandwiching an additional PLA microfiber mesh between the Si-PVH and PLA microfiber meshes (Si-PVH/PLA membrane). In this study, the influence of gamma irradiation, used for sterilization, on biological properties of the Si-PVH/PLA membrane was evaluated with osteoblasts and fibroblasts. After gamma irradiation, while the average molecular weight of the Si-PVH/PLA membrane decreased, the Si-PVH/PLA membrane promoted cell proliferation and differentiation (alkaline phosphatase activity and calcification) of osteoblasts, compared with the poly(lactide-co-glycolide) membrane. These results suggest that the gamma-irradiated Si-PVH/PLA membrane is biocompatible with both fibroblasts and osteoblasts, and may have an application for GBR. PMID:21946495

  1. Nuclear Magnetic Resonance Studies of Water in Perfluorinated Ion Exchange Membranes.

    NASA Astrophysics Data System (ADS)

    Chen, Rensheng

    Perfluorinated ion-exchange membranes such as NAFION (DuPont) serve as both electrolyte and separators employed in fuel cells. The presence of the water in these membranes is critical to fuel cell operation. Water molecular diffusion and charge transport across the membrane are correlated. Through the availability of water isotopically enriched in deuterium or ^ {17} O, nuclear magnetic resonance (NMR) can be employed to study molecular dynamics by utilizing quadrupolar nuclei as probes. In this thesis, Deuteron and oxygen-17 NMR measurements in NAFION-117 membranes with variable water (D_{2}O or H_ {2}^{17}O) content (3 ~18% by weight) have been carried out. Measurements were taken at variable temperature (room T down to 115 K), high pressure (up to 0.25 GPa), and on stretched samples. One of the main results concerns the observation of anisotropic molecular motion in the membrane plane, with dramatic enhancement of the anisotropy in modestly stretched membranes. Glassy behavior of the water domains at low temperature is evidenced by the specific nature of the ^{2}H NMR line shapes at 109 K. Activation energies extracted from both ^{2}H and ^ {17}O spin-lattice relaxation data exhibit a steady increase with increasing water content. Activation volumes extracted from both ^{1} H and ^{2}H T _{1} pressure dependence show a decrease with increasing water content, at room temperature. Analysis of these observations suggests a water cluster model for water organization in NAFION membranes. The relatively free water and motionally restricted (by interaction with the polymer host) water exchange each other rapidly yielding an averaged response at room T, while the hydrogen bonds become more rigid at low temperature. Deuteron and oxygen -17 NMR studies of NAFION-117 containing either deuterated methanol (CH_{3}OD) or oxygen-17 enriched methanol (CH_{3 } ^{17}OH) demonstrate that the methanol molecular motion in NAFION-117 is considerably faster than for water in NAFION

  2. Preparation and characterization of sulfonated PEEK-WC membranes for fuel cell applications. A comparison between polymeric and composite membranes

    NASA Astrophysics Data System (ADS)

    Regina, A.; Fontananova, E.; Drioli, E.; Casciola, M.; Sganappa, M.; Trotta, F.

    Sulfonated poly(etheretherketone) with a cardo group (SPEEK-WC) exhibiting a wide range of degree of sulfonation (DS) was used to prepare polymeric membranes and composite membranes obtained by incorporation of an amorphous zirconium phosphate sulfophenylenphosphonate (Zr(HPO 4)(O 3PC 6H 4SO 3H), hereafter Zr(SPP)) in a SPEEK-WC matrix. The nominal composition of the composite membranes was fixed at 20 wt% of Zr(SPP). Both types of membrane were characterized for their proton conductivity, methanol permeability, water and/or methanol uptake, morphology by SEM and mechanical properties. For comparison, a commercial Nafion 117 membrane was characterized under the same operative conditions. The composite membranes exhibited a reduced water uptake in comparison with the polymeric membranes especially at high DS values and temperature higher than 50 °C. As a result, the water uptake into composite membranes remained about constant in the range 20-70 °C. The methanol permeability (P) of both polymeric and composite membranes was always lower than that of a commercial Nafion 117 membrane. At 22 °C and 100% relative humidity (RH), the proton conductivities (σ) of the polymeric membranes increased from 6 × 10 -4 to 1 × 10 -2 S cm -1 with the increase of DS from 0.1 to 1.04. The higher conductivity value was comparable with that of Nafion 117 membrane (3 × 10 -2 S cm -1) measured under the same operative conditions. The conductivities of the composite membranes are close to that of the corresponding polymeric membranes, but they are affected to a lesser extent by the polymer DS. The maximum value of the σ/ P ratio (about 7 × 10 4 at 25 °C) was found for the composite membrane with DS = 0.2 and was 2.5 times higher than the corresponding value of the Nafion membrane.

  3. Conductivity Measurements of Synthesized Heteropoly Acid Membranes for Proton Exchange Membrane Fuel Cells

    SciTech Connect

    Record, K.A.; Haley, B.T.; Turner, J.

    2006-01-01

    Fuel cell technology is receiving attention due to its potential to be a pollution free method of electricity production when using renewably produced hydrogen as fuel. In a Proton Exchange Membrane (PEM) fuel cell H2 and O2 react at separate electrodes, producing electricity, thermal energy, and water. A key component of the PEM fuel cell is the membrane that separates the electrodes. DuPont’s Nafion® is the most commonly used membrane in PEM fuel cells; however, fuel cell dehydration at temperatures near 100°C, resulting in poor conductivity, is a major hindrance to fuel cell performance. Recent studies incorporating heteropoly acids (HPAs) into membranes have shown an increase in conductivity and thus improvement in performance. HPAs are inorganic materials with known high proton conductivities. The primary objective of this work is to measure the conductivity of Nafion, X-Ionomer membranes, and National Renewable Energy Laboratory (NREL) Developed Membranes that are doped with different HPAs at different concentrations. Four-point conductivity measurements using a third generation BekkTech conductivity test cell are used to determine membrane conductivity. The effect of multiple temperature and humidification levels is also examined. While the classic commercial membrane, Nafion, has a conductivity of approximately 0.10 S/cm, measurements for membranes in this study range from 0.0030 – 0.58 S/cm, depending on membrane type, structure of the HPA, and the relative humidity. In general, the X-ionomer with H6P2W21O71 HPA gave the highest conductivity and the Nafion with the 12-phosphotungstic (PW12) HPA gave the lowest. The NREL composite membranes had conductivities on the order of 0.0013 – 0.025 S/cm.

  4. Integrating sol-gel with cold plasmas modified porous polycaprolactone membranes for the drug-release of silver-sulfadiazine and ketoprofen

    NASA Astrophysics Data System (ADS)

    Mangindaan, Dave; Chen, Chao-Ting; Wang, Meng-Jiy

    2012-12-01

    A controlled release system composed of surface modified porous polycaprolactone (PCL) membranes combined with a layer of tetraorthosilicate (TEOS)-chitosan sol-gel was reported in this study. PCL is a hydrophobic, semi-crystalline, and biodegradable polymer with a relatively slow degradation rate. The drugs chosen for release experiments were silver-sulfadiazine (AgSD) and ketoprofen which were impregnated in the TEOS-chitosan sol-gel. The surface modification was achieved by O2 plasma and the surfaces were characterized by water contact angle (WCA) measurements, atomic force microscope (AFM), scanning electron microscope and electron spectroscopy for chemical analysis (ESCA). The results showed that the release of AgSD on O2 plasma treated porous PCL membranes was prolonged when compared with the pristine sample. On the contrary, the release rate of ketoprofen revealed no significant difference on pristine and plasma treated PCL membranes. The prepared PCL membranes showed good biocompatibility for the wound dressing biomaterial applications.

  5. Direct Measurement of Cyclic Current-Voltage Responses of Integral Membrane Proteins at a Self-Assembled Lipid-Bilayer-Modified Electrode: Cytochrome f and Cytochrome c Oxidase

    NASA Astrophysics Data System (ADS)

    Salamon, Z.; Hazzard, J. T.; Tollin, G.

    1993-07-01

    Direct cyclic voltage-current responses, produced in the absence of redox mediators, for two detergent-solubilized integral membrane proteins, spinach cytochrome f and beef heart cytochrome c oxidase, have been obtained at an optically transparent indium oxide electrode modified with a self-assembled lipid-bilayer membrane. The results indicate that both proteins interact with the lipid membrane so as to support quasi-reversible electron transfer redox reactions at the semiconductor electrode. The redox potentials that were obtained from analysis of the cyclic "voltammograms," 365 mV for cytochrome f and 250 and 380 mV for cytochrome c oxidase (vs. normal hydrogen electrode), compare quite well with the values reported by using conventional titration methods. The ability to obtain direct electrochemical measurements opens up another approach to the investigation of the properties of integral membrane redox proteins.

  6. Direct measurement of cyclic current-voltage responses of integral membrane proteins at a self-assembled lipid-bilayer-modified electrode: Cytochrome f and cytochrome c oxidase

    SciTech Connect

    Salamon, Z.; Hazzard, J.T.; Tollin, G. )

    1993-07-15

    Direct cyclic voltage-current responses, produced in the absence of redox mediators, for two detergent-solubilized integral membrane proteins, spinach cytochrome f and beef heart cytochrome c oxidase, have been obtained at an optically transparent indium oxide electrode modified with a self-assembled lipid-bilayer membrane. The results indicate that both proteins interact with the lipid membrane so as to support quasi-reversible electron transfer redox reactions at the semiconductor electrode. The redox potentials that were obtained from analysis of the cyclic [open quotes]voltammograms,[close quotes] 365 mV for cytochrome f and 250 and 380 mV for cytochrome c oxidase (vs. normal hydrogen electrode), compare quite well with the values reported by using conventional titration methods. The ability to obtain direct electrochemical measurements opens up another approach to the investigation of the properties of integral membrane redox proteins. 63 refs., 2 figs., 1 tab.

  7. Electric field induced transformation of carbon nanotube to graphene nanoribbons using Nafion as a solid polymer electrolyte

    SciTech Connect

    Jaison, M. J.; Vikram, K.; Narayanan, Tharangattu N. E-mail: vk.pillai@ncl.res.in; Pillai, Vijayamohanan K. E-mail: vk.pillai@ncl.res.in

    2014-04-14

    We report a remarkable transformation of multiwalled carbon nanotubes (MWCNTs, average diameter 40 nm) to graphene nanoribbons (GNRs) in response to a field gradient of ∼25 V/cm, in a sandwich configuration using a solid state proton conducting polymer electrolyte like a thin perfluorosulphonated membrane, Nafion. In response to the application of a constant voltage for a sustained period of about 24 h at both room temperature and elevated temperatures, an interesting transformation of MWCNTs to GNRs has been observed with reasonable yield. GNRs prepared by this way are believed to be better for energy storage applications due to their enhanced surface area with more active smooth edge planes. Moreover, possible morphological changes in CNTs under electric field can impact on the performance and long term stability of devices that use CNTs in their electronic circuitry.

  8. Develpment of Higher Temperature Membrane and Electrode Assembly (MEA) for Proton Exchange Membrane Fuel Cell Devices

    SciTech Connect

    Susan Agro, Anthony DeCarmine, Shari Williams

    2005-12-30

    Our work will fucus on developing higher temperature MEAs based on SPEKK polymer blends. Thse MEAs will be designed to operatre at 120 degrees C Higher temperatures, up to 200 degrees C will also be explored. This project will develop Nafion-free MEAs using only SPEKK blends in both membrane and catalytic layers.

  9. Structural and membrane modifying properties of suzukacillin, a peptide antibiotic related to alamethicin. Part A. Sequence and conformation.

    PubMed

    Jung, G; König, W A; Leibfritz, D; Ooka, T; Janko, K; Boheim, G

    1976-04-16

    The primary structure and conformation of the polypeptide antibiotic suzukacillin A are investigated. Suzukacillin A is isolated from the Trichoderma viride strain 1037 and exhibits membrane modifying and lysing properties similar to those of alamethicin. A combined gas chromatographic mass spectrometric analysis of the trifluoroacetylated peptide methyl esters of partial hydrolysates revealed a tentative sequence of 23 residues including 10 2-methylalanines and one phenylalaninol, which shows many fragments known from alamethicin: Ac-Aib-Pro-Val-Aib-Val-Ala-Aib-Ala-Aib-Aib-Gln-Aib-Leu-Aib-Gly-Leu-Aib-Pro-Val-Aib-Aib-Glu(Pheol)-Gln-OH. All chiral amino acids and phenylalainol have L-configuration. Ultraviolet and infrared spectroscopy, circular dichroism in various solvents and in particular 13C nuclear magnetic resonance have been used for a comparative study of suzukacillin with alamethicin. Suzukacillin has a partially alpha-helical structure and the helix content increases largely from polar to lipophilic solvents. Suzukacillin aggregates more strongly than alamethicin in aqueous medis due to a longer alpha-helical part and higher number of aliphatic residues. A part of the alpha-helix is exceptionally stabilized due to 2-methylalanine residues shielding the peptide bonds from interactions with polar solvents. In lipophilic solvents and lecithin vesicles particularly large temperature induced reductions of the high alpha-helix content are found for alamethicin. Suzukacillin shows similar temperature coefficients in lipophilic media, however, in contrast to alamethicin a more linear change in intensity of the Cotton effects is observed. PMID:1260057

  10. Study of carbamate-modified disiloxane in porous PVDF-HFP membranes: new electrolytes/separators for lithium-ion batteries.

    PubMed

    Jeschke, Steffen; Mutke, Monika; Jiang, Zhongxiang; Alt, Burkhard; Wiemhöfer, Hans-Dieter

    2014-06-23

    A gel electrolyte membrane is obtained through the absorption of a carbamate-modified liquid disiloxane-containing lithium bis(trifluoromethane)sulfonimide (LiTFSI) by using macroporous poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) membranes. The porous membranes are prepared by means of a phase inversion technique. The resulting gel electrolyte membrane is studied by using differential scanning calorimetry, Fourier-transform infrared (FTIR) spectroscopy, and microscope mapping through coherent anti-Stokes Raman scattering (CARS) confocal microscopy and impedance spectroscopy. The ionic conductivity of the gel electrolyte is 10(-4) S cm(-1) at 20 °C. FTIR spectroscopy reveals interactions between LiTFSI and the carbonyl moiety of the disiloxane. No interactions between LiTFSI and PVDF-HFP or between disiloxane and PVDF-HFP are detected by FTIR spectroscopy. Furthermore, the distribution of the α and β/γ phases of PVDF-HFP and the homogeneous distribution of disiloxane/LiTFSI in the gel electrolyte membranes are examined by FTIR mapping. CARS confocal microscopy is used to image the three-dimensional interconnectivity, which reveals a reticulated structure of macrovoids in the porous PVDF-HFP framework. Owing to properties such as electrochemical and thermal stability of the disiloxane-based liquid electrolyte and the mechanical stability of the porous PVDF-HFP membrane, the gel electrolyte membranes presented herein are promising candidates for applications as electrolytes/separators in lithium-ion batteries.

  11. Study of carbamate-modified disiloxane in porous PVDF-HFP membranes: new electrolytes/separators for lithium-ion batteries.

    PubMed

    Jeschke, Steffen; Mutke, Monika; Jiang, Zhongxiang; Alt, Burkhard; Wiemhöfer, Hans-Dieter

    2014-06-23

    A gel electrolyte membrane is obtained through the absorption of a carbamate-modified liquid disiloxane-containing lithium bis(trifluoromethane)sulfonimide (LiTFSI) by using macroporous poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) membranes. The porous membranes are prepared by means of a phase inversion technique. The resulting gel electrolyte membrane is studied by using differential scanning calorimetry, Fourier-transform infrared (FTIR) spectroscopy, and microscope mapping through coherent anti-Stokes Raman scattering (CARS) confocal microscopy and impedance spectroscopy. The ionic conductivity of the gel electrolyte is 10(-4) S cm(-1) at 20 °C. FTIR spectroscopy reveals interactions between LiTFSI and the carbonyl moiety of the disiloxane. No interactions between LiTFSI and PVDF-HFP or between disiloxane and PVDF-HFP are detected by FTIR spectroscopy. Furthermore, the distribution of the α and β/γ phases of PVDF-HFP and the homogeneous distribution of disiloxane/LiTFSI in the gel electrolyte membranes are examined by FTIR mapping. CARS confocal microscopy is used to image the three-dimensional interconnectivity, which reveals a reticulated structure of macrovoids in the porous PVDF-HFP framework. Owing to properties such as electrochemical and thermal stability of the disiloxane-based liquid electrolyte and the mechanical stability of the porous PVDF-HFP membrane, the gel electrolyte membranes presented herein are promising candidates for applications as electrolytes/separators in lithium-ion batteries. PMID:24737746

  12. Nafion coated sulfur-carbon electrode for high performance lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Tang, Qiwei; Shan, Zhongqiang; Wang, Li; Qin, Xue; Zhu, Kunlei; Tian, Jianhua; Liu, Xuesheng

    2014-01-01

    In this paper, a nafion coated electrode is prepared to improve the performance of lithium sulfur batteries. It is demonstrated from a series of measurements that the nafion layer is quite effective in reducing shuttle effect and enhancing the stability and the reversibility of the electrode. When measured under the rate of 0.2 C, the initial discharge capacity of the nafion coated electrode can reach 1084 mAh g-1, with a Columbic efficiency of about 100%. After 100 charge/discharge cycles, this electrode can also deliver a reversible capacity of as high as 879 mAh g-1. Significantly, the charge-transfer resistance of the electrode tends to be reducing after coated with an appropriate thickness of nafion film. The cation conductivity as well as anion inconductivity is considered to be the dominant factor for the superior electrochemical properties.

  13. Determination of the diffusion coefficient of protons in Nafion thin films by ac-electrogravimetry.

    PubMed

    Sel, Ozlem; To Thi Kim, L; Debiemme-Chouvy, Catherine; Gabrielli, Claude; Laberty-Robert, Christel; Perrot, Hubert

    2013-11-12

    This letter deals with an adaptation of the ac-electrogravimetry technique to extract separately the dynamic properties of H(+) and water in Nafion nanometric thin films (average thickness of 400 nm). An original theoretical approach was developed to extract the representative parameters from ac-electrogravimetry data. The concentration change of the exchanged species and the diffusion coefficient of the protons in a Nafion nanometric thin film (D = 0.5 × 10(-6) cm(2) s(-1) at 0.3 V vs SCE) were estimated for the first time according to the applied potential. The conductivity value of Nafion thin films was calculated from the Nernst-Einstein equation using diffusion coefficients and concentration values extracted from ac-electrogravimetry data. The calculated conductivity results agree well with the experimental proton conductivity values of Nafion thin films. PMID:24131383

  14. Epidermal Stem Cells Cultured on Collagen-Modified Chitin Membrane Induce In Situ Tissue Regeneration of Full-Thickness Skin Defects in Mice

    PubMed Central

    Shen, Yan; Dai, Libing; Li, Xiaojian; Liang, Rong; Guan, Guangxiong; Zhang, Zhi; Cao, Wenjuan; Liu, Zhihe; Mei, Shirley; Liang, Weiguo; Qin, Shennan; Xu, Jiake; Chen, Honghui

    2014-01-01

    A Large scale of full-thickness skin defects is lack of auto-grafts and which requires the engineered skin substitutes for repair and regeneration. One major obstacle in skin tissue engineering is to expand epidermal stem cells (ESCs) and develop functional substitutes. The other one is the scaffold of the ESCs. Here, we applied type I collagen-modified chitin membrane to form collagen-chitin biomimetic membrane (C-CBM), which has been proved to have a great biocompatibility and degraded totally when it was subcutaneously transplanted into rat skin. ESCs were cultured, and the resulting biofilm was used to cover full-thickness skin defects in nude mice. The transplantation of ESCs- collagen- chitn biomimetic membrane (ESCs-C-CBM) has achieved in situ skin regeneration. In nude mice, compared to controls with collagen-chitin biomimetic membrane (C-CBM) only, the ESCs-C-CBM group had significantly more dermatoglyphs on the skin wound 10 w after surgery, and the new skin was relatively thick, red and elastic. In vivo experiments showed obvious hair follicle cell proliferation in the full-thickness skin defect. Stem cell markers examination showed active ESCs in repair and regeneration of skin. The results indicate that the collagen-modified chitin membrane carry with ESCs has successfully regenerated the whole skin with all the skin appendages and function. PMID:24516553

  15. Epidermal stem cells cultured on collagen-modified chitin membrane induce in situ tissue regeneration of full-thickness skin defects in mice.

    PubMed

    Shen, Yan; Dai, Libing; Li, Xiaojian; Liang, Rong; Guan, Guangxiong; Zhang, Zhi; Cao, Wenjuan; Liu, Zhihe; Mei, Shirley; Liang, Weiguo; Qin, Shennan; Xu, Jiake; Chen, Honghui

    2014-01-01

    A Large scale of full-thickness skin defects is lack of auto-grafts and which requires the engineered skin substitutes for repair and regeneration. One major obstacle in skin tissue engineering is to expand epidermal stem cells (ESCs) and develop functional substitutes. The other one is the scaffold of the ESCs. Here, we applied type I collagen-modified chitin membrane to form collagen-chitin biomimetic membrane (C-CBM), which has been proved to have a great biocompatibility and degraded totally when it was subcutaneously transplanted into rat skin. ESCs were cultured, and the resulting biofilm was used to cover full-thickness skin defects in nude mice. The transplantation of ESCs- collagen- chitn biomimetic membrane (ESCs-C-CBM) has achieved in situ skin regeneration. In nude mice, compared to controls with collagen-chitin biomimetic membrane (C-CBM) only, the ESCs-C-CBM group had significantly more dermatoglyphs on the skin wound 10 w after surgery, and the new skin was relatively thick, red and elastic. In vivo experiments showed obvious hair follicle cell proliferation in the full-thickness skin defect. Stem cell markers examination showed active ESCs in repair and regeneration of skin. The results indicate that the collagen-modified chitin membrane carry with ESCs has successfully regenerated the whole skin with all the skin appendages and function.

  16. Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

    NASA Astrophysics Data System (ADS)

    Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

    2015-10-01

    A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

  17. Glucose oxidase/colloidal gold nanoparticles immobilized in Nafion film on glassy carbon electrode: Direct electron transfer and electrocatalysis.

    PubMed

    Zhao, Shuang; Zhang, Kai; Bai, Yu; Yang, Weiwei; Sun, Changqing

    2006-10-01

    The direct electron transfer of glucose oxidase (GOD) was achieved based on the immobilization of GOD/colloidal gold nanoparticles on a glassy carbon electrode by a Nafion film. The immobilized GOD displayed a pair of well-defined and nearly reversible redox peaks with a formal potential (Eo ') of -0.434 V in 0.1 M pH 7.0 phosphate buffer solution and the response showed a surface-controlled electrode process. The dependence of Eo ' on solution pH indicated that the direct electron transfer reaction of GOD was a two-electron-transfer coupled with a two-proton-transfer reaction process. The experimental results also demonstrated that the immobilized GOD retained its electrocatalytic activity for the oxidation of glucose. So the resulting modified electrode can be used as a biosensor for detecting glucose. PMID:16556513

  18. Membrane Development for Vanadium Redox Flow Batteries

    SciTech Connect

    Schwenzer, Birgit; Zhang, Jianlu; Kim, Soowhan; Li, Liyu; Liu, Jun; Yang, Zhenguo

    2011-10-17

    Large-scale energy storage has become a main bottleneck for increasing the percentage of renewable energy in our electricity grids. Redox flow batteries are considered to be among the best options for electricity storage in the megawatt range, and large demonstration systems have already been installed. Although the full technological potential of these systems has not been reached yet, currently the main problem hindering more widespread commercialization is the high cost of redox flow batteries. Nafion{reg_sign} as the preferred membrane material is responsible for {approx}11% of the overall cost of a 1 MW/8 MWh system. Therefore in recent years two main membrane-related research threads have emerged: (a) chemical and physical modification of Nafion membranes to optimize their properties with regard to vanadium redox flow battery (VRFB) application; and (b) replacement of the Nafion membranes with different, less expensive materials. This review summarizes the underlying basic science issues associated with membrane use in VRFBs and presents an overview of membrane-related research approaches aimed at improving the efficiency of VRFBs and making the technology cost-competitive. Promising research strategies and materials are identified and suggestions are provided on how materials issues could be overcome.

  19. Membrane development for vanadium redox flow batteries.

    PubMed

    Schwenzer, Birgit; Zhang, Jianlu; Kim, Soowhan; Li, Liyu; Liu, Jun; Yang, Zhenguo

    2011-10-17

    Large-scale energy storage has become the main bottleneck for increasing the percentage of renewable energy in our electricity grids. Redox flow batteries are considered to be among the best options for electricity storage in the megawatt range and large demonstration systems have already been installed. Although the full technological potential of these systems has not been reached yet, currently the main problem hindering more widespread commercialization is the high cost of redox flow batteries. Nafion, as the preferred membrane material, is responsible for about 11% of the overall cost of a 1 MW/8 MWh system. Therefore, in recent years two main membrane related research threads have emerged: 1) chemical and physical modification of Nafion membranes to optimize their properties with regard to vanadium redox flow battery (VRFB) application; and 2) replacement of the Nafion membranes with different, less expensive materials. This review summarizes the underlying basic scientific issues associated with membrane use in VRFBs and presents an overview of membrane-related research approaches aimed at improving the efficiency of VRFBs and making the technology cost-competitive. Promising research strategies and materials are identified and suggestions are provided on how materials issues could be overcome.

  20. Preparation and properties of sulfonated poly(fluorenyl ether ketone) membrane for vanadium redox flow battery application

    NASA Astrophysics Data System (ADS)

    Chen, Dongyang; Wang, Shuanjin; Xiao, Min; Meng, Yuezhong

    In order to develop novel membranes for vanadium redox flow battery (VRB) with low self-discharge rate and low cost, sulfonated poly(fluorenyl ether ketone) (SPFEK) was synthesized directly via aromatic nucleophilic polycondensation of bisphenol fluorene with 60% sulfonated difluorobenzophenone and 40% difluorobenzophenone. The SPFEK membrane shows the lower permeability of vanadium ions. The open circuit voltage evaluation demonstrates that the SPFEK membrane is superior to Nafion 117 membrane in self-discharge test. Both energy efficiencies (EE) and power densities of the VRB single cell based on the SPFEK membrane are higher than those of the VRB with Nafion 117 membrane at the same current densities. The highest coulombic efficiency (CE) of VRB with SPFEK membrane is 80.3% while the highest CE of the VRB with Nafion 117 membrane is 77.0%. The SPFEK membrane shows the comparative stability to Nafion 117 membrane in VO 2 + electrolyte. The experimental results suggest that SPFEK membrane is a promising ion exchange membrane for VRB.

  1. Proton-conducting membranes with high selectivity from cross-linked poly(vinyl alcohol) and poly(vinyl pyrrolidone) for direct methanol fuel cell applications

    NASA Astrophysics Data System (ADS)

    Huang, Y. F.; Chuang, L. C.; Kannan, A. M.; Lin, C. W.

    A series of hydrocarbon membranes consisting of poly(vinyl alcohol) (PVA), sulfosuccinic acid (SSA) and poly(vinyl pyrrolidone) (PVP) were synthesized and characterized for direct methanol fuel cell (DMFC) applications. Fourier transform infrared (FT-IR) spectra confirm a semi-interpenetrating (SIPN) structure based on a cross-linked PVA/SSA network and penetrating PVP molecular chains. A SIPN membrane with 20% PVP (SIPN-20) exhibits a proton conductivity value comparable to Nafion ® 115 (1.0 × 10 -2 S cm -1 for SIPN-20 and 1.4 × 10 -2 S cm -1 for Nafion ® 115). Specifically, SIPN membranes reveal excellent methanol resistance for both sorption and transport properties. The methanol self-diffusion coefficient through a SIPN-20 membrane conducted by pulsed field-gradient nuclear magnetic resonance (PFG-NMR) technology measures 7.67 × 10 -7 cm 2 s -1, which is about one order of magnitude lower than that of Nafion ® 115. The methanol permeability of SIPN-20 membrane is 5.57 × 10 -8 cm 2 s -1, which is about one and a half order of magnitude lower than Nafion ® 115. The methanol transport behaviors of SIPN-20 and Nafion ® 115 membranes correlate well with their sorption characteristics. Methanol uptake in a SIPN-20 membrane is only half that of Nafion ® 115. An extended study shows that a membrane-electrode assembly (MEA) made of SIPN-20 membrane exhibits a power density comparable to Nafion ® 115 with a significantly higher open current voltage. Accordingly, SIPN membranes with a suitable PVP content are considered good methanol barriers, and suitable for DMFC applications.

  2. NMR studies of methanol transport in membranes for fuel cell applications.

    SciTech Connect

    Every, H. A.; Zawodzinski, T. A. , Jr.

    2001-01-01

    Characterization of the methanol diffusion process in Nafion 117 was achieved with the use of a modified pulsed field gradient NMR technique. To ensure that the concentration of methanol was constant throughout the entire experiment, the membrane was continually immersed in the methanol solution. When using the standard pulsed field gradient NMR method, the diffusion of the methanol in the membrane is strongly influenced by the diffusion of methanol in solution. Application of a filter gradient suppresses the signal from the methanol in solution, enabling the methanol diffusion in the membrane to be observed unambiguously. Complete suppression of the solution signal was achieved when a 60% filter gradient was employed. Under such circumstances, the coefficient for diffusion of methanol within the membrane was calculated to be 4x10-6cm2s-1, which is similar to the values reported in the literature. Consequently, the use of NMR filter gradient measurements is a valid method for studying the diffusion coefficient of methanol within fuel cell membranes.

  3. Selectivity of Direct Methanol Fuel Cell Membranes.

    PubMed

    Aricò, Antonino S; Sebastian, David; Schuster, Michael; Bauer, Bernd; D'Urso, Claudia; Lufrano, Francesco; Baglio, Vincenzo

    2015-11-24

    Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion(®) were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems, and composite zirconium phosphate-PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC). The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion(®) 115-based MEA (77 mW·cm(-2) vs. 64 mW·cm(-2)). This result was due to a lower methanol crossover (47 mA·cm(-2) equivalent current density for s-PEEK vs. 120 mA·cm(-2) for Nafion(®) 115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance (0.15 Ohm cm² for s-PEEK vs. 0.22 Ohm cm² for Nafion(®) 115).

  4. Selectivity of Direct Methanol Fuel Cell Membranes

    PubMed Central

    Aricò, Antonino S.; Sebastian, David; Schuster, Michael; Bauer, Bernd; D’Urso, Claudia; Lufrano, Francesco; Baglio, Vincenzo

    2015-01-01

    Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems, and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC). The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion® 115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2). This result was due to a lower methanol crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion® 115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance (0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115). PMID:26610582

  5. Modification and evaluation of fuel cell membranes

    NASA Astrophysics Data System (ADS)

    Nalawade, Amol Prataprao

    The primary goals of this study were modification of existing NafionRTM membranes and characterization of newly developed hydrocarbon-based membranes for high temperature fuel cell applications. Various NafionRTM/silicate nanocomposites were formulated via in situ sol-gel reactions for tetraethylorthosilicate. Different silicate composition profiles generated across membrane cross-sections were investigated by EDAX/ESEM. Composite water uptake, proton conductivity and fuel cell performance were comparable to that of unmodified Nafion RTM. Tafel analysis showed better electrode kinetics for composites having more silicate in the middle and less or no silicate at electrolyte-electrode interfaces. All composites showed reduced fuel cross-over and superior mechanical as well as chemical durability than unmodified NafionRTM. Poly(cyclohexadiene) (PCHD) materials were characterized in the interest of developing alternative low-cost proton exchange membranes. All cross-linked sulfonated (xsPCHD) membranes showed significantly higher water uptake at 80 °C and higher proton conductivity at 120 °C at all relative humidities (RH), compared to the current benchmark membrane, NafionRTM. A xsPCHD-poly(ethylene glycol) (PEG) copolymer and a xsPCHD-PEG blend surpassed the DOE target by exhibiting proton conductivities of 141.44 and 322.40 mS/cm, respectively, at 50 % RH. Although the PCHD-based PEMs exhibited thermal stability up to 150 °C, they showed poor mechanical properties which would cause poor membrane durability during fuel cell operation. Atomic force microscopy studies demonstrated nanophase separated morphology of xsPCHD having a higher degree of connectedness of hydrophilic domains in the copolymer and blends relative to the xsPCHD homopolymer. Broadband dielectric spectroscopy (BDS) was used to study sub-Tg relaxations in annealed poly(2,5-benzimidazole) (ABPBI) fuel cell precursor materials. A trend in degree of connectivity of charge migration pathways and

  6. Sulfonated Nanoplates in Proton Conducting Membranes for Fuel Cells

    SciTech Connect

    Chen, W.F.; Ni’mah, H.; Yu-Cheng Shen, Y.-C.; Kuo, P.-L.

    2011-09-29

    Surface-functionalized nanoplates are synthesized by anchoring sulfonic acid containing siloxanes on zirconium phosphate, and in turn blended with Nafion to fabricate proton conducting membranes. The effects of these sulfonated nanoplates on proton conduction, hydro-characteristics and fuel cell performance are reported.

  7. Application of nano TiO2 modified hollow fiber membranes in algal membrane bioreactors for high-density algae cultivation and wastewater polishing.

    PubMed

    Hu, Weiming; Yin, Jun; Deng, Baolin; Hu, Zhiqiang

    2015-10-01

    Polyvinylidene fluoride (PVDF) hollow fiber membranes with nano-TiO2 (5% of PVDF by mass, average size = 25 nm) additives were fabricated and applied for high-density algae (Chlorella vulgaris) cultivation. At the average light intensity of 121 μmol/m(2)/s, the algal membrane bioreactors (A-MBR) operated at a hydraulic retention time of 0.5d and an average solids retention time of 25d had an average algae biomass concentration of 2350 ± 74 mg/L (in COD units) and algal biomass production rate of 6.5 ± 0.1g/m(2)/d. The A-MBRs removed an average of 78% of phosphorus from the wastewater at the initial total phosphorus concentrations ranging from 3.5 to 8.6 mg/L. The nano TiO2-embedded membranes had improved surface hydrophilicity with its total resistance about 50% lower than that of the control. This study demonstrated that PVDF/TiO2 nanocomposite membranes had a better antifouling property for high-density algae cultivation and wastewater polishing.

  8. Myoglobin within graphene oxide sheets and Nafion composite films as highly sensitive biosensor

    PubMed Central

    Guo, Changchun; Sun, Hong; Zhao, X.S.

    2012-01-01

    A highly sensitive biosensor was fabricated by incorporating myoglobin (Mb) within graphene oxide (GO) sheets and Nafion composite films. The stable composite Mb–GO–Nafion films were characterized by electrochemistry, scanning electron microscopy, Fourier transform infrared spectroscopy and UV–vis spectroscopy. It was found that Mb in Mb–GO–Nafion films retained its secondary structure similar to its native states. Cyclic voltammetry of Mb–GO–Nafion films showed a pair of well defined, quasi-reversible peaks at about −0.312 V vs saturated calomel electrode (SCE) at pH 5.5, corresponding to direct electron transfer (DET) between Mb and the glassy carbon electrode. Electrochemical parameter of Mb in Mb–GO–Nafion film such as apparent heterogeneous electron transfer rate constant (ks) and formal potential (Eo′) were obtained. The dependence of Eo′ on solution pH indicated that the DET reaction of Mb was coupled with proton transfer. Mb in the films displayed good electrocatalytic activities towards various substrates such as hydrogen peroxide, nitrite and oxygen, indicating that the composite films have potential applications in fabricating novel biosensors without using mediators. PMID:23576844

  9. Enhancement of retention and antifouling capability for PVDF UF membrane modified by nano-TiO2 sol

    NASA Astrophysics Data System (ADS)

    Jia, Li M.; Wen, Chen; Xu, Jing Y.; Xiao, Chang F.

    2009-07-01

    Novel PVDF/TiO2 hybrid membranes were prepared by phase inversion process from a PVDF/DMAc/PVP/tetrabutyltitanate/water system. The membrane characteristics such as morphology, thermal properties, porosity, water contact angle, tensile strength and separability were investigated by a series of analytical methods including atomic force microscope (AFM), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and zeta potential measurements. The performances and surface properties of hybrid and PVDF membranes were tested by the removal of bovine serum albumin (BSA) from aqueous solution, evaluated by using two dyes with different charge (congo red and methylene blue). Based on the experimental results, TiO2 nanoparticles of a quantum size (~8 nm or less) in anatase crystal structure were obtained from the controlled hydrolysis of tetrabutyltitanate. Besides, TiO2 sol was introduced into polymer molecule for the hybrid membrane with less than 12 vol % TiO2 sol to PVDF and contributed to a smooth surface and more apertures due to both the interaction and compatibility between polymer and TiO2 sol, to which the improvement in hydrophilicity, thermal stability, mechanical strength and antifouling ability is attributed. The observed rejections were optimized for PVDF/TiO2 hybrid membrane with respect to PVDF membrane. In particular, the pure water permeation flux was increased from126.6 to166.7 L/m2•h for hybrid membrane with a relative flux of 80 % compared to 50 % of relative flux observed for PVDF membrane.

  10. Preparation of 3D electrode microarrays of multi-walled carbon nanotubes/nafion nanocomposites for microfluidic biofuel cells.

    PubMed

    Choi, Jin Ho; Kim, Young Ho; Choi, Sung Deuk; Kim, Gyu Man

    2014-12-01

    Three-dimensional (3D) electrode microarrays with multi-walled carbon nanotubes (MWCNTs) reinforced Nafion nanocomposites were prepared for microfluidic biofuel cells. The oxidized MWCNTs (ox-MWCNTs) were prepared using chemical reactions with 60% nitric acid solution with pristine MWCNTs at 120 degrees C for 12 hrs with a nitrogen gas flow environment. Ox-MWCNTs in the range of 1 to 20 wt.% based on the Nafion polymer weight were reinforced to Nafion nanocomposites by solution casting. The micro-porous structure of the ox-MWCNTs reinforced Nafion nanocomposites was prepared by plasma etching for 5 to 20 min. The 10 wt.% ox-MWCNTs reinforced Nafion nanocomposite produced stable micro-porous structures of 3D electrodes by 10 min plasma etching. Micro-scale 3D structures of MWCNTs reinforced Nafion nanocomposites in a diameter range of 47 to 300 μm were prepared by the micro-stencil assisted casting. To characterize the 3D electrode microarrays, the physical geometry and the reinforced MWCNT dispersion in the nanocomposite structure were examined using a scanning electron microscope (SEM) and an optical microscope. Thermal property measurements of the ox-MWCNTs reinforced Nafion nanocomposites with 10 min of plasma etching, and without plasma etching were made. Both showed stable thermal properties over 300 degrees C. The proposed 3D electrode microarray of MWCNT/Nafion nanocomposites with micro-porous structures can be applied to miniaturized fuel cell devices. PMID:25971059

  11. Double-side active TiO2-modified nanofiltration membranes in continuous flow photocatalytic reactors for effective water purification.

    PubMed

    Romanos, G Em; Athanasekou, C P; Katsaros, F K; Kanellopoulos, N K; Dionysiou, D D; Likodimos, V; Falaras, P

    2012-04-15

    A chemical vapour deposition (CVD) based innovative approach was applied with the purpose to develop composite TiO(2) photocatalytic nanofiltration (NF) membranes. The method involved pyrolytic decomposition of titanium tetraisopropoxide (TTIP) vapor and formation of TiO(2) nanoparticles through homogeneous gas phase reactions and aggregation of the produced intermediate species. The grown nanoparticles diffused and deposited on the surface of γ-alumina NF membrane tubes. The CVD reactor allowed for online monitoring of the carrier gas permeability during the treatment, providing a first insight on the pore efficiency and thickness of the formed photocatalytic layers. In addition, the thin TiO(2) deposits were developed on both membrane sides without sacrificing the high yield rates. Important innovation was also introduced in what concerns the photocatalytic performance evaluation. The membrane efficiency to photo degrade typical water pollutants, was evaluated in a continuous flow water purification device, applying UV irradiation on both membrane sides. The developed composite NF membranes were highly efficient in the decomposition of methyl orange exhibiting low adsorption-fouling tendency and high water permeability. PMID:21999989

  12. Electrocatalytic determination of paraquat using a nafion film coated glassy carbon electrode.

    PubMed

    Lu, T H; Sun, I W

    2000-11-01

    A nafion film coated glassy carbon electrode (NFGCE) was employed for the determination of paraquat. Paraquat was accumulated onto NFGCE by the cation-exchange feature of nafion at open circuit potential in basic medium followed by cathodic differential pulse voltammetric (CDPV) determination in a medium containing permanganate ions. The sensitivity for the determination of paraquat was improved through the electrocatalytic reduction of permanganate by the reduced paraquat. With 3-min accumulation, the analytical signal versus concentration dependence was linear from 1.0 to 100 ppb with a detection limit of 0.5 ppb. The interference from common metal ions was minimized by addition of ethylenediaminetetraacetate (EDTA) into the sample solution. The use of nafion also improves the resistance to interference from surfactants.

  13. Molecular sieve/sulfonated poly(ether ketone ether sulfone) composite membrane as proton exchange membrane

    NASA Astrophysics Data System (ADS)

    Changkhamchom, Sairung; Sirivat, Anuvat

    2012-02-01

    A proton exchange membrane (PEM) is an electrolyte membrane used in both polymer electrolyte membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFCs). Currently, PEMs typically used for PEMFCs are mainly the commercially available Nafion^ membranes, which is high cost and loss of proton conductivity at elevated temperature. In this work, the Sulfonated poly(ether ketone ether sulfone), (S-PEKES), was synthesized by the nucleophilic aromatic substitution polycondensation between bisphenol S and 4,4'-dichlorobenzophenone, and followed by the sulfonation reaction with concentrated sulfuric acid. The molecular sieve was added in the S-PEKES matrix at various ratios to form composite membranes to be the candidate for PEM. Properties of both pure sulfonated polymer and composite membranes were compared with the commercial Nafion^ 117 membrane from Dupont. S-PEKES membranes cast from these materials were evaluated as a polymer electrolyte membrane for direct methanol fuel cells. The main properties investigated were the proton conductivity, methanol permeability, thermal, chemical, oxidative, and mechanical stabilities by using a LCR meter, Gas Chromatography, Thermogravimetric Analysis, Fourier Transform Infrared Spectroscopy, Fenton's reagent, and Universal Testing Machine. The addition of the molecular sieve helped to increase both the proton conductivity and the methanol stability. These composite membranes are shown as to be potential candidates for use as a Proton Exchange Membrane (PEM).

  14. A modified CDC biofilm reactor to produce mature biofilms on the surface of peek membranes for an in vivo animal model application.

    PubMed

    Williams, Dustin L; Woodbury, Kassie L; Haymond, Bryan S; Parker, Albert E; Bloebaum, Roy D

    2011-06-01

    Biofilm-related infections have become a major clinical concern. Typically, animal models that involve inoculation with planktonic bacteria have been used to create positive infection signals and examine antimicrobial strategies for eradicating or preventing biofilm-related infection. However, it is estimated that 99.9% of bacteria in nature dwell in established biofilms. As such, open wounds have significant potential to become contaminated with bacteria that reside in a well-established biofilm. In this study, a modified CDC biofilm reactor was developed to repeatably grow mature biofilms of Staphylococcus aureus on the surface of polyetheretherketone (PEEK) membranes for inoculation in a future animal model of orthopaedic implant biofilm-related infection. Results indicated that uniform, mature biofilms repeatably grew on the surface of the PEEK membranes.

  15. Phase states of water near the surface of a polymer membrane. Phase microscopy and luminescence spectroscopy experiments

    SciTech Connect

    Bunkin, N. F.; Gorelik, V. S.; Kozlov, V. A. Shkirin, A. V. Suyazov, N. V.

    2014-11-15

    Phase microscopy is used to show that the refractive index in the near-surface layer of water at the surface of a polymer Nafion membrane increases by a factor of 1.1 as compared to bulk water. Moreover, this layer exhibits birefringence. Experiments on UV irradiation of dry (anhydrous) and water-soaked Nafion are performed in grazing-incidence geometry to study their stimulated luminescence spectra. These spectra are found to be identical in both cases. For dry Nafion, luminescence can only be excited if probing radiation illuminates the polymer surface. The luminescence of water-soaked Nafion can also be excited if the distance between the optical axis and the surface is several hundred micrometers.

  16. The immobilization of gossypol derivative on N-polyvinylpyrrolidone increases its water solubility and modifies membrane-active properties.

    PubMed

    Ionov, Maksim; Gordiyenko, Nataliya; Olchowik, Ewa; Baram, Nina; Zijaev, Khairulla; Salakhutdinov, Bakhtiyar; Bryszewska, Maria; Zamaraeva, Maria

    2009-07-23

    The conjugate of the gossypol derivative megosin (1) with N-polyvinylpyrrolidone named rometin (2) was synthesized. The effects of 1 and 2 on the structure and permeability of human erythrocytes and rat liver mitochondria were compared. Compound 1 induced dose-dependent erythrocyte hemolysis and increased mitochondrial permeability, with concomitant changes in membrane structure as determined by ESR and fluorescence anisotropy methods. Immobilization of 1 on N-polyvinylpyrrolidone (compound 2) increased its water solubility and reduced the intensity of its effects on erythrocyte membrane integrity and mitochondrial permeability, which correlated with a decrease in the membranes structural changes induced by the compound. Although the same concentrations of free and N-polyvinylpyrrolidone bound 1 were used, far less (14)C-labeled 1 was incorporated into the membranes from complex than free 1. The increase in water solubility and the reduction of membrane-active properties of 1 after immobilization on N-polyvinylpyrrolidone could explain our previous observation of the decreased toxicity of 1.

  17. Fabrication of TiO2-modified polytetrafluoroethylene ultrafiltration membranes via plasma-enhanced surface graft pretreatment

    NASA Astrophysics Data System (ADS)

    Qian, Yingjia; Chi, Lina; Zhou, Weili; Yu, Zhenjiang; Zhang, Zhongzhi; Zhang, Zhenjia; Jiang, Zheng

    2016-01-01

    Surface hydrophilic modification of polymer ultrafiltration membrane using metal oxide represents an effective yet highly challenging solution to improve water flux and antifouling performance. Via plasma-enhanced graft of poly acryl acid (PAA) prior to coating TiO2, we successfully fixed TiO2 functional thin layer on super hydrophobic polytetrafluoroethylene (PTFE) ultrafiltration (UF) membranes. The characterization results evidenced TiO2 attached on the PTFE-based UF membranes through the chelating bidentate coordination between surface-grafted carboxyl group and Ti4+. The TiO2 surface modification may greatly reduce the water contact angle from 115.8° of the PTFE membrane to 35.0° without degradation in 30-day continuous filtration operations. The novel TiO2/PAA/PTFE membranes also exhibited excellent antifouling and self-cleaning performance due to the intrinsic hydrophilicity and photocatalysis properties of TiO2, which was further confirmed by the photo-degradation of MB under Xe lamp irradiation.

  18. Comparative evaluation of modified m-FC and m-TEC media for membrane filter enumeration of Escherichia coli in water.

    PubMed Central

    Ciebin, B W; Brodsky, M H; Eddington, R; Horsnell, G; Choney, A; Palmateer, G; Ley, A; Joshi, R; Shears, G

    1995-01-01

    Two media used to detect fecal coliforms in water by membrane filtration, m-FC and m-TEC, were modified and supplemented with the chromogenic substrate 5-bromo-6-chloro-3-indoyl-beta-D-glucuronide (BCIG) and were compared for quantitative recovery of Escherichia coli. Student's t test of data from 181 water samples of sewage, rivers, lakes, and wells did not demonstrate any statistically significant differences (P = 0.05) in the enumeration of E. coli with these media. Target colonies were confirmed to be E. coli at rates of 98.6 and 97.3% by using FC-BCIG and TEC-BCIG media, respectively. Glucuronidase-negative isolates of E. coli were encountered at the same frequency (6.0%) on both media. This collaborative study demonstrated that either modified basal medium could be used successfully for detection of E. coli in various nontreated waters within 24 h. PMID:8526507

  19. Ethylene production by ODHE in catalytically modified Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) membrane reactors.

    PubMed

    Lobera, M Pilar; Escolástico, Sonia; Garcia-Fayos, Julio; Serra, José M

    2012-08-01

    Process intensification by the integration of membranes and high-temperature reactors offers several advantages with regard to conventional process schemes, that is, energy saving, safe operation, reduced plant/unit size, and higher process performance, for example, higher productivity, catalytic activity, selectivity, or stability. We present the study of oxidative dehydrogenation of ethane at 850 °C on a catalytic membrane reactor based on a mixed ionic-electronic conducting membrane. The surface of the membrane made of Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) has been activated by using different porous catalytic layers based on perovskites. The layer was deposited by screen printing, and the porosity and thickness was studied for the catalyst composition. The different catalyst formulations are based on partial substitution of A- and B-site atoms of doped strontium ferrite/cobaltites (A(0.6)Sr(0.4)Co(0.5)Fe(0.5)O(3-δ) and Ba(0.6)Sr(0.4)BO(3-δ)) and were synthesized by an ethylenediaminetetraacetic acid-citrate complexation route. The use of a disk-shaped membrane in the reactor enabled the direct contact of gaseous oxygen and hydrocarbons to be avoided, and thus, the ethylene content increased. High ethylene yields (up to ≈81 %) were obtained by using a catalytic coating based on Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ), which included macropores produced by the addition of graphite platelets into the screen-printing ink. The promising catalytic results obtained with this catalytically modified membrane reactor are attributed to the combination of 1) the high activity, as a result of the high temperature and oxygen species diffusing through the membrane; 2) the control of oxygen dosing and the low concentration of molecules in the gas phase; and 3) suitable fluid dynamics, which enables appropriate feed contact with the membrane and the rapid removal of products.

  20. Ethylene production by ODHE in catalytically modified Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) membrane reactors.

    PubMed

    Lobera, M Pilar; Escolástico, Sonia; Garcia-Fayos, Julio; Serra, José M

    2012-08-01

    Process intensification by the integration of membranes and high-temperature reactors offers several advantages with regard to conventional process schemes, that is, energy saving, safe operation, reduced plant/unit size, and higher process performance, for example, higher productivity, catalytic activity, selectivity, or stability. We present the study of oxidative dehydrogenation of ethane at 850 °C on a catalytic membrane reactor based on a mixed ionic-electronic conducting membrane. The surface of the membrane made of Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) has been activated by using different porous catalytic layers based on perovskites. The layer was deposited by screen printing, and the porosity and thickness was studied for the catalyst composition. The different catalyst formulations are based on partial substitution of A- and B-site atoms of doped strontium ferrite/cobaltites (A(0.6)Sr(0.4)Co(0.5)Fe(0.5)O(3-δ) and Ba(0.6)Sr(0.4)BO(3-δ)) and were synthesized by an ethylenediaminetetraacetic acid-citrate complexation route. The use of a disk-shaped membrane in the reactor enabled the direct contact of gaseous oxygen and hydrocarbons to be avoided, and thus, the ethylene content increased. High ethylene yields (up to ≈81 %) were obtained by using a catalytic coating based on Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ), which included macropores produced by the addition of graphite platelets into the screen-printing ink. The promising catalytic results obtained with this catalytically modified membrane reactor are attributed to the combination of 1) the high activity, as a result of the high temperature and oxygen species diffusing through the membrane; 2) the control of oxygen dosing and the low concentration of molecules in the gas phase; and 3) suitable fluid dynamics, which enables appropriate feed contact with the membrane and the rapid removal of products. PMID:22791570

  1. Evolution of nano-rheological properties of Nafion¯ thin films during pH modification by strong base treatment: A static and dynamic force spectroscopy study

    NASA Astrophysics Data System (ADS)

    Eslami, Babak; López-Guerra, Enrique A.; Raftari, Maryam; Solares, Santiago D.

    2016-04-01

    Addition of a strong base to Nafion® proton exchange membranes is a common practice in industry to increase their overall performance in fuel cells. Here, we investigate the evolution of the nano-rheological properties of Nafion thin films as a function of the casting pH, via characterization with static and dynamic, contact and intermittent-contact atomic force microscopy (AFM) techniques. The addition of KOH causes non-monotonic changes in the viscoelastic properties of the films, which behave as highly dissipative, softer materials near neutral pH values, and as harder, more elastic materials at extreme pH values. We quantify this behavior through calculation of the temporal evolution of the compliance and the glassy compliance under static AFM measurements. We complement these observations with dynamic AFM metrics, including dissipated power and virial (for intermittent-contact-mode measurements), and contact resonance frequency and quality factor (for dynamic contact-mode measurements). We explain the non-monotonic material property behavior in terms of the degree of ionic crosslinking and moisture content of the films, which vary with the addition of KOH. This work focuses on the special case study of the addition of strong bases, but the observed mechanical property changes are broadly related to water plasticizing effects and ionic crosslinking, which are also important in other types of films.

  2. Electrospun nanofiber membranes for electrically activated shape memory nanocomposites

    NASA Astrophysics Data System (ADS)

    Zhang, Fenghua; Zhang, Zhichun; Liu, Yanju; Leng, Jinsong

    2014-06-01

    A novel shape memory nanocomposite system, consisting of a thermoplastic Nafion polymer and ultrathin electrospun polyacrylonitrile (PAN)-based carbonization nanofiber membranes, is successfully synthesized. PAN-based carbonization nanofiber networks that offer responses to deformations are considered to be an excellent actuation source. Significant improvement in the electrical conductivity of carbon nanofiber membranes is found by adjusting the applied voltage power in the electrospinning PAN process varying from 7.85 to 12.30 S cm-1. The porous structure of the carbon nanofiber membranes provides a large specific surface area and interfacial contact area when combined with the polymer matrix. Shape memory Nafion nanocomposites filled with interpenetrating non-woven electrospun PAN carbonization membranes can be actuated by applying 14 V electrical voltage within 5 s. The results, as demonstrated through morphology, electrical and thermal measurements and a shape recovery test, suggest a valuable route to producing soft nanocomposites.

  3. α-Tocopherols modify the membrane dipole potential leading to modulation of ligand binding by P-glycoprotein.

    PubMed

    Davis, Sterenn; Davis, Benjamin M; Richens, Joanna L; Vere, Kelly-Ann; Petrov, Peter G; Winlove, C Peter; O'Shea, Paul

    2015-08-01

    α-Tocopherol (vitamin E) has attracted considerable attention as a potential protective or palliative agent. In vitro, its free radical-scavenging antioxidant action has been widely demonstrated. In vivo, however, vitamin E treatment exhibits negligible benefits against oxidative stress. α-Tocopherol influences lipid ordering within biological membranes and its derivatives have been suggested to inhibit the multi-drug efflux pump, P-glycoprotein (P-gp). This study employs the fluorescent membrane probe, 1-(3-sulfonatopropyl)-4-[β[2-(di-n-octylamino)-6-naphthyl]vinyl] pyridinium betaine, to investigate whether these effects are connected via influences on the membrane dipole potential (MDP), an intrinsic property of biological membranes previously demonstrated to modulate P-gp activity. α-Tocopherol and its non-free radical-scavenging succinate analog induced similar decreases in the MDP of phosphatidylcholine vesicles. α-Tocopherol succinate also reduced the MDP of T-lymphocytes, subsequently decreasing the binding affinity of saquinavir for P-gp. Additionally, α-tocopherol succinate demonstrated a preference for cholesterol-treated (membrane microdomain enriched) cells over membrane cholesterol-depleted cells. Microdomain disruption via cholesterol depletion decreased saquinavir's affinity for P-gp, potentially implicating these structures in the influence of α-tocopherol succinate on P-gp. This study provides evidence of a microdomain dipole potential-dependent mechanism by which α-tocopherol analogs influence P-gp activity. These findings have implications for the use of α-tocopherol derivatives for drug delivery across biological barriers.

  4. Selecting a Roof Membrane.

    ERIC Educational Resources Information Center

    Waldron, Larry W.

    1990-01-01

    Offers a brief synopsis of the unique characteristics of the following roof membranes: (1) built-up roofing; (2) elastoplastic membranes; (3) modified bitumen membranes; (4) liquid applied membranes; and (5) metal roofing. A chart compares the characteristics of the raw membranes only. (MLF)

  5. The local anesthetic proparacaine modifies sodium transport in toad skin and perturbs the structures of model and cell membranes.

    PubMed

    Suwalsky, Mario; Schneider, Carlos; Norris, Beryl; Villena, Fernando; Cárdenas, Hernán; Cuevas, Francisco; Sotomayor, Carlos P

    2002-01-01

    Experimental results indicate a significant decrease in the potential difference (PD) and in the short-circuit current (Isc) after the application of proparacaine to isolated toad skin, which may reflect an inhibition of the active transport of ions. This finding was explained on the basis of the results obtained from membrane models incubated with proparacaine. These consisted of human erythrocytes, isolated unsealed human erythrocyte membranes (IUM), phospholipid multilayers built-up of dimyristoylphosphatidylcholine (DMPC) and dimyristoylphosphatidylethanolamine (DMPE), representatives of phospholipid classes located in the outer and inner monolayers of the human erythrocyte membrane, respectively, and in large unilamellar vesicles (LUV) of DMPC X-ray diffraction showed that proparacaine interaction with DMPC and DMPE bilayers perturbed both structures, especially DMPC. This result, confirmed by fluorescence spectroscopy of DMPC LUV at 18 degrees C, demonstrated that the local anesthetic (LA) could interact with the lipid moiety of cell membranes. However, effects observed by scanning electron microscopy (SEM) of human erythrocytes and by fluorescence spectroscopy of IUM might also imply proparacaine-protein interactions. Thus, the LA may alter epitheial sodium channels through interaction with the lipid matrix and with channel protein residues. PMID:12440736

  6. Electricity generation coupled with wastewater treatment using a microbial fuel cell composed of a modified cathode with a ceramic membrane and cellulose acetate film.

    PubMed

    Seo, Ha Na; Lee, Woo Jin; Hwang, Tae Sik; Park, Doo Hyun

    2009-09-01

    A noncompartmented microbial fuel cell (NCMFC) composed of a Mn(IV)-carbon plate and a Fe(III)-carbon plate was used for electricity generation from organic wastewater without consumption of external energy. The Fe(III)-carbon plate, coated with a porous ceramic membrane and a semipermeable cellulose acetate film, was used as a cathode, which substituted for the catholyte and cathode. The Mn(IV)-carbon plate was used as an anode without a membrane or film coating. A solar cell connected to the NCMFC activated electricity generation and bacterial consumption of organic matter contained in the wastewater. More than 99 degrees of the organic matter was biochemically oxidized during wastewater flow through the four NCMFC units. A predominant bacterium isolated from the anode surface in both the conventional and the solar cell-linked NCMFC was found to be more than 99 degrees similar to a Mn(II)-oxidizing bacterium and Burkeholderia sp., based on 16S rDNA sequence analysis. The isolate reacted electrochemically with the Mn(IV)-modified anode and produced electricity in the NCMFC. After 90 days of incubation, a bacterial species that was enriched on the Mn(IV)-modified anode surface in all of the NCMFC units was found to be very similar to the initially isolated predominant species by comparing 16S rDNA sequences.

  7. Poly(phenyl sulfone) anion exchange membranes with pyridinium groups for vanadium redox flow battery applications

    NASA Astrophysics Data System (ADS)

    Zhang, Bengui; Zhang, Enlei; Wang, Guosheng; Yu, Ping; Zhao, Qiuxia; Yao, Fangbo

    2015-05-01

    To develop high performance and cost-effective membranes with low permeability of vanadium ions for vanadium redox flow battery (VRFB) application, poly(phenyl sulfone) anion exchange membranes with pyridinium groups (PyPPSU) are prepared and first investigated for VRFB application. PyPPSU membranes show much lower vanadium ions permeability (0.07 × 10-7-0.15 × 10-7 cm2 min-1) than that of Nafion 117 membrane (31.3 × 10-7 cm2 min-1). As a result, the self-discharge duration of the VRFB cell with PyPPSU membrane (418 h) is about four times longer than that of VRFB cell with Nafion 117 membrane (110 h). Furthermore, the VRFB cell with PyPPSU membrane exhibits higher battery efficiency (coulombic efficiency of 97.8% and energy efficiency of 80.2%) compare with that of VRFB cell with Nafion 117 membrane (coulombic efficiency of 96.1% and energy efficiency of 77.2%) at a high current density of 100 mA cm-2. In addition, PyPPSU membrane exhibits stable performance in 100-cycle test. The results indicate that PyPPSU membrane is high performance and low-cost alternative membrane for VRFB application.

  8. Structural and membrane modifying porperties of suzukacillin, a peptide antibiotic related to alamethicin. Part B. Pore formation in black lipid films.

    PubMed

    Boheim, G; Janko, K; Leibfritz, D; Ooka, T; König, W A; Jung, G

    1976-04-16

    Suzukacillin, a polypeptide consisting of presumably 23 amino acids and 1 phenylalaninol, is produced by a Trichoderma viride strain No. 1037 and it can be isolated from the culture medium. It shows membrane-modifying properties similar to those of alamethicin. Discrete condustance fluctuations indicate the formation of oligomer pores of varying diameter. On the basis of voltage jump relaxation experiments evidence is given that the dimer is the nucleation state from which pore formation starts and the oligomer disappears. According to the voltage-current characteristics, voltage-dependent and voltage-independent conductances are observed. A slow process is involved, which can be interpreted as a change in the equilibrium distribution between different conformations of the suzukacillin monomer at the membrane interphase. This change results from its interaction with the lipid matrix. Differences in experimental observations between suzukacillin and alamethicin are attributed to the relatively larger alpha-helix and higher number of aliphatic side chains of the suzukacillin monomer and to a more intense interaction with the lipid membrane. This leads to a higher probability of forming dimers from monomers and to the occurrence of "inactivation". PMID:1260058

  9. Intermediates to ethylene glycol: carbonylation of formaldehyde catalyzed by Nafion solid perfluorosulfonic acid resin

    SciTech Connect

    Hendriksen, D.E.

    1983-01-01

    Details of a series of reactions for the production of ethylene glycol using a catalyst of Nafion solid perfluorosulfonic acid resin was detailed. The reactions included the carbonylation of formaldehyde and esterification and then hydrogenation of the product of the carbonylation, glycolic acid. Other preparations included in the work included methyl glycolate, acetylglycolic acid, methyl acetylglycolate, and methyl methoxyacetate.

  10. Preparation of glycerol carbonate esters by using hybrid Nafion-silica catalyst.

    PubMed

    Climent, María J; Corma, Avelino; Iborra, Sara; Martínez-Silvestre, Sergio; Velty, Alexandra

    2013-07-01

    Glycerol carbonate esters (GCEs), which are valuable biomass-derivative compounds, have been prepared through the direct esterification of glycerol carbonate and long organic acids with different chain lengths, in the absence of solvent, and with heterogeneous catalysts, including acidic-organic resins, zeolites, and hybrid organic-inorganic acids. The best results, in terms of activity and selectivity towards GCEs, were obtained using a Nafion-silica composite. A full reaction scheme has been established, and it has been demonstrated that an undesired competing reaction results in the generation of glycerol and esters derived from a secondary hydrolysis of the endocyclic ester group, which is attributed to water formed during the esterification reaction. The influence of temperature, substrate ratio, catalyst-to-substrate ratio, and the use of solvent has been studied and, under optimized reaction conditions and with the adequate catalyst, it was possible to achieve 95% selectivity for the desired product at 98% conversion. It was demonstrated that the reaction rate decreased as the number of carbon atoms in the linear alkyl chain of the carboxylic acid increased for both p-toluenesulfonic acid and Nafion-silica nanocomposite (Nafion SAC-13) catalysts. After fitting the experimental data to a mechanistically based kinetic model, the reaction kinetic parameters for Nafion SAC-13 catalysis were determined and compared for reactions involving different carboxylic acids. A kinetic study showed that the reduced reactivity of carboxylic acids with increasing chain lengths could be explained by inductive as well as steric effects.

  11. Preparation of glycerol carbonate esters by using hybrid Nafion-silica catalyst.

    PubMed

    Climent, María J; Corma, Avelino; Iborra, Sara; Martínez-Silvestre, Sergio; Velty, Alexandra

    2013-07-01

    Glycerol carbonate esters (GCEs), which are valuable biomass-derivative compounds, have been prepared through the direct esterification of glycerol carbonate and long organic acids with different chain lengths, in the absence of solvent, and with heterogeneous catalysts, including acidic-organic resins, zeolites, and hybrid organic-inorganic acids. The best results, in terms of activity and selectivity towards GCEs, were obtained using a Nafion-silica composite. A full reaction scheme has been established, and it has been demonstrated that an undesired competing reaction results in the generation of glycerol and esters derived from a secondary hydrolysis of the endocyclic ester group, which is attributed to water formed during the esterification reaction. The influence of temperature, substrate ratio, catalyst-to-substrate ratio, and the use of solvent has been studied and, under optimized reaction conditions and with the adequate catalyst, it was possible to achieve 95% selectivity for the desired product at 98% conversion. It was demonstrated that the reaction rate decreased as the number of carbon atoms in the linear alkyl chain of the carboxylic acid increased for both p-toluenesulfonic acid and Nafion-silica nanocomposite (Nafion SAC-13) catalysts. After fitting the experimental data to a mechanistically based kinetic model, the reaction kinetic parameters for Nafion SAC-13 catalysis were determined and compared for reactions involving different carboxylic acids. A kinetic study showed that the reduced reactivity of carboxylic acids with increasing chain lengths could be explained by inductive as well as steric effects. PMID:23754795

  12. Chemically modified carbon paste and membrane sensors for the determination of benzethonium chloride and some anionic surfactants (SLES, SDS, and LABSA): Characterization using SEM and AFM.

    PubMed

    Issa, Yousry M; Mohamed, Sabrein H; Baset, Mohamed Abd-El

    2016-08-01

    Chemically modified carbon-paste (CMCP) and membrane- sensors based on incorporating benzothonium-tetraphenylborate (BT-TPB) were constructed for the analysis of benzethonium chloride, and some other surfactants such as sodium lauryl ether sulphate (SLES), sodium dodecyl sulphate (SDS), and linear alkylbenzene sulphonic acid (LABSA). All sensors showed good sensitivity and reverse wide linearity over a concentration range of 5.97×10(-7) to 1.00×10(-3) and 5.96×10(-7) to 3.03×10(-3)molL(-1) with limit of detection of 3.92×10(-7)and 3.40×10(-7)molL(-1) for membrane and chemically modified carbon paste sensors, respectively, with respect to benzethonium chloride (BT.Cl). They could be used over a wide pH range of 2.0-10.0. The thermal coefficients of membrane and CMCP sensors are 5.40×10(-4), 1.17×10(-4)V/°C, respectively. The sensors indicated a wide selectivity over different inorganic cations. The effect of soaking on the surface morphology of the membrane sensor was studied using EDX-SEM and AFM techniques. The response time was <10s The freshly prepared, exhausted membrane, and CMCP sensors were successfully applied for the potentiometric determination of the pure BT.Cl solution. They were also used for the determination of its pharmaceutical formulation Dermoplast(®) antibacterial spray (20% benzocaine+0.2% benzethonium chloride) with recovery values ranging from 97.54±1.70 to 101.25±1.12 and from 96.32±2.49 to 101.23±2.15%. The second goal of these sensors is the potentiometric determination of different surfactants such as SLES, SDS, and LABSA with good recovery values using BT.Cl as a titrant in their pure forms, and in samples containing one of them (shampoo, Touri(®) dishwashing liquid, and waste water). The statistical analysis of the obtained data was studied.

  13. Chemically modified carbon paste and membrane sensors for the determination of benzethonium chloride and some anionic surfactants (SLES, SDS, and LABSA): Characterization using SEM and AFM.

    PubMed

    Issa, Yousry M; Mohamed, Sabrein H; Baset, Mohamed Abd-El

    2016-08-01

    Chemically modified carbon-paste (CMCP) and membrane- sensors based on incorporating benzothonium-tetraphenylborate (BT-TPB) were constructed for the analysis of benzethonium chloride, and some other surfactants such as sodium lauryl ether sulphate (SLES), sodium dodecyl sulphate (SDS), and linear alkylbenzene sulphonic acid (LABSA). All sensors showed good sensitivity and reverse wide linearity over a concentration range of 5.97×10(-7) to 1.00×10(-3) and 5.96×10(-7) to 3.03×10(-3)molL(-1) with limit of detection of 3.92×10(-7)and 3.40×10(-7)molL(-1) for membrane and chemically modified carbon paste sensors, respectively, with respect to benzethonium chloride (BT.Cl). They could be used over a wide pH range of 2.0-10.0. The thermal coefficients of membrane and CMCP sensors are 5.40×10(-4), 1.17×10(-4)V/°C, respectively. The sensors indicated a wide selectivity over different inorganic cations. The effect of soaking on the surface morphology of the membrane sensor was studied using EDX-SEM and AFM techniques. The response time was <10s The freshly prepared, exhausted membrane, and CMCP sensors were successfully applied for the potentiometric determination of the pure BT.Cl solution. They were also used for the determination of its pharmaceutical formulation Dermoplast(®) antibacterial spray (20% benzocaine+0.2% benzethonium chloride) with recovery values ranging from 97.54±1.70 to 101.25±1.12 and from 96.32±2.49 to 101.23±2.15%. The second goal of these sensors is the potentiometric determination of different surfactants such as SLES, SDS, and LABSA with good recovery values using BT.Cl as a titrant in their pure forms, and in samples containing one of them (shampoo, Touri(®) dishwashing liquid, and waste water). The statistical analysis of the obtained data was studied. PMID:27216669

  14. Zirconium/polyvinyl alcohol modified flat-sheet polyvinyldene fluoride membrane for decontamination of arsenic: Material design and optimization, study of mechanisms, and application prospects.

    PubMed

    Zhao, Dandan; Yu, Yang; Chen, J Paul

    2016-07-01

    Arsenic contamination in industrial wastewater and groundwater has become an important environmental issue. In this study, a novel zirconium/polyvinyl alcohol (PVA) modified polyvinyldene fluoride (PVDF) membrane was developed for arsenate removal from simulated contaminated water. A PVDF flat-sheet membrane was first fabricated; it was then soaked in a zirconium-PVA solution and dried, and finally reacted with a glutaraldehyde solution, by which the zirconium ions were impregnated onto the PVDF surface through the ether and hydroxyl groups according to the cross-linkage mechanism. The fabrication procedure was optimized by the Box-Behnken experimental design approach. The adsorption kinetics study showed that most of uptake occurred in 5 h and the equilibrium was established in 24 h. The acidic condition was beneficial for the arsenate removal and the optimal removal efficiency can be obtained at pH 2.0. The experimental data of the adsorption isotherm was better described by Langmuir equation than Freundlich equation. The maximum adsorption capacity of 128 mg-As/g was achieved at pH 2.0. In the filtration study, the modified membrane with an area of 12.56 cm(2) could treat 15.6 L arsenate solution (equivalent to 75,150 bed volumes) with an influent concentration of 98.6 μg/L to meet the maximum contaminate level of 10 μg/L. Several instrumental studies revealed that the removal was mainly associated with ion exchange between chloride and arsenate ions.

  15. Zirconium/polyvinyl alcohol modified flat-sheet polyvinyldene fluoride membrane for decontamination of arsenic: Material design and optimization, study of mechanisms, and application prospects.

    PubMed

    Zhao, Dandan; Yu, Yang; Chen, J Paul

    2016-07-01

    Arsenic contamination in industrial wastewater and groundwater has become an important environmental issue. In this study, a novel zirconium/polyvinyl alcohol (PVA) modified polyvinyldene fluoride (PVDF) membrane was developed for arsenate removal from simulated contaminated water. A PVDF flat-sheet membrane was first fabricated; it was then soaked in a zirconium-PVA solution and dried, and finally reacted with a glutaraldehyde solution, by which the zirconium ions were impregnated onto the PVDF surface through the ether and hydroxyl groups according to the cross-linkage mechanism. The fabrication procedure was optimized by the Box-Behnken experimental design approach. The adsorption kinetics study showed that most of uptake occurred in 5 h and the equilibrium was established in 24 h. The acidic condition was beneficial for the arsenate removal and the optimal removal efficiency can be obtained at pH 2.0. The experimental data of the adsorption isotherm was better described by Langmuir equation than Freundlich equation. The maximum adsorption capacity of 128 mg-As/g was achieved at pH 2.0. In the filtration study, the modified membrane with an area of 12.56 cm(2) could treat 15.6 L arsenate solution (equivalent to 75,150 bed volumes) with an influent concentration of 98.6 μg/L to meet the maximum contaminate level of 10 μg/L. Several instrumental studies revealed that the removal was mainly associated with ion exchange between chloride and arsenate ions. PMID:27174848

  16. Development of nanocomposite membranes containing modified Si nanoparticles in PEBAX-2533 as a block copolymer and 6FDA-durene diamine as a glassy polymer.

    PubMed

    Nafisi, Vajiheh; Hägg, May-Britt

    2014-09-24

    Nanocomposite membranes of modified Si nanoparticles as inorganic filler in two different polymers from two different categories were developed. Synthesized 6FDA-durene diamine as a glassy polymer and PEBAX-2533 as a block copolymer were used as the polymer matrix to develop the nanocomposite membranes of modified Si nanoparticles in polymer matrix. The scanning transmission electron microscopy (STEM) results showed nice nano size dispersion of inorganic nanofillers in the polymer matrix in both cases. Pure gas permeation for the gases CO2, CH4, N2, and O2 and mixed gas of CO2-N2 was carried out at 2 and 6 bar for single gas and 2.6 bar for mixed gas using the developed nanocomposite membranes. The loading of inorganic fillers in the PEBAX-2533 polymer matrix resulted in a dramatic increase in gas permeability for all tested gases, while a decrease was observed for CO2/N2 and CO2/CH4 selectivities with small amounts of loading of filler. With higher loading of inorganic filler, the selectivity did not change, which is probably due to the formation of nanogap around the nanoparticles in the polymer matrix. The dispersion of the nanoparticle inorganic fillers in 6FDA-durene polymer matrix caused an increase on the fractional free volume of the polymer matrix due to the disruption of the polymer chain in the presence of the inorganic fillers. Hence, this disruption resulted in an increase of gas permeability for both single and mixed gases, also with an increase in CO2/N2 and CO2/CH4 selectivities.

  17. Efficiency and temperature dependence of water removal by membrane dryers

    NASA Technical Reports Server (NTRS)

    Leckrone, K. J.; Hayes, J. M.

    1997-01-01

    The vapor pressure of water in equilibrium with sorption sites within a Nafion membrane is given by log P(WN) = -3580/T + 10.01, where P(WN) is expressed in Torr and T is the membrane temperature, in kelvin. The efficiency of dryers based on selective permeation of water through Nafion can thus be enhanced by cooling the membrane. Residual water in effluents exceeds equilibrium levels if insufficient time is allowed for water to diffuse to the membrane surface as gas passes through the dryer. For tubular configurations, this limitation can be avoided if L > or = Fc(10(3.8)/120 pi D), where L is the length of the tubular membrane, in centimeters, Fc is the gas flow rate, in mL/ min, and D is the diffusion coefficient for water in the carrier gas at the operating temperature of the dryer, in cm2/s. An efficient dryer that at room temperature dries gas to a dew point of -61 degrees C is described; the same dryer maintained at 0 degrees C yields a dew point of -80 degrees C and removes water as effectively as Mg(ClO4)2 or a dry ice/acetone slush. The use of Nafion membranes to construct devices capable of delivering gas streams with low but precisely controlled humidities is discussed.

  18. Design of Peptide-Membrane Interactions to Modulate Single-File Water Transport through Modified Gramicidin Channels

    PubMed Central

    Portella, Guillem; Polupanow, Tanja; Zocher, Florian; Boytsov, Danila A.; Pohl, Peter; Diederichsen, Ulf; de Groot, Bert L.

    2012-01-01

    Water permeability through single-file channels is affected by intrinsic factors such as their size and polarity and by external determinants like their lipid environment in the membrane. Previous computational studies revealed that the obstruction of the channel by lipid headgroups can be long-lived, in the range of nanoseconds, and that pore-length-matching membrane mimetics could speed up water permeability. To test the hypothesis of lipid-channel interactions modulating channel permeability, we designed different gramicidin A derivatives with attached acyl chains. By combining extensive molecular-dynamics simulations and single-channel water permeation measurements, we show that by tuning lipid-channel interactions, these modifications reduce the presence of lipid headgroups in the pore, which leads to a clear and selective increase in their water permeability. PMID:23083713

  19. Design of peptide-membrane interactions to modulate single-file water transport through modified gramicidin channels.

    PubMed

    Portella, Guillem; Polupanow, Tanja; Zocher, Florian; Boytsov, Danila A; Pohl, Peter; Diederichsen, Ulf; de Groot, Bert L

    2012-10-17

    Water permeability through single-file channels is affected by intrinsic factors such as their size and polarity and by external determinants like their lipid environment in the membrane. Previous computational studies revealed that the obstruction of the channel by lipid headgroups can be long-lived, in the range of nanoseconds, and that pore-length-matching membrane mimetics could speed up water permeability. To test the hypothesis of lipid-channel interactions modulating channel permeability, we designed different gramicidin A derivatives with attached acyl chains. By combining extensive molecular-dynamics simulations and single-channel water permeation measurements, we show that by tuning lipid-channel interactions, these modifications reduce the presence of lipid headgroups in the pore, which leads to a clear and selective increase in their water permeability.

  20. Preparation of thin film nanofibrous composite NF membrane based on EDC/NHS modified PAN-AA nanofibrous substrate

    NASA Astrophysics Data System (ADS)

    Yang, Y.; Wang, X.; Hsiao, B. S.

    2016-07-01

    A novel kind of thin-film nanofibrous composite (TFNC) nanofiltration (NF) membranes consisting of a polyamide (PA) barrier layer were successfully fabricated by interfacial polymerization (IFP) based on electrospun double-layer nanofibrous substrates, which have an ultrathin poly (acrylonitrile-co-acrylic acid) (PAN-AA) nanofibrous layer as top layer and a thicker polyacrylonitrile (PAN) nanofiber layer as bottom porous support layer. Immersing PAN/PAN-AA nanofibrous substrates into 1-ethyl-(3-3-dimethylaminopropyl) carbodiimide hydrochloride/N-hydroxysuccinimide (EDC/NHS) aqueous solution and piperazine (PIP) aqueous solution (0.20 wt%) sequentially for a period of time, the carboxyl groups on PAN-AA nanofibers were activated by carbodiimide and then reacted with the amide groups. The as prepared composite membrane has an integrated structure with high rejection rate (98.0%); high permeate flux (40.4 L/m2h) for MgSO4 aqueous solution (2 g/L).

  1. Knocking Down of Isoprene Emission Modifies the Lipid Matrix of Thylakoid Membranes and Influences the Chloroplast Ultrastructure in Poplar1

    PubMed Central

    Velikova, Violeta; Müller, Constanze; Ghirardo, Andrea; Rock, Theresa Maria; Aichler, Michaela; Walch, Axel; Schmitt-Kopplin, Philippe

    2015-01-01

    Isoprene is a small lipophilic molecule with important functions in plant protection against abiotic stresses. Here, we studied the lipid composition of thylakoid membranes and chloroplast ultrastructure in isoprene-emitting (IE) and nonisoprene-emitting (NE) poplar (Populus × canescens). We demonstrated that the total amount of monogalactosyldiacylglycerols, digalactosyldiacylglycerols, phospholipids, and fatty acids is reduced in chloroplasts when isoprene biosynthesis is blocked. A significantly lower amount of unsaturated fatty acids, particularly linolenic acid in NE chloroplasts, was associated with the reduced fluidity of thylakoid membranes, which in turn negatively affects photosystem II photochemical efficiency. The low photosystem II photochemical efficiency in NE plants was negatively correlated with nonphotochemical quenching and the energy-dependent component of nonphotochemical quenching. Transmission electron microscopy revealed alterations in the chloroplast ultrastructure in NE compared with IE plants. NE chloroplasts were more rounded and contained fewer grana stacks and longer stroma thylakoids, more plastoglobules, and larger associative zones between chloroplasts and mitochondria. These results strongly support the idea that in IE species, the function of this molecule is closely associated with the structural organization and functioning of plastidic membranes. PMID:25975835

  2. Mechanical properties and microstructure changes of proton exchange membrane under immersed conditions

    SciTech Connect

    Shi, Shouwen; Liu, Dan; Liu, Dazhi; Tae, Patrick J; Gao, Carrie Y; Yan, Lei; An, Ke; Chen, Xu

    2013-01-01

    In this study, mechanical tensile stress strain response and microstructure changes of proton exchange membranes (PEM) in immersed conditions are studied. The effects of water pretreatment and immersion time on stress strain responses of NafionVR2212 membranes are discussed. It is found that in the water immersion it took 24 h for the membrane to reach saturation equilibrium. Compared with dry membrane, immersed Nafion membrane shows a lower stress level at 30C, but a higher stress level at 70C. In situ small angle neutron scattering (SANS) experiments show that with the increase of temperature and water uptake, domains of the membrane become ordered and stay stable at around 60C. Based on the observation, the relationship between the microstructure and mechanical properties is explained.

  3. Highly efficient sulfonated polybenzimidazole as a proton exchange membrane for microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Singha, Shuvra; Jana, Tushar; Modestra, J. Annie; Naresh Kumar, A.; Mohan, S. Venkata

    2016-06-01

    Although microbial fuel cells (MFCs) represent a promising bio-energy technology with a dual advantage (i.e., electricity production and waste-water treatment), their low power densities and high installation costs are major impediments. To address these bottlenecks and replace highly expensive Nafion, which is a proton exchange membrane (PEM), the current study focuses for the first time on membranes made from an easily synthesizable and more economical oxy-polybenzimidazole (OPBI) and its sulfonated analogue (S-OPBI) as alternate PEMs in single-chambered MFCs. The S-OPBI membrane exhibits better properties, with high water uptake, ion exchange capacity (IEC) and proton conductivity and a comparatively smaller degree of swelling compared to Nafion. The membrane morphology is characterized by atomic force microscopy, and the bright and dark regions of the S-OPBI membrane reveals the formation of ionic domains in the matrix, forming continuous water nanochannels when doped with water. These water-filled nanochannels are responsible for faster proton conduction in S-OPBI than in Nafion; therefore, the power output in the MFC with S-OPBI as the PEM is higher than in other MFCs. The open circuit voltage (460 mV), current generation (2.27 mA) and power density profile (110 mW/m2) as a function of time, as well as the polarization curves, exhibits higher current and power density (87.8 mW/m2) with S-OPBI compared to Nafion as the PEM.

  4. A comparative study of water uptake by and transport through ionomeric fuel cell membranes

    SciTech Connect

    Zawodzinski, T.A.Jr.; Springer, T.E.; Davey, J.; Jestel, R.; Lopez, C.; Valerio, J.; Gottesfeld, S. . Electronics Materials and Device Research)

    1993-07-01

    Water uptake and transport parameters measured at 30 C for several available perfluorosulfonic acid membranes are compared. The water sorption characteristics, diffusion coefficient of water, electroosmotic drag, and protonic conductivity were determined for Nafion 117, Membrane C, and Dow XUS 13204.10 developmental fuel cell membrane. The diffusion coefficient and conductivity of each of these membranes were determined as functions of membrane water content. Experimental determination of transport parameters, enables one to compare membranes without the skewing effects of extensive features such as membrane thickness which contributes in a nonlinear fashion to performance in polymer electrolyte fuel cells.

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  6. Development of a membrane alkaline fuel cell for caustic concentration in the chlor-alkali industry

    SciTech Connect

    Taylor, E.J.; Gelb, A.; Waterhouse, R.

    1986-01-01

    Nafion 901 and seven DuPont developmental membranes have been studied for the chlorine/caustic soda production process. Initial screening in 30 wt % anolyte/catholyte and 25 wt % NaOH anolyte/40 wt % NaOH catholyte has indicated the DuPont development membrane A1 to be the most promising. To date, the performance of an advanced cation exchange membrane has been demonstrated. (DLC)

  7. Omniphobic Membrane for Robust Membrane Distillation

    SciTech Connect

    Lin, SH; Nejati, S; Boo, C; Hu, YX; Osuji, CO; Ehmelech, M

    2014-11-01

    In this work, we fabricate an omniphobic microporous membrane for membrane distillation (MD) by modifying a hydrophilic glass fiber membrane with silica nanoparticles followed by surface fluorination and polymer coating. The modified glass fiber membrane exhibits an anti-wetting property not only against water but also against low surface tension organic solvents that easily wet a hydrophobic polytetrafluoroethylene (PTFE) membrane that is commonly used in MD applications. By comparing the performance of the PTFE and omniphobic membranes in direct contact MD experiments in the presence of a surfactant (sodium dodecyl sulfate, SDS), we show that SDS wets the hydrophobic PTFE membrane but not the omniphobic membrane. Our results suggest that omniphobic membranes are critical for MD applications with feed waters containing surface active species, such as oil and gas produced water, to prevent membrane pore wetting.

  8. Nanoclay and swift heavy ions induced piezoelectric and conducting nanochannel based polymeric membrane for fuel cell

    NASA Astrophysics Data System (ADS)

    Jana, Karun Kumar; Srivastava, Anshuman; Parkash, Om; Avasthi, Devesh K.; Rana, Dipak; Shahi, Vinod K.; Maiti, Pralay

    2016-01-01

    Through nanochannels are fabricated in poly(vinylidene fluoride-co-hexafluoro propylene) films by bombarding swift heavy ions (SHI) of energy 80 MeV and thereby creating latent tracks in the ion passage followed by chemical etching of the amorphous track. The dimension of the nanochannel is varied from 34 to 65 nm using different fluences and by dispersing organically modified nanoclay in polymer matrix. The nanochannels are grafted with polystyrene using the free radicals caused by SHI irradiation followed by their sulfonation. Nanoclay nucleates piezoelectric β-phase in copolymer whose extent gets enhanced after irradiation, grafting and sulfonation leading to a better material. The efficiency of functionalized nanochannel conduction is studied through dc conductivity of the bulk film in the semiconducting range against the insulating nature of the pristine copolymer. Current-voltage (I-V) characteristic of the membrane exhibits strong fluence dependency and shows superior conduction in functionalized nanohybrid. Proton conductivity of the functionalized nanohybrid is 6.2 × 10-2 S cm-1, while methanol permeability drastically reduces indicating higher values of the selective parameter of the developed membrane as compared to Nafion. Membrane electrode assembly studies of functionalized nanohybrid show 0.63 V as open circuit voltage leading to power density of 30.8 mW/cm2, considerably higher than the functionalized copolymer.

  9. A sensitive label-free amperometric CEA immunosensor based on graphene-nafion nanocomposite film as an enhanced sensing platform.

    PubMed

    Li, Yan; Yang, Wei-Kang; Fan, Man-Qi; Liu, Ao

    2011-01-01

    A novel approach to fabricate a label-free amperometric immunosensor for the detection of carcinoembryonic antigen (CEA) was described. Herein, methylene blue (MB), gold nanoparticles (AuNPs) and carcinoembryonic antibody (anti-CEA) were layer-by-layer assembled on the graphene-Nafion nanocomposite film-modified electrode by means of a self-assembling technique and the opposite-charged adsorption. Subsequently, the stepwise self-assembling procedure of the immunosensor was further characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The factors influencing the performance of the resulting immunosensor were studied in detail. The developed procedure showed improved features, including larger amount and higher immunoactivity of the immobilized antibody and repeatable regeneration of the sensor, as well as direct, rapid and simple determination for the antigen without multiple separation and labeling steps. The immunosensor could detect the target protein in a range of 0.5 to 120 ng/mL with a limit of 0.17 ng/mL (at 3σ). Finally, the immunosensing system was evaluated on several clinical samples. Analytical results were found to be in satisfactory agreement with those detected by the enzyme-linked immunosorbent assay (ELISA) method, indicating that this new method was a promising alternative tool for clinical diagnosis.

  10. Identification of viral membrane proteins required for cell fusion and viral dissemination that are modified during vaccinia virus persistence.

    PubMed

    Ortiz, M A; Paez, E

    1994-01-01

    Wild-type vaccinia virus WR strain forms non-fusogenic (F-) large plaques and is hemagglutinin positive (HA+) under normal conditions of virus infection. We have analyzed a collection of spontaneous, highly attenuated mutants of vaccinia virus isolated from persistently infected Friend erythroleukemia cells (E. Paez, S. Dallo, and M. Esteban, J. Virol. 61, 2642-2647, 1987) for the ability to express HA during virus infection. After 14 cell passages, all the mutants isolated were hemadsorption negative (HAD-) and did not synthesize a HA that could be recognized by anti-HA monoclonal antibodies. All these HA- mutants induced extensive cell-cell fusion (F+), with the exception of two mutants (65-16 and 101-14) isolated from late cell passages. Nucleotide sequence analysis of the HA gene in these two mutants confirmed the HA- phenotype. A frameshift mutation very close to the initiation codon resulted in premature translational termination. The truncated gene now only encodes the first 25 amino acids. Analysis of progeny from "wild-type," like early serial passage virus (5-3) X mutant back crosses, shows that for one late passage non-fusogenic small-plaque mutant (101-14) among large plaque progeny there is good correspondence between the ability to fuse and the absence of a viral HA and that each large plaque mutant contains a normal 14 kDa membrane protein. However, with a second serial passage mutant 65-16, which, like 101-14, is a nonfusogenic small-plaque variant, there is again an excellent correlation between the inability to synthesize HA and the ability to fuse, but there is no correlation of plaque size with a normal 14 kDa viral membrane protein, as most large plaque mutants encode a larger, i.e., 17 kDa protein. Rescue experiments of 65-16 with bona fide cloned 14 kDa protein gene confirm that the ability to regulate plaque size and cell fusion in this mutant is due to a protein other than the 14 kDa protein. Marker rescue experiments indicated that the map

  11. Immobilization of imidazole moieties in polymer electrolyte composite membrane for elevated temperature fuel cells

    NASA Astrophysics Data System (ADS)

    Li, Ke; Zhou, Bei; Ye, Gongbo; Pan, Mu; Zhang, Haining

    2015-12-01

    Development of membrane electrolyte with reasonable proton conductivity at elevated temperature without external humidification is essential for practical applications of elevated temperature proton exchange membrane fuel cells. Herein, a novel polymer electrolyte composite membrane using imidazole as anhydrous proton carriers for elevated temperature fuel cells is investigated. The imidazole moieties are immobilized inside the Nafion/poly(tetrafluoroethylene) (PTFE) composite membrane through in situ formation of imidazole functionalized silica nanoparticles in Nafion dispersion. The thus-formed membrane exhibits strong Coulombic interaction between negatively charged sulfonic acid groups of Nafion and protonated imidazole moieties, leading to an anhydrous proton conductivity of 0.018 S cm-1 at 180 °C. With the introduction of PTFE matrix, the mechanical strength of the membrane is greatly improved. The peak power density of a single cell assembled from the hybrid membrane is observed to be 130 mW cm-2 under 350 mA cm-2 at 110 °C without external humidification and it remains stable for 20 h continuous operation. The obtained results demonstrate that the developed composite membranes could be utilized as promising membrane electrolytes for elevated temperature fuel cells.

  12. Strongly Coupled Nafion Molecules and Ordered Porous CdS Networks for Enhanced Visible-Light Photoelectrochemical Hydrogen Evolution.

    PubMed

    Zheng, Xue-Li; Song, Ji-Peng; Ling, Tao; Hu, Zhen Peng; Yin, Peng-Fei; Davey, Kenneth; Du, Xi-Wen; Qiao, Shi-Zhang

    2016-06-01

    Strongly coupled Nafion molecules and ordered porous CdS networks are fabricated for visible-light photoelectrochemical (PEC) hydrogen evolution. The Nafion layer coating shifts the band position of CdS upward and accelerates charge transfer in the photoelectrode/electrolyte interface. It is highly expected that the strong coupling effect between organic and inorganic materials will provide new routes to advance PEC water splitting. PMID:27038367

  13. Effects of toluene and benzoic acid on the kinetics of ferrous oxidation on Pt and nafion-coated Pt electrodes

    SciTech Connect

    Ye, J.H.; Fedkiw, P.S. . Dept. of Chemical Engineering)

    1994-06-01

    The electrochemical kinetics of Fe[sup 2+] oxidation to Fe[sup 3+] have been investigated by cyclic and ring disk electrode voltammetry in the absence and presence of the contaminants toluene (7 mM, saturated solution) or benzoic acid (16 mM) in 1M H[sub 2]SO[sub 4] electrolyte on (1) smooth Pt electrodes, (2) Nafion-coated smooth Pt electrodes, and (3) Pt electrodes electrodeposited within a Nafion film coated onto a glassy carbon (GC) substrate. On uncoated Pt, the kinetics are adversely affected by these two organics: both the anodic transfer coefficient and the apparent standard rate constant are decreased. A 3.7 [mu]m Nafion coating, however, effectively buffers the smooth Pt electrode from toluene, but, nevertheless, benzoic acid still affects the reaction rate. In contrast, the transfer coefficient and rate constant for Fe[sup 2+] oxidation on the Pt/Nafion/GC electrode are essentially unaffected by either toluene or benzoic acid. Qualitative features of the voltammograms also indicate that the Nafion film protects the Pt from contamination by these aromatics: two current plateaus are observed using an uncoated Pt electrode in the presence of toluene or benzoic acid with a ratio which increased with rotation rate; with the Nafion coating on a smooth Pt electrode and in the presence of toluene, however, there is only one current plateau; in the presence of benzoic acid, two current plateaus remain, but the ratio is nearer unity and less sensitive to rotation rate. In contrast, only a single plateau current is observed using the Pt/Nafion/GC electrode. The Nafion coating is apparently an effective buffer layer against these two aromatics, but concurrently affects a decrease in the mass-transfer limited current due to the diffusional resistance of the film.

  14. Strongly Coupled Nafion Molecules and Ordered Porous CdS Networks for Enhanced Visible-Light Photoelectrochemical Hydrogen Evolution.

    PubMed

    Zheng, Xue-Li; Song, Ji-Peng; Ling, Tao; Hu, Zhen Peng; Yin, Peng-Fei; Davey, Kenneth; Du, Xi-Wen; Qiao, Shi-Zhang

    2016-06-01

    Strongly coupled Nafion molecules and ordered porous CdS networks are fabricated for visible-light photoelectrochemical (PEC) hydrogen evolution. The Nafion layer coating shifts the band position of CdS upward and accelerates charge transfer in the photoelectrode/electrolyte interface. It is highly expected that the strong coupling effect between organic and inorganic materials will provide new routes to advance PEC water splitting.

  15. Electrocatalytic oxidation and determination of insulin at nickel oxide nanoparticles-multiwalled carbon nanotube modified screen printed electrode.

    PubMed

    Rafiee, Banafsheh; Fakhari, Ali Reza

    2013-08-15

    Nickel oxide nanoparticles modified nafion-multiwalled carbon nanotubes screen printed electrode (NiONPs/Nafion-MWCNTs/SPE) were prepared using pulsed electrodeposition of NiONPs on the MWCNTs/SPE surface. The size, distribution and structure of the NiONPs/Nafion-MWCNTs were characterized by transmission electron microscopy (TEM) and x-ray diffraction (XRD) and also the results show that NiO nanoparticles were homogeneously electrodeposited on the surfaces of MWCNTs. Also, the electrochemical behavior of NiONPs/Nafion-MWCNTs composites in aqueous alkaline solutions of insulin was studied by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy (EIS). It was found that the prepared nanoparticles have excellent electrocatalytic activity towards insulin oxidation due to special properties of NiO nanoparticles. Cyclic voltammetric studies showed that the NiONPs/Nafion-MWCNTs film modified SPE, lowers the overpotentials and improves electrochemical behavior of insulin oxidation, as compared to the bare SPE. Amperometry was also used to evaluate the analytical performance of modified electrode in the quantitation of insulin. Excellent analytical features, including high sensitivity (1.83 μA/μM), low detection limit (6.1 nM) and satisfactory dynamic range (20.0-260.0 nM), were achieved under optimized conditions. Moreover, these sensors show good repeatability and a high stability after a while or successive potential cycling.

  16. Transport properties of proton-exchange membranes: Effect of supercritical-fluid processing and chemical functionality

    NASA Astrophysics Data System (ADS)

    Pulido Ayazo

    NafionRTM membranes commonly used in direct methanol fuel cells (DMFC), are tipically limited by high methanol permeability (also known as the cross-over limitation). These membranes have phase segregated sulfonated ionic domains in a perfluorinated backbone, which makes processing challenging and limited by phase equilibria considerations. This study used supercritical fluids (SCFs) as a processing alternative, since the gas-like mass transport properties of SCFs allow a better penetration into the membranes and the use of polar co-solvents influenced their morphology, fine-tuning the physical and transport properties in the membrane. Measurements of methanol permeability and proton conductivity were performed to the NafionRTM membranes processed with SCFs at 40ºC and 200 bar and the co-solvents as: acetone, tetrahydrofuran (THF), isopropyl alcohol, HPLC-grade water, acetic acid, cyclohexanone. The results obtained for the permeability data were of the order of 10 -8-10-9 cm2/s, two orders of magnitude lower than unprocessed Nafion. Proton conductivity results obtained using AC impedance electrochemical spectroscopy was between 0.02 and 0.09 S/cm, very similar to the unprocessed Nafion. SCF processing with ethanol as co-solvent reduced the methanol permeability by two orders of magnitude, while the proton conductivity was only reduced by 4%. XRD analysis made to the treated samples exhibited a decreasing pattern in the crystallinity, which affects the transport properties of the membrane. Also, SAXS profiles of the Nafion membranes processed were obtained with the goal of determining changes produced by the SCF processing in the hydrophilic domains of the polymer. With the goal of searching for new alternatives in proton exchange membranes (PEMs) triblock copolymer of poly(styrene-isobutylene-styrene) (SIBS) and poly(styrene-isobutylene-styrene) SEBS were studied. These sulfonated tri-block copolymers had lower methanol permeabilities, but also lower proton

  17. Structure of Membrane-active Toxin from Crab Spider Heriaeus melloteei Suggests Parallel Evolution of Sodium Channel Gating Modifiers in Araneomorphae and Mygalomorphae*

    PubMed Central

    Berkut, Antonina A.; Peigneur, Steve; Myshkin, Mikhail Yu.; Paramonov, Alexander S.; Lyukmanova, Ekaterina N.; Arseniev, Alexander S.; Grishin, Eugene V.; Tytgat, Jan; Shenkarev, Zakhar O.; Vassilevski, Alexander A.

    2015-01-01

    We present a structural and functional study of a sodium channel activation inhibitor from crab spider venom. Hm-3 is an insecticidal peptide toxin consisting of 35 amino acid residues from the spider Heriaeus melloteei (Thomisidae). We produced Hm-3 recombinantly in Escherichia coli and determined its structure by NMR spectroscopy. Typical for spider toxins, Hm-3 was found to adopt the so-called “inhibitor cystine knot” or “knottin” fold stabilized by three disulfide bonds. Its molecule is amphiphilic with a hydrophobic ridge on the surface enriched in aromatic residues and surrounded by positive charges. Correspondingly, Hm-3 binds to both neutral and negatively charged lipid vesicles. Electrophysiological studies showed that at a concentration of 1 μm Hm-3 effectively inhibited a number of mammalian and insect sodium channels. Importantly, Hm-3 shifted the dependence of channel activation to more positive voltages. Moreover, the inhibition was voltage-dependent, and strong depolarizing prepulses attenuated Hm-3 activity. The toxin is therefore concluded to represent the first sodium channel gating modifier from an araneomorph spider and features a “membrane access” mechanism of action. Its amino acid sequence and position of the hydrophobic cluster are notably different from other known gating modifiers from spider venom, all of which are described from mygalomorph species. We hypothesize parallel evolution of inhibitor cystine knot toxins from Araneomorphae and Mygalomorphae suborders. PMID:25352595

  18. Structure of membrane-active toxin from crab spider Heriaeus melloteei suggests parallel evolution of sodium channel gating modifiers in Araneomorphae and Mygalomorphae.

    PubMed

    Berkut, Antonina A; Peigneur, Steve; Myshkin, Mikhail Yu; Paramonov, Alexander S; Lyukmanova, Ekaterina N; Arseniev, Alexander S; Grishin, Eugene V; Tytgat, Jan; Shenkarev, Zakhar O; Vassilevski, Alexander A

    2015-01-01

    We present a structural and functional study of a sodium channel activation inhibitor from crab spider venom. Hm-3 is an insecticidal peptide toxin consisting of 35 amino acid residues from the spider Heriaeus melloteei (Thomisidae). We produced Hm-3 recombinantly in Escherichia coli and determined its structure by NMR spectroscopy. Typical for spider toxins, Hm-3 was found to adopt the so-called "inhibitor cystine knot" or "knottin" fold stabilized by three disulfide bonds. Its molecule is amphiphilic with a hydrophobic ridge on the surface enriched in aromatic residues and surrounded by positive charges. Correspondingly, Hm-3 binds to both neutral and negatively charged lipid vesicles. Electrophysiological studies showed that at a concentration of 1 μm Hm-3 effectively inhibited a number of mammalian and insect sodium channels. Importantly, Hm-3 shifted the dependence of channel activation to more positive voltages. Moreover, the inhibition was voltage-dependent, and strong depolarizing prepulses attenuated Hm-3 activity. The toxin is therefore concluded to represent the first sodium channel gating modifier from an araneomorph spider and features a "membrane access" mechanism of action. Its amino acid sequence and position of the hydrophobic cluster are notably different from other known gating modifiers from spider venom, all of which are described from mygalomorph species. We hypothesize parallel evolution of inhibitor cystine knot toxins from Araneomorphae and Mygalomorphae suborders.

  19. Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications

    NASA Astrophysics Data System (ADS)

    Zhang, Bengui; Zhang, Shouhai; Weng, Zhihuan; Wang, Guosheng; Zhang, Enlei; Yu, Ping; Chen, Xiaomeng; Wang, Xinwei

    2016-09-01

    Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes (QADMPEK) are prepared and investigated for vanadium redox flow batteries (VRFB) application. The bulky, rigid and highly hydrophobic adamantane segment incorporated into the backbone of membrane material makes QADMPEK membranes have low water uptake and swelling ratio, and the as-prepared membranes display significantly lower permeability of vanadium ions than that of Nafion117 membrane. As a consequence, the VRFB cell with QADMPEK-3 membrane shows higher coulombic efficiency (99.4%) and energy efficiency (84.0%) than those for Nafion117 membrane (95.2% and 80.5%, respectively) at the current density of 80 mA cm-2. Furthermore, at a much higher current density of 140 mA cm-2, QADMPEK membrane still exhibits better coulombic efficiency and energy efficiency than Nafion117 membrane (coulombic efficiency 99.2% vs 96.5% and energy efficiency 76.0% vs 74.0%). Moreover, QADMPEK membranes show high stability in in-situ VRFB cycle test and ex-situ oxidation stability test. These results indicate that QADMPEK membranes are good candidates for VRFB applications.

  20. Electrocatalytic reduction of nitrate and nitrite at Nafion-coated electrodes in concentrated sodium hydroxide solution

    SciTech Connect

    Li, H. |; Chambers, J.Q.; Hobbs, D.T.

    1988-12-31

    The electrochemical reduction of nitrate ions in alkaline solution has been studied using various cathode materials and is the basis for a patent describing the conversion of nitrate into hydroxide ion in carbonate solutions. Recently, Taniguchi et al. have reported that certain well studied transition metal cyclic amine complexes, namely Co(III)-cyclam and Ni(II)-cyclam where cyclam is 1,4,8,11-tetraazacyclotetradecane, efficiently electrocatalyze the reduction of nitrate and nitrite to hydroxylamine at mercury electrodes. Here the authors report that the metal cyclam catalyst can be incorporated into a Nafion film electrode, and that the reduction of nitrate and nitrite proceeds efficiently at these electrodes in concentrated NaOH solution. Nafion is a perfluoroalkanesulfonated cation exchange material that has been widely used to immobilize redox couples at electrode surfaces, including electrocatalysis species.

  1. Interfacial Water-Transport Effects in Proton-Exchange Membranes

    SciTech Connect

    Kienitz, Brian; Yamada, Haruhiko; Nonoyama, Nobuaki; Weber, Adam

    2009-11-19

    It is well known that the proton-exchange membrane is perhaps the most critical component of a polymer-electrolyte fuel cell. Typical membranes, such as Nafion(R), require hydration to conduct efficiently and are instrumental in cell water management. Recently, evidence has been shown that these membranes might have different interfacial morphology and transport properties than in the bulk. In this paper, experimental data combined with theoretical simulations will be presented that explore the existence and impact of interfacial resistance on water transport for Nafion(R) 21x membranes. A mass-transfer coefficient for the interfacial resistance is calculated from experimental data using different permeation cells. This coefficient is shown to depend exponentially on relative humidity or water activity. The interfacial resistance does not seem to exist for liquid/membrane or membrane/membrane interfaces. The effect of the interfacial resistance is to flatten the water-content profiles within the membrane during operation. Under typical operating conditions, the resistance is on par with the water-transport resistance of the bulk membrane. Thus, the interfacial resistance can be dominant especially in thin, dry membranes and can affect overall fuel-cell performance.

  2. Modified T-Graft for Extracorporeal Membrane Oxygenation in a Patient with Small-Caliber Femoral Arteries

    PubMed Central

    Calderon, Daniel; El-Banayosy, Aly; Koerner, Michael M.; Reed, Amy B.

    2015-01-01

    Extracorporeal membrane oxygenation (ECMO) is generally used as a last resort to provide cardiopulmonary support in patients whose advanced cardiac or respiratory failure does not respond to less invasive treatments. Lower-limb ischemia secondary to the large diameter of the arterial cannula is one of ECMO's major limitations: in patients who have small-caliber arteries, the cannulas can reduce native blood flow. The creation of a T-graft—a well-described technique to avoid limb ischemia—enables flow into the ECMO cannula without jeopardizing blood flow to the limb. However, leaving the graft exposed through an open groin wound can result in dislodgment, and it increases the risk of infection. We describe our modification of a conventional T-graft in an 18-year-old woman who had systolic heart failure, acute respiratory distress syndrome, and small-caliber femoral vessels. We tunneled a polytetrafluoroethylene graft inside a Dacron graft, then ran the combined graft through a subcutaneous tunnel similar to that created for a peripheral bypass. Thus, the graft was protected from environmental exposure and the risk of infection. Our technique seems safer and more secure than the original T-graft technique, and we recommend its consideration during ECMO cannulation. PMID:26664305

  3. Alnus peptides modify membrane porosity and induce the release of nitrogen-rich metabolites from nitrogen-fixing Frankia

    PubMed Central

    Carro, Lorena; Pujic, Petar; Alloisio, Nicole; Fournier, Pascale; Boubakri, Hasna; Hay, Anne E; Poly, Franck; François, Philippe; Hocher, Valerie; Mergaert, Peter; Balmand, Severine; Rey, Marjolaine; Heddi, Abdelaziz; Normand, Philippe

    2015-01-01

    Actinorhizal plant growth in pioneer ecosystems depends on the symbiosis with the nitrogen-fixing actinobacterium Frankia cells that are housed in special root organs called nodules. Nitrogen fixation occurs in differentiated Frankia cells known as vesicles. Vesicles lack a pathway for assimilating ammonia beyond the glutamine stage and are supposed to transfer reduced nitrogen to the plant host cells. However, a mechanism for the transfer of nitrogen-fixation products to the plant cells remains elusive. Here, new elements for this metabolic exchange are described. We show that Alnus glutinosa nodules express defensin-like peptides, and one of these, Ag5, was found to target Frankia vesicles. In vitro and in vivo analyses showed that Ag5 induces drastic physiological changes in Frankia, including an increased permeability of vesicle membranes. A significant release of nitrogen-containing metabolites, mainly glutamine and glutamate, was found in N2-fixing cultures treated with Ag5. This work demonstrates that the Ag5 peptide is central for Frankia physiology in nodules and uncovers a novel cellular function for this large and widespread defensin peptide family. PMID:25603394

  4. Alnus peptides modify membrane porosity and induce the release of nitrogen-rich metabolites from nitrogen-fixing Frankia.

    PubMed

    Carro, Lorena; Pujic, Petar; Alloisio, Nicole; Fournier, Pascale; Boubakri, Hasna; Hay, Anne E; Poly, Franck; François, Philippe; Hocher, Valerie; Mergaert, Peter; Balmand, Severine; Rey, Marjolaine; Heddi, Abdelaziz; Normand, Philippe

    2015-08-01

    Actinorhizal plant growth in pioneer ecosystems depends on the symbiosis with the nitrogen-fixing actinobacterium Frankia cells that are housed in special root organs called nodules. Nitrogen fixation occurs in differentiated Frankia cells known as vesicles. Vesicles lack a pathway for assimilating ammonia beyond the glutamine stage and are supposed to transfer reduced nitrogen to the plant host cells. However, a mechanism for the transfer of nitrogen-fixation products to the plant cells remains elusive. Here, new elements for this metabolic exchange are described. We show that Alnus glutinosa nodules express defensin-like peptides, and one of these, Ag5, was found to target Frankia vesicles. In vitro and in vivo analyses showed that Ag5 induces drastic physiological changes in Frankia, including an increased permeability of vesicle membranes. A significant release of nitrogen-containing metabolites, mainly glutamine and glutamate, was found in N2-fixing cultures treated with Ag5. This work demonstrates that the Ag5 peptide is central for Frankia physiology in nodules and uncovers a novel cellular function for this large and widespread defensin peptide family. PMID:25603394

  5. Alnus peptides modify membrane porosity and induce the release of nitrogen-rich metabolites from nitrogen-fixing Frankia.

    PubMed

    Carro, Lorena; Pujic, Petar; Alloisio, Nicole; Fournier, Pascale; Boubakri, Hasna; Hay, Anne E; Poly, Franck; François, Philippe; Hocher, Valerie; Mergaert, Peter; Balmand, Severine; Rey, Marjolaine; Heddi, Abdelaziz; Normand, Philippe

    2015-08-01

    Actinorhizal plant growth in pioneer ecosystems depends on the symbiosis with the nitrogen-fixing actinobacterium Frankia cells that are housed in special root organs called nodules. Nitrogen fixation occurs in differentiated Frankia cells known as vesicles. Vesicles lack a pathway for assimilating ammonia beyond the glutamine stage and are supposed to transfer reduced nitrogen to the plant host cells. However, a mechanism for the transfer of nitrogen-fixation products to the plant cells remains elusive. Here, new elements for this metabolic exchange are described. We show that Alnus glutinosa nodules express defensin-like peptides, and one of these, Ag5, was found to target Frankia vesicles. In vitro and in vivo analyses showed that Ag5 induces drastic physiological changes in Frankia, including an increased permeability of vesicle membranes. A significant release of nitrogen-containing metabolites, mainly glutamine and glutamate, was found in N2-fixing cultures treated with Ag5. This work demonstrates that the Ag5 peptide is central for Frankia physiology in nodules and uncovers a novel cellular function for this large and widespread defensin peptide family.

  6. A high selectivity quaternized polysulfone membrane for alkaline direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Abuin, Graciela C.; Franceschini, Esteban A.; Nonjola, Patrick; Mathe, Mkhulu K.; Modibedi, Mmalewane; Corti, Horacio R.

    2015-04-01

    Alkaline membranes based on quaternized poly(arylene ether sulfone) (QPAES) were characterized in relation to their water and methanol uptake, methanol permeability, electrical conductivity, and mechanical properties. The performance of QPAES as electrolyte in alkaline direct methanol fuel cells was studied using a free-breathing single fuel cell at room temperature. Methanol uptake by QPAES membranes is lower than water, while their methanol permeability, determined in the temperature range from 30 °C to 75 °C, was much lower than for Nafion membranes. Young modulus of QPAES membranes decrease with the degree of alkalization of the membrane, although mechanical properties are still satisfactory for fuel cell applications for membrane alkalized with 2 M KOH, which additionally exhibit optimal hydroxide conductivity. Although the specific conductivity of QPAES membranes was lower than that reported for Nafion, its methanol selectivity (conductivity/methanol permeability ratio), is much higher than that reported for Nafion 117, and a commercial amminated polysulfone. In view of these results, QPAES membranes are expected to exhibit promising performance as an electrolyte in alkaline direct methanol fuel cells.

  7. Water uptake and swelling hysteresis in a nafion thin film measured with neutron reflectometry.

    PubMed

    Kalisvaart, W Peter; Fritzsche, Helmut; Mérida, Walter

    2015-05-19

    Water uptake and swelling in a thin (∼15 nm) Nafion film on SiO2 native oxide on a Si wafer is studied as a function of relative humidity (8-97%) at room temperature and as a function of temperature (25-60 °C) at 97% relative humidity by neutron reflectometry. This is the first report on the behavior of thin Nafion films at elevated temperatures and high humidity. Large hysteresis is observed during the temperature cycle. The observed swelling strain in the film at 60 °C is 48% as compared to the as-deposited state, which is far above any previously observed trend at room temperature. A small decrease in the average SLD suggests that part of the additional swelling is due to thermal expansion, but the estimated D2O/SO3 ratio also increases by 70%. Half of the "excess" absorption and 73% of the additional swelling are retained during cooling back to room temperature. The results provide new insights into the dynamics of Nafion on nanometer scales under fuel cell operating conditions. PMID:25901752

  8. Amniotic Membrane Modifies the Genetic Program Induced by TGFß, Stimulating Keratinocyte Proliferation and Migration in Chronic Wounds

    PubMed Central

    Alcaraz, Antonia; Mrowiec, Anna; Insausti, Carmen Luisa; Bernabé-García, Ángel; García-Vizcaíno, Eva María; López-Martínez, María Concepción; Monfort, Asunción; Izeta, Ander; Moraleda, José María; Castellanos, Gregorio; Nicolás, Francisco José

    2015-01-01

    Background Post-traumatic large-surface or deep wounds often cannot progress to reepithelialisation because they become irresponsive in the inflammatory stage, so intervention is necessary to provide the final sealing epidermis. Previously we have shown that Amniotic Membrane (AM) induced a robust epithelialisation in deep traumatic wounds. Methods and Findings To better understand this phenomenon, we used keratinocytes to investigate the effect of AM on chronic wounds. Using keratinocytes, we saw that AM treatment is able to exert an attenuating effect upon Smad2 and Smad3 TGFß-induced phosphorylation while triggering the activation of several MAPK signalling pathways, including ERK and JNK1, 2. This also has a consequence for TGFß-induced regulation on cell cycle control key players CDK1A (p21) and CDK2B (p15). The study of a wider set of TGFß regulated genes showed that the effect of AM was not wide but very concrete for some genes. TGFß exerted a powerful cell cycle arrest; the presence of AM however prevented TGFß-induced cell cycle arrest. Moreover, AM induced a powerful cell migration response that correlates well with the expression of c-Jun protein at the border of the healing assay. Consistently, the treatment with AM of human chronic wounds induced a robust expression of c-Jun at the wound border. Conclusions The effect of AM on the modulation of TGFß responses in keratinocytes that favours proliferation together with AM-induced keratinocyte migration is the perfect match that allows chronic wounds to move on from their non-healing state and progress into epithelialization. Our results may explain why the application of AM on chronic wounds is able to promote epithelialisation. PMID:26284363

  9. High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode

    PubMed Central

    Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

    2016-01-01

    We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance. PMID:27210793

  10. High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode

    NASA Astrophysics Data System (ADS)

    Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

    2016-05-01

    We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance.

  11. SiO2@Au core-shell nanospheres self-assemble to form colloidal crystals that can be sintered and surface modified to produce pH-controlled membranes.

    PubMed

    Ignacio-de Leon, Patricia Anne A; Zharov, Ilya

    2013-03-19

    We prepared colloidal crystals by self-assembly of gold-coated silica nanospheres, and free-standing nanoporous membranes by sintering these colloidal crystals. We modified the nanopore surface with ionizable functional groups, by forming a monolayer of L-cysteine or by surface-initiated polymerization of methacrylic acid. Diffusion experiments for the cationic dye Rhodamine B through L-cysteine-modified membranes showed a decrease in flux upon addition of an acid due to the nanopore surface becoming positively charged. Diffusion experiments for the neutral dye, ferrocenecarboxaldehyde, through the PMAA-modified membranes showed a 13-fold increase in flux upon addition of an acid resulting from the protonated polymer collapsing onto the nanopore surface leading to larger pore size. Our results demonstrate that SiO2@Au core-shell nanospheres can self-assemble into colloidal crystals and that transport through the corresponding surface-modified Au-coated colloidal membranes can be controlled by pH.

  12. Characterization of proton exchange membrane materials for fuel cells by solid state nuclear magnetic resonance

    SciTech Connect

    Kong, Zueqian

    2010-01-01

    Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-state NMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-angle X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel model gives the measured S/V ratios in the normal hydration range of a working fuel cell, while dispersed water molecules and polymer ribbons account for the structures at low and high hydration levels, respectively.

  13. Ionomer-Membrane Water Processing Apparatus

    NASA Technical Reports Server (NTRS)

    MacCallum, Taber K. (Inventor); Kelsey, Laura (Inventor)

    2016-01-01

    This disclosure provides water processing apparatuses, systems, and methods for recovering water from wastewater such as urine. The water processing apparatuses, systems, and methods can utilize membrane technology for extracting purified water in a single step. A containment unit can include an ionomer membrane, such as Nafion(Registered Trademark), over a hydrophobic microporous membrane, such as polytetrafluoroethylene (PTFE). The containment unit can be filled with wastewater, and the hydrophobic microporous membrane can be impermeable to liquids and solids of the wastewater but permeable to gases and vapors of the wastewater, and the ionomer membrane can be permeable to water vapor but impermeable to one or more contaminants of the gases and vapors. The containment unit can be exposed to a dry purge gas to maintain a water vapor partial pressure differential to drive permeation of the water vapor, and the water vapor can be collected and processed into potable water.

  14. Communication: Nanoscale ion fluctuations in Nafion polymer electrolyte

    SciTech Connect

    Rumberger, Brant; Bennett, Mackenzie; Zhang, Jingyun; Israeloff, N. E.; Dura, J. A.

    2014-08-21

    Ion conduction mechanisms and the nanostructure of ion conduction networks remain poorly understood in polymer electrolytes which are used as proton-exchange-membranes (PEM) in fuel cell applications. Here we study nanoscale surface-potential fluctuations produced by Brownian ion dynamics in thin films of low-hydration Nafion™, the prototype PEM. Images and power spectra of the fluctuations are used to derive the local conductivity-relaxation spectrum, in order to compare with bulk behavior and hopping-conductivity models. Conductivity relaxation-times ranged from hours to milliseconds, depending on hydration and temperature, demonstrating that the observed fluctuations are produced by water-facilitated hydrogen-ion hopping within the ion-channel network. Due to the small number of ions probed, non-Gaussian statistics of the fluctuations can be used to constrain ion conduction parameters and mechanisms.

  15. Rapid determination of sulfonamide residues in pork by surface-modified hydrophilic electrospun nanofibrous membrane solid-phase extraction combined with ultra-performance liquid chromatography.

    PubMed

    Chen, Rong; Yang, Yingying; Qu, Bin; Li, Yue; Lu, Yong; Tian, Lingling; Shen, Weiyang; Ramakrishna, Seeram

    2016-08-01

    This study aimed to rapidly determine 13 representative sulfonamide (SA) residues in pork by using a surface-modified hydrophilic polystyrene sulfonic acid (PSSA) electrospun nanofibrous membrane as the solid-phase extraction (SPE) pretreatment sorbent, followed by ultra-performance liquid chromatography (UPLC) analysis. The highly hydrophilic nature of PSSA nanofibrous membrane created by vacuum plasma treatment was characterized using Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), water contact angle, and X-ray photoelectron spectroscopy (XPS) measurements. In the pretreatment procedures, 13 SA standards, which were spiked in the fatty pork samples, were extracted, enriched, and purified by the SPE procedure based on the principle of ion exchange with the sulfonic groups on the PSSA chains. Under the optimized conditions, the calibration curves of 13 SA compounds showed good linearities with correlation coefficients (r) of more than 0.99 in the range of 50.0-200 μg kg(-1). The mean recoveries of 13 SAs at the spiked concentrations of 50, 100, and 200 μg kg(-1) were in the range of 70.3-92.5 % with average RSDs (n = 6) of less than 15 % (except for sulfacetamide, 56.9-61.6 %). Compared with other pretreatment methods reported previously, less organic solvent (especially without degreasing the extract with n-hexane) was used in this time-saving SPE procedure, which avoids the possibility of emulsification and therefore enhances the recoveries. The developed and validated analysis method was sensitive, accurate, rapid, convenient, environmentally friendly, and was successfully applied for the detection of 13 SA residues in commercially available pork samples. PMID:27235160

  16. Sensitivity of Hollow Fiber Spacesuit Water Membrane Evaporator Systems to Potable Water Constituents, Contaminants and Air Bubbles

    NASA Technical Reports Server (NTRS)

    Bue, Grant C.; Trevino, Luis A.; Fritts, Sharon; Tsioulos, Gus

    2008-01-01

    The Spacesuit Water Membrane Evaporator (SWME) is the baseline heat rejection technology selected for development for the Constellation lunar suit. The first SWME prototype, designed, built, and tested at Johnson Space Center in 1999 used a Teflon hydrophobic porous membrane sheet shaped into an annulus to provide cooling to the coolant loop through water evaporation to the vacuum of space. This present study describes the test methodology and planning and compares the test performance of three commercially available hollow fiber materials as alternatives to the sheet membrane prototype for SWME, in particular, a porous hydrophobic polypropylene, and two variants that employ ion exchange through non-porous hydrophilic modified Nafion. Contamination tests will be performed to probe for sensitivities of the candidate SWME elements to ordinary constituents that are expected to be found in the potable water provided by the vehicle, the target feedwater source. Some of the impurities in potable water are volatile, such as the organics, while others, such as the metals and inorganic ions are nonvolatile. The non-volatile constituents will concentrate in the SWME as evaporated water from the loop is replaced by the feedwater. At some point in the SWME mission lifecycle as the concentrations of the non-volatiles increase, the solubility limits of one or more of the constituents may be reached. The resulting presence of precipitate in the coolant water may begin to plug pores and tube channels and affect the SWME performance. Sensitivity to macroparticles, lunar dust simulant, and air bubbles will also be investigated.

  17. Production of D-lactic acid in a continuous membrane integrated fermentation reactor by genetically modified Saccharomyces cerevisiae: enhancement in D-lactic acid carbon yield.

    PubMed

    Mimitsuka, Takashi; Sawai, Kenji; Kobayashi, Koji; Tsukada, Takeshi; Takeuchi, Norihiro; Yamada, Katsushige; Ogino, Hiroyasu; Yonehara, Tetsu

    2015-01-01

    Poly d-lactic acid is an important polymer because it improves the thermostability of poly l-lactic acid by stereo complex formation. To demonstrate potency of continuous fermentation using a membrane-integrated fermentation reactor (MFR) system, continuous fermentation using genetically modified Saccharomyces cerevisiae which produces d-lactic acid was performed at the low pH and microaerobic conditions. d-Lactic acid continuous fermentation using the MFR system by genetically modified yeast increased production rate by 11-fold compared with batch fermentation. In addition, the carbon yield of d-lactic acid in continuous fermentation was improved to 74.6 ± 2.3% compared to 39.0 ± 1.7% with batch fermentation. This dramatic improvement in carbon yield could not be explained by a reduction in carbon consumption to form cells compared to batch fermentation. Further detailed analysis at batch fermentation revealed that the carbon yield increased to 76.8% at late stationary phase. S. cerevisiae, which exhibits the Crabtree-positive effect, demonstrated significant changes in metabolic activities at low sugar concentrations (Rossignol et al., Yeast, 20, 1369-1385, 2003). Moreover, lactate-producing S. cerevisiae requires ATP supplied not only from the glycolytic pathway but also from the TCA cycle (van Maris et al., Appl. Environ. Microbiol., 70, 2898-2905, 2004). Our finding was revealed that continuous fermentation, which can maintain the conditions of both a low sugar concentration and air supply, results in Crabtree-positive and lactate-producing S. cerevisiae for suitable conditions of d-lactic acid production with respect to redox balance and ATP generation because of releasing the yeast from the Crabtree effect.

  18. An investigation of structure-property relationships in several categories of proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Rodgers, Marianne Phelan

    The chemical and structural features of proton exchange membranes (PEMs) are related to their fuel cell relevant properties. The objective of this work is to understand structure-property relationships in PEMs through the fabrication and characterization of several classes of membranes. Incorporation of linear and angled monomers into the main chain of a polyimide permitted investigation of the effect of kinked versus linear polymers on membrane properties. The conductivity of angled sulfonated polyimide membranes is greater than those prepared from linear polymers, but water uptakes are lower. These differences are attributed to increased entanglements of angled polymers, which limit the degree of swelling and lead to increased proton concentration. Polyelectrolytes were incorporated into reinforcing materials to study the effect of incorporating and confining polyelectrolytes in the pores of reinforcing materials. The employment of reinforcing materials reduces conductivity, mobility, and permeance due to decreased ionomer content and connectivity of the ionomer. However, membranes are stronger and thinner, which compensates for these losses in terms of lower resistance and increased dimensional stability. Incorporating zirconium hydrogen phosphate (ZrP) and silicon dioxide (SiO2) into NafionRTM membranes permitted investigation of their effect on membrane properties. Data for NafionRTM/ZrP membranes support the theory that ZrP disrupts cohesive forces in Nafion RTM, causing it to absorb more water. The increased water content of the membranes does not result in increased conductivity because there is a concurrent decrease in proton concentration and mobility due to poorly conducting ZrP disrupting the conduction pathway and increased water content diluting protons and separating proton conduction sites. The decreasing density of the NafionRTM/SiO2 composite membranes with increasing SiO2 content and the increased dimensional stability of the membranes increasing

  19. Hollow Fiber Space Suit Water Membrane Evaporator Development for Lunar Missions

    NASA Technical Reports Server (NTRS)

    Bue, Grant C.; Trevino, Luis A.; Hanford, Anthony J.; Mitchell, Keith

    2009-01-01

    The Space Suit Water Membrane Evaporator (SWME) is the baseline heat rejection technology selected for development for the Constellation lunar suit. The Hollow Fiber (HoFi) SWME is being considered for service in the Constellation Space Suit Element (CSSE) Portable Life Support Subsystem (PLSS) to provide cooling to the thermal loop through water evaporation to the vacuum of space. Previous work described the test methodology and planning to compare the test performance of three commercially available hollow fiber materials as alternatives to the sheet membrane prototype for SWME: 1) porous hydrophobic polypropylene, 2) porous hydrophobic polysulfone, and 3) ion exchange through nonporous hydrophilic modified Nafion. Contamination tests were performed to probe for sensitivities of the candidate SWME elements to organics and non-volative inorganics expected to be found in the target feedwater source, i.e., potable water provided by the vehicle. The resulting presence of precipitate in the coolant water could plug pores and tube channels and affect the SWME performance. From this prior work, a commercial porous hydrophobic hollow fiber was selected to satisfy both the sensitivity question and the need to provide 800 W of heat rejection. This paper describes the trade studies, the design methodology, and the hollow fiber test data used to design a full

  20. Evaluation and Characterization of Membranes for HI/H2O/I2 Water Separation for the S-I Cycle

    SciTech Connect

    Frederick F. Stewart

    2005-09-01

    In the Sulfur-Iodine (S-I) thermochemical cycle, iodine is added to the product of the Bunsen reaction to facilitate the separation of sulfuric acid (H2SO4) from hydriodic acid (HI). The amount of iodine can be as high as 83% of the overall mass load of the Bunsen product stream, which potentially introduces a large burden on the cycle’s efficiency. Removal of water from the HI and I2 mixture would substantially reduce the amount of required additional iodine. In this work, Nafion® membranes have been studied for their use as de-watering membranes. Specifically, two thicknesses of Nafion membranes have been found to be effective in this application. The thicker membrane, Nafion-117®, produces moderate fluxes of water with very high separation factors. On the other hand, the thinner membrane, Nafion-112®, yielded very large fluxes of water, however with smaller separation factors. All membranes were found to be durable and did not degrade in contact with the feed stream over periods of time up to three months.

  1. MOR Is Not Enough: Identification of Novel mu-Opioid Receptor Interacting Proteins Using Traditional and Modified Membrane Yeast Two-Hybrid Screens

    PubMed Central

    Jin, Jay; Wong, Victoria; Kittanakom, Saranya; Ferraro, Thomas N.; Stagljar, Igor; Levenson, Robert

    2013-01-01

    The mu-opioid receptor (MOR) is the G-protein coupled receptor primarily responsible for mediating the analgesic and rewarding properties of opioid agonist drugs such as morphine, fentanyl, and heroin. We have utilized a combination of traditional and modified membrane yeast two-hybrid screening methods to identify a cohort of novel MOR interacting proteins (MORIPs). The interaction between the MOR and a subset of MORIPs was validated in pulldown, co-immunoprecipitation, and co-localization studies using HEK293 cells stably expressing the MOR as well as rodent brain. Additionally, a subset of MORIPs was found capable of interaction with the delta and kappa opioid receptors, suggesting that they may represent general opioid receptor interacting proteins (ORIPS). Expression of several MORIPs was altered in specific mouse brain regions after chronic treatment with morphine, suggesting that these proteins may play a role in response to opioid agonist drugs. Based on the known function of these newly identified MORIPs, the interactions forming the MOR signalplex are hypothesized to be important for MOR signaling and intracellular trafficking. Understanding the molecular complexity of MOR/MORIP interactions provides a conceptual framework for defining the cellular mechanisms of MOR signaling in brain and may be critical for determining the physiological basis of opioid tolerance and addiction. PMID:23840749

  2. Solid phase extraction of copper (II) by sorption on octadecyl silica membrane disk modified with a new Schiff base and determination with atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Mashhadizadeh, Mohammad Hossein; Pesteh, Mahnaz; Talakesh, Mahzad; Sheikhshoaie, Iran; Ardakani, Mohammad Mazloum; Karimi, Mohammad Ali

    2008-08-01

    A simple, selective and reliable method for rapid extraction and determination of trace amounts of Cu (II) ions from aqueous samples using octadecyl-bonded silica membrane disks modified with bis-(3-methoxy salicylaldehyde)-1,6-diaminohexane and flame atomic absorption spectrometry (FAAS) is presented. Extraction efficiency, the influence of pH, flow rates, amount of ligand, and type and least amount of eluant were investigated. The linear dynamic range of the proposed method for Cu (II) ions was found in a wide concentration range of 1.0 (± 0.2)-150 (± 2) μg l - 1 . The detection limit and preconcentration factor of this method were found 30.0 (± 0.7) ng l - 1 and 100 respectively. The reproducibility of the procedure is at the most 2.0%. The effects of various cationic interferences on the percent recovery of copper ion were studied. The method was used to the recovery of copper ion from different synthetic, alloys and biological samples.

  3. Sunlight mediated diesel degradation under saline conditions using ionic silver coated sand via nanoreduction: use of impregnated form of thiourea modified chitosan membranes for ex situ application.

    PubMed

    Das, Devlina; Das, Nilanjana

    2014-08-15

    The present research investigates the use of ionic silver coated sand dust (ISSD) for the sunlight mediated degradation of diesel under saline conditions. Sand dust was used as a template for reduction of silver ions by effective removal of chloride ions. Diesel degradation was estimated in terms of degradation (%), chloride removal, volume reduction and nanoparticle synthesis, respectively. The process was optimized using a 7-level Box-Behnken design. Among several factors, time (B), Tween 80 (C), ISSD dosage (D) and silver(I) concentration (F) were found to be most significant. Maximum diesel degradation 99.8% was obtained in a period of 14 h which was analyzed by gas chromatography. XPS analysis confirmed silver reduction as the underlying phenomena. TEM analysis and albeit first approximation method confirmed that enhanced degradation occurred due to physical contact between diesel components and ISSD. First order kinetic model exhibited the best fit. Light microscopy results showed the various stages in diesel degradation by a reduction in bubble size. Ex situ application was carried out using ISSD impregnated thiourea modified chitosan/PVA membranes by surface floatation technique for the remediation of diesel contaminated sea water. Complete diesel degradation was noted after 48 h of sunlight exposure.

  4. Combination of Microporous Hollow Carbon Spheres and Nafion for the Individual Metal-free Stripping Detection of Pb(2+) and Cd(2.).

    PubMed

    Niu, Xiangheng; Zhang, Hongwei; Yu, Meihua; Zhao, Hongli; Lan, Minbo; Yu, Chengzhong

    2016-01-01

    Here, the combination of Nafion with microporous hollow carbon spheres (MHCS) is first proposed to fabricate a disposable metal-free electrode for heavy metal stripping sensing. The MHCS-Nafion composite film electrode is prepared by drop-casting a mixture of MHCS and Nafion onto the lab-made screen-printed carbon electrode (SPCE(*)). Results demonstrate that the interfusion of MHCS into Nafion offers enhanced performance for the electro-enrichment and stripping of lead and cadmium over the only Nafion film: 1) abundant MHCS immobilized on the electrode surface serve as effective nucleation sites for metal ion reduction; 2) the mixing of MHCS into Nafion enlarges the active surface of negative-charged Nafion for the electrostatic adsorption of metal cations. The proposed MHCS-Nafion/SPCE(*) provides linear responses for Pb(2+) and Cd(2+) in the range of 2 - 200 μg/L, with a detection limit of 1.37 and 1.63 μg/L, respectively. Practical applications of the sensor in water sample detection with good accuracy have also been confirmed.

  5. Combination of Microporous Hollow Carbon Spheres and Nafion for the Individual Metal-free Stripping Detection of Pb(2+) and Cd(2.).

    PubMed

    Niu, Xiangheng; Zhang, Hongwei; Yu, Meihua; Zhao, Hongli; Lan, Minbo; Yu, Chengzhong

    2016-01-01

    Here, the combination of Nafion with microporous hollow carbon spheres (MHCS) is first proposed to fabricate a disposable metal-free electrode for heavy metal stripping sensing. The MHCS-Nafion composite film electrode is prepared by drop-casting a mixture of MHCS and Nafion onto the lab-made screen-printed carbon electrode (SPCE(*)). Results demonstrate that the interfusion of MHCS into Nafion offers enhanced performance for the electro-enrichment and stripping of lead and cadmium over the only Nafion film: 1) abundant MHCS immobilized on the electrode surface serve as effective nucleation sites for metal ion reduction; 2) the mixing of MHCS into Nafion enlarges the active surface of negative-charged Nafion for the electrostatic adsorption of metal cations. The proposed MHCS-Nafion/SPCE(*) provides linear responses for Pb(2+) and Cd(2+) in the range of 2 - 200 μg/L, with a detection limit of 1.37 and 1.63 μg/L, respectively. Practical applications of the sensor in water sample detection with good accuracy have also been confirmed. PMID:27682398

  6. Selective Electrochemical Detection of Ciprofloxacin with a Porous Nafion/Multiwalled Carbon Nanotube Composite Film Electrode.

    PubMed

    Gayen, Pralay; Chaplin, Brian P

    2016-01-27

    This study focuses on the development of electrochemical sensors for the detection of Ciprofloxacin (CFX) in natural waters and wastewater effluents. The sensors are prepared by depositing a layer of multiwalled carbon nanotubes (MWCNTs) dispersed in a porous Nafion film on to a boron-doped diamond (BDD) electrode substrate. The porous-Nafion-MWCNT/BDD electrode enhanced detection of CFX due to selective adsorption, which was accomplished by a combination of electrostatic attraction at -SO3(-) sites in the porous Nafion film and the formation of charge assisted hydrogen bonding between CFX and -COOH MWCNT surface functional groups. By contrast, the bare BDD electrode did not show any activity for CFX oxidation. The sensors were selective for CFX detection in the presence of other antibiotics (i.e., amoxicillin) and other nontarget water constituents (i.e., Cl(-), Ca(2+), humic acid, sodium dodecylbenzenesulfonate, salicylic acid, 4-aminobenzoic acid, and 4-hydroxybenzoic acid). A limit of detection of 5 nM (S/N = 5.04 ± 0.26) in a 0.1 M KH2PO4 supporting electrolyte (pH = 4.5) was obtained using differential pulse voltammetry. The linear dynamic ranges with respect to CFX concentration were 0.005-0.05 μM and 0.05-10 μM, and the sensitivities were 41 ± 5.2 μA μM(-1) and 2.1 ± 0.22 μA μM(-1), respectively. Sensor fouling was observed at high concentrations of some organic compounds such as 1 mM 4-aminobenzoic acid and 4-hydroxybenzoic acid. However, a short cathodic treatment fully restores sensor response. The results indicate that these sensors have application in detecting CFX in natural waters and wastewater effluents. PMID:26711553

  7. Selective Electrochemical Detection of Ciprofloxacin with a Porous Nafion/Multiwalled Carbon Nanotube Composite Film Electrode.

    PubMed

    Gayen, Pralay; Chaplin, Brian P

    2016-01-27

    This study focuses on the development of electrochemical sensors for the detection of Ciprofloxacin (CFX) in natural waters and wastewater effluents. The sensors are prepared by depositing a layer of multiwalled carbon nanotubes (MWCNTs) dispersed in a porous Nafion film on to a boron-doped diamond (BDD) electrode substrate. The porous-Nafion-MWCNT/BDD electrode enhanced detection of CFX due to selective adsorption, which was accomplished by a combination of electrostatic attraction at -SO3(-) sites in the porous Nafion film and the formation of charge assisted hydrogen bonding between CFX and -COOH MWCNT surface functional groups. By contrast, the bare BDD electrode did not show any activity for CFX oxidation. The sensors were selective for CFX detection in the presence of other antibiotics (i.e., amoxicillin) and other nontarget water constituents (i.e., Cl(-), Ca(2+), humic acid, sodium dodecylbenzenesulfonate, salicylic acid, 4-aminobenzoic acid, and 4-hydroxybenzoic acid). A limit of detection of 5 nM (S/N = 5.04 ± 0.26) in a 0.1 M KH2PO4 supporting electrolyte (pH = 4.5) was obtained using differential pulse voltammetry. The linear dynamic ranges with respect to CFX concentration were 0.005-0.05 μM and 0.05-10 μM, and the sensitivities were 41 ± 5.2 μA μM(-1) and 2.1 ± 0.22 μA μM(-1), respectively. Sensor fouling was observed at high concentrations of some organic compounds such as 1 mM 4-aminobenzoic acid and 4-hydroxybenzoic acid. However, a short cathodic treatment fully restores sensor response. The results indicate that these sensors have application in detecting CFX in natural waters and wastewater effluents.

  8. Economics of vanadium redox flow battery membranes

    NASA Astrophysics Data System (ADS)

    Minke, Christine; Turek, Thomas

    2015-07-01

    The membrane is a key component of the vanadium redox flow battery (VRFB) in terms of electrochemical performance as well as costs. The standard material Nafion® is cost intensive and therefore several alternative materials are in the focus of research. In this paper a substantial analytical approach is presented in order to quantify bottom price limits for different types of membranes. An in-depth analysis of material and production cost allows statements concerning cost potentials of different ion exchange membranes (IEM) and nano filtration membranes (NFM). The final result reveals that expected costs of IEM and NFM at high production volumes differ by one order of magnitude. Moreover, an analysis of the current market situation is made to provide a framework for economic considerations at present.

  9. High Temperature Membrane with Humidification-Independent Cluster Structure

    SciTech Connect

    Lipp, Ludwig

    2015-07-10

    The objective of this project was to develop high temperature membranes to facilitate the wide-spread deployment of hydrogen fuel cells. High temperature membranes offer significant advantages in PEM system operation, overall capital and operating costs. State-of-the-art Nafion-based membranes are inadequate for the high temperature operation. These conventional membranes become unstable at higher temperatures (90-120°C) and lose their conductivity, particularly at low relative humidity. In this program, alternate materials were developed to enable fabrication of novel high performance composite membranes. FCE’s concept for the multi-component composite membrane, named mC2, has been used in the design of more conductive membranes.

  10. Cryogenic trapping of reduced sulfur compounds using a nafion drier and cotton wadding as an oxidant scavenger

    NASA Astrophysics Data System (ADS)

    Hofmann, U.; Hofmann, R.; Kesselmeier, J.

    A commercially available Nafion drier (Perma-Pure) was tested under laboratory and field conditions and shown to be suitable for measurements of reduced sulfur compounds such as H 2S, COS, CH 3SH, CH 3SCH 3 (DMS) and CS 2 in dry and humid air in the pptv-range. For the scavenging of oxidants we combined the Nafion drier technique with a cotton oxidant scrubber. Results obtained under laboratory conditions with humidified samples and in the course of a small field experiment confirm the oxidant scrubber qualities of cotton and indicate that the cotton oxidant scrubber in combination with a Nafion drier is suitable for measurements of nearly all reduced sulfur compounds except CH 3SH.

  11. An Evaluation of the Performance and Economics of Membranes and Separators in Single Chamber Microbial Fuel Cells Treating Domestic Wastewater.

    PubMed

    Christgen, Beate; Scott, Keith; Dolfing, Jan; Head, Ian M; Curtis, Thomas P

    2015-01-01

    The cost of materials is one of the biggest barriers for wastewater driven microbial fuel cells (MFCs). Many studies use expensive materials with idealistic wastes. Realistically the choice of an ion selective membrane or nonspecific separators must be made in the context of the cost and performance of materials available. Fourteen membranes and separators were characterized for durability, oxygen diffusion and ionic resistance to enable informed membrane selection for reactor tests. Subsequently MFCs were operated in a cost efficient reactor design using Nafion, ethylene tetrafluoroethylene (ETFE) or polyvinylidene fluoride (PVDF) membranes, a nonspecific separator (Rhinohide), and a no-membrane design with a carbon-paper internal gas diffusion cathode. Peak power densities during polarisation, from MFCs using no-membrane, Nafion and ETFE, reached 67, 61 and 59 mWm(-2), and coulombic efficiencies of 68±11%, 71±12% and 92±6%, respectively. Under 1000 Ω, Nafion and ETFE achieved an average power density of 29 mWm(-2) compared to 24 mWm(-2) for the membrane-less reactors. Over a hypothetical lifetime of 10 years the generated energy (1 to 2.5 kWhm(-2)) would not be sufficient to offset the costs of any membrane and separator tested.

  12. An Evaluation of the Performance and Economics of Membranes and Separators in Single Chamber Microbial Fuel Cells Treating Domestic Wastewater

    PubMed Central

    Christgen, Beate; Scott, Keith; Dolfing, Jan; Head, Ian M.; Curtis, Thomas P.

    2015-01-01

    The cost of materials is one of the biggest barriers for wastewater driven microbial fuel cells (MFCs). Many studies use expensive materials with idealistic wastes. Realistically the choice of an ion selective membrane or nonspecific separators must be made in the context of the cost and performance of materials available. Fourteen membranes and separators were characterized for durability, oxygen diffusion and ionic resistance to enable informed membrane selection for reactor tests. Subsequently MFCs were operated in a cost efficient reactor design using Nafion, ethylene tetrafluoroethylene (ETFE) or polyvinylidene fluoride (PVDF) membranes, a nonspecific separator (Rhinohide), and a no-membrane design with a carbon-paper internal gas diffusion cathode. Peak power densities during polarisation, from MFCs using no-membrane, Nafion and ETFE, reached 67, 61 and 59 mWm-2, and coulombic efficiencies of 68±11%, 71±12% and 92±6%, respectively. Under 1000Ω, Nafion and ETFE achieved an average power density of 29 mWm-2 compared to 24 mWm-2 for the membrane-less reactors. Over a hypothetical lifetime of 10 years the generated energy (1 to 2.5 kWhm-2) would not be sufficient to offset the costs of any membrane and separator tested. PMID:26305330

  13. Enhancement of water retention in UV-exposed fuel-cell proton exchange membranes studied using terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Ray, Shaumik; Devi, Nirmala; Dash, Jyotirmayee; Rambabu, Gutru; Bhat, Santoshkumar D.; Pesala, Bala

    2016-02-01

    Proton Exchange Membrane (PEM) fuel cells are increasingly gaining importance as a clean energy source. PEMs need to possess high proton conductivity and should be chemically and mechanically stable in the fuel cell environment. Proton conductivity of PEM in fuel cells is directly proportional to water content in the membrane. Among the various PEMs available, Nafion has high proton conductivity even with low water content compared to SPEEK (Sulfonated Poly(ether ether ketone)) but is also expensive. SPEEK membranes and it's composites have better mechanical properties and have comparatively higher thermal stability. Operating the fuel cell at higher temperatures and at the same time maintaining the water content of the membrane is always a great challenge. In this paper, to increase water retention capacity, Nafion, SPEEK and it's composite (SPEEK PSSA-CNT) membranes are exposed to Ultra-Violet (UV) radiation for varied times. Terahertz Spectroscopy, in both pulsed and CW mode has been used as an efficient tool to quantify the water retention of the membrane. Results using Terahertz spectroscopy show that even though the initial water absorption capacity of Nafion membranes is more, SPEEK membranes and it's composites show considerable improvement in the water retention capacity upon high intensity UV irradiation.

  14. TiO2/bi A-SPAES(Ds 1.0) composite membranes for proton exchange membrane in direct methanol fuel cell (DMFC).

    PubMed

    Zhang, Ni; Zhong, Chuanqing; Xie, Bing; Liu, Huiling; Wang, Xingzu

    2014-09-01

    A series of TiO2/bi A-SPAES(Ds 1.0) composite membranes with various contents of nano-sized TiO2 particles were prepared through sol-gel method. Scanning electron microscopy (SEM) images indicated the TiO2 particles were well dispersed within polymer matrix. These membranes were used for proton exchange membrane (PEM) for performance evaluation in direct methanol fuel cell (DMFC). These composite membranes showed good thermal stability and mechanical strength. It was found that the water uptake of these membranes enhanced with the TiO2 amount increasing in these composite membranes. Meanwhile, the introduction of TiO2 particles increased the proton conductivity and reduced the methanol permeability. The proton conductivities of these composite membranes with 8% TiO2 particles (0.120 S/cm and 0.128 S/cm) were higher than those of Nafion 117 membrane (0.114 S/cm and 0.117 S/cm) at 80 degrees C and 100 degrees C. Specially, the methanol diffusion coefficient (1.2 x 10(-7) cm2/s) of the composite membrane with 8% TiO2 content was much lower than that of Nafion 117 membrane (2.1 x 10(-6) cm2/s). As a result, the TiO2/bi A-SPAES composite membrane was considered as a promising material for PEM in DMFC.

  15. Infrared spectroscopy of bis[(perfluoroalkyl)sulfonyl] imide ionomer membrane materials.

    PubMed

    Byun, Chang Kyu; Sharif, Iqbal; Desmarteau, Darryl D; Creager, Stephen E; Korzeniewski, Carol

    2009-05-01

    Structural properties of the proton-exchanged forms of bis[(perfluoroalkyl)sulfonyl] imide (PFSI) ionomer materials were investigated. The hydration and dehydration of samples prepared as thin films and freestanding membrane were probed by applying transmission infrared spectroscopy. Spectral bands were assigned and effects of water incorporation into membrane pores and channels were understood by drawing upon results from related measurements performed on the structurally similar, perfluorosulfonic acid ionomer, Nafion. Both PFSI and Nafion membrane materials display a prominent infrared absorbance band near 1060 cm(-1) that arises from a vibrational mode of the ionizable group present on the side chains that extend from the poly(tetrafluoroethylene) backbone on the polymers. The mode can be traced to symmetric stretching of the -SO(3)(-) (sulfonate) group in Nafion and to antisymmetric S-N-S stretching within the sulfonyl imide end group (-SO(2)(N(-))SO(2)CF(3)) in the PFSI materials. For Nafion samples, the position and width of the band near 1060 cm(-1) are strongly sensitive to membrane hydration, whereas the band position and shape change only slightly during hydration and dehydration of PFSI materials. The possibility for greater charge delocalization over the sulfonyl imide moiety and shielding of hydrophilic species by the terminal -CF(3) group are suggested to explain the differences. These effects also likely influence the stretching modes of the side chain C-O-C groups. A pair of bands, sensitive to hydration and traceable to different C-O-C groups in a side chain, is present in the 970-990 cm(-1) region of Nafion. However, the two features are not well resolved and are less sensitive to hydration in spectra of PFSI samples. The most intense ionomer spectral bands arise from modes involving C-F stretching motion and appear between 1150 and 1250 cm(-1). Toward the high energy side of the envelope, there is substantial overlap with features of sulfonate

  16. Correlating Humidity-Dependent Ionically Conductive Surface Area with Transport Phenomena in Proton-Exchange Membranes

    SciTech Connect

    He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T.; Clark, Kyle; Weber, Adam Z.; Kostecki, Robert

    2011-08-01

    The objective of this effort was to correlate the local surface ionic conductance of a Nafion? 212 proton-exchange membrane with its bulk and interfacial transport properties as a function of water content. Both macroscopic and microscopic proton conductivities were investigated at different relative humidity levels, using electrochemical impedance spectroscopy and current-sensing atomic force microscopy (CSAFM). We were able to identify small ion-conducting domains that grew with humidity at the surface of the membrane. Numerical analysis of the surface ionic conductance images recorded at various relative humidity levels helped determine the fractional area of ion-conducting active sites. A simple square-root relationship between the fractional conducting area and observed interfacial mass-transport resistance was established. Furthermore, the relationship between the bulk ionic conductivity and surface ionic conductance pattern of the Nafion? membrane was examined.

  17. Nanoporous Polytetrafluoroethylene/Silica Composite Separator as a High-Performance All-Vanadium Redox Flow Battery Membrane

    SciTech Connect

    Wei, Xiaoliang; Nie, Zimin; Luo, Qingtao; Li, Bin; Chen, Baowei; Simmons, Kevin L.; Sprenkle, Vincent L.; Wang, Wei

    2013-09-02

    Driven by the motivation of searching for low-cost membrane alternatives, a novel nanoporous polytetrafluoroethylene/silica composite separator has been prepared and evaluated for its use in all-vanadium mixed-acid redox flow battery. This separator consisting of silica particles enmeshed in a polytetrafluoroethylene fibril matrix has no ion exchange capacity and is featured with unique nanoporous structures, which function as the ion transport channels in redox flow battery operation, with an average pore size of 38nm and a porosity of 48%. This separator has produced excellent electrochemical performance in the all-vanadium mixed-acid system with energy efficiency delivery comparable to Nafion membrane and superior rate capability and temperature tolerance. The separator also demonstrates an exceptional capacity retention capability over extended cycling, offering additional operational latitude towards conveniently mitigating the capacity decay that is inevitable for Nafion. Because of the inexpensive raw materials and simple preparation protocol, the separator is particularly low-cost, estimated to be at least an order of magnitude more inexpensive than Nafion. Plus the proven chemical stability due to the same backbone material as Nafion, this separator possesses a good combination of critical membrane requirements and shows great potential to promote market penetration of the all-vanadium redox flow battery by enabling significant reduction of capital and cycle costs.

  18. Polymer electrolyte membranes from fluorinated polyisoprene-block-sulfonated polystyrene: Membrane structure and transport properties

    SciTech Connect

    Sodeye, Akinbode; Huang, Tianzi; Gido, Samuel; Mays, Jimmy

    2011-01-01

    With a view to optimizing morphology and ultimately properties, membranes have been cast from relatively inexpensive block copolymer ionomers of fluorinated polyisoprene-block-sulfonated polystyrene (FISS) with various sulfonation levels, in both the acid form and the cesium neutralized form. The morphology of these membranes was characterized by transmission electron microscopy and ultra-small angle X-ray scattering, as well as water uptake, proton conductivity and methanol permeability within the temperature range from 20 to 60 C. Random phase separated morphologies were obtained for all samples except the cesium sample with 50 mol% sulfonation. The transport properties increased with increasing degree of sulfonation and temperature for all samples. The acid form samples absorbed more water than the cesium samples with a maximum swelling of 595% recorded at 60 C for the acid sample having 50 mol% sulfonation. Methanol permeability for the latter sample was more than an order of magnitude less than for Nafion 112 but so was the proton conductivity within the plane of the membrane at 20 C. Across the plane of the membrane this sample had half the conductivity of Nafion 112 at 60 C.

  19. Inorganic-based proton conductive composite membranes for elevated temperature and reduced relative humidity PEM fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Chunmei

    Proton exchange membrane (PEM) fuel cells are regarded as highly promising energy conversion systems for future transportation and stationary power generation and have been under intensive investigations for the last decade. Unfortunately, cutting edge PEM fuel cell design and components still do not allow economically commercial implementation of this technology. The main obstacles are high cost of proton conductive membranes, low-proton conductivity at low relative humidity (RH), and dehydration and degradation of polymer membranes at high temperatures. The objective of this study was to develop a systematic approach to design a high proton conductive composite membrane that can provide a conductivity of approximately 100 mS cm-1 under hot and dry conditions (120°C and 50% RH). The approach was based on fundamental and experimental studies of the proton conductivity of inorganic additives and composite membranes. We synthesized and investigated a variety of organic-inorganic Nafion-based composite membranes. In particular, we analyzed their fundamental properties, which included thermal stability, morphology, the interaction between inorganic network and Nafion clusters, and the effect of inorganic phase on the membrane conductivity. A wide range of inorganic materials was studied in advance in order to select the proton conductive inorganic additives for composite membranes. We developed a conductivity measurement method, with which the proton conductivity characteristics of solid acid materials, zirconium phosphates, sulfated zirconia (S-ZrO2), phosphosilicate gels, and Santa Barbara Amorphous silica (SBA-15) were discussed in detail. Composite membranes containing Nafion and different amounts of functionalized inorganic additives (sulfated inorganics such as S-ZrO2, SBA-15, Mobil Composition of Matter MCM-41, and S-SiO2, and phosphonated inorganic P-SiO2) were synthesized with different methods. We incorporated inorganic particles within Nafion clusters

  20. The investigation of resin degradation in catalyst layer of proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Xiao, Shaohua; Zhang, Huamin

    2014-01-01

    In order to separate resin degradation in catalyst layer (CL) from membrane degradation of proton exchange membrane fuel cell (PEMFC), Fluorine emission rate (FER) was specially selected to highlight the degradation of Nafion® resin in CL by employing hydrocarbon membrane as membrane. The drain water from the cathode and anode was collected and analyzed separately. It is found that FERs of drain water are 0.065 μmol cm-2 h-1 (cathode) and 0.049 μmol cm-2 h-1 (anode), suggesting resin degradation happened in CLs and the predominant degradation occurred in the cathode in open circuit operation.

  1. Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

    EPA Science Inventory

    An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

  2. Cross-linked poly (vinyl alcohol)/sulfosuccinic acid polymer as an electrolyte/electrode material for H2-O2 proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Ebenezer, D.; Deshpande, Abhijit P.; Haridoss, Prathap

    2016-02-01

    Proton exchange membrane fuel cell (PEMFC) performance with a cross-linked poly (vinyl alcohol)/sulfosuccinic acid (PVA/SSA) polymer is compared with Nafion® N-115 polymer. In this study, PVA/SSA (≈5 wt. % SSA) polymer membranes are synthesized by a solution casting technique. These cross-linked PVA/SSA polymers and Nafion are used as electrolytes and ionomers in catalyst layers, to fabricate different membrane electrode assemblies (MEAs) for PEMFCs. Properties of each MEA are evaluated using scanning electron microscopy, contact angle measurements, impedance spectroscopy and hydrogen pumping technique. I-V characteristics of each cell are evaluated in a H2-O2 fuel cell testing fixture under different operating conditions. PVA/SSA ionomer causes only an additional ≈4% loss in the anode performance compared to Nafion ionomer. The maximum power density obtained from PVA/SSA based cells range from 99 to 117.4 mW cm-2 with current density range of 247 to 293.4 mA cm-2. Ionic conductivity of PVA/SSA based cells is more sensitive to state of hydration of MEA, while maximum power density obtained is less sensitive to state of hydration of MEA. Maximum power density of cross-linked PVA/SSA membrane based cell is about 35% that of Nafion® N-115 based cell. From these results, cross-linked PVA/SSA polymer is identified as potential candidate for PEMFCs.

  3. The carboxyl modifier 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide (EDC) inhibits half of the high-affinity Mn-binding site in photosystem II membrane fragments

    SciTech Connect

    Preston, C.; Seibert, M. )

    1991-10-08

    The diphenylcarbazide (DPC)/Mn{sup 2+} assay was used to assess the amount of the high-affinity Mn-binding site in manganese-depleted photosystem II (PS II) membrane fragments from spinach and Scenedesmus obliquus. The assay mechanism at high DPC concentration was shown to involve noncompetitive inhibition of only half of the control level of DPC donation to PS II by micromolar concentrations of Mn at pH 6.5. At low DPC concentration both DPC and Mn{sup 2+} donate to PS II additively. Treatment with the carboxyl amino acid modifier 1-ethyl-3-(3(dimethylamino) propyl) carbodiimide (EDC) inhibited half of the high affinity Mn-binding site in spinach and Scenedesmus WT PS II membranes and all of the available site in Scenedesmus LF-1 mutant PS II membranes. A similar EDC concentration dependence was observed in all cases. This protection was specific for Mn{sup 2+}; six other divalent cations were ineffective. The authors conclude that EDC modifies that half of the high-affinity Mn-binding site that is insensitive to the histidine modifier diethyl pyrocarbonate (DEPC) and directly affects ligands that bind Mn. The effects of EDC and DEPC that influence the high-affinity site are mutually exclusive and are specific to the lumenal side of the PS II membrane. They suggest that carboxyl residues on reaction center proteins are associated with half of the high-affinity Mn-binding site in PS II and are involved along with histidine residues in binding Mn functional in the O{sub 2}-evolving process.

  4. Achieving highly effective non-biofouling performance for polypropylene membranes modified by UV-induced surface graft polymerization of two oppositely charged monomers.

    PubMed

    Zhao, Yong-Hong; Zhu, Xiao-Ying; Wee, Kin-Ho; Bai, Renbi

    2010-02-25

    A major problem in membrane technology for applications such as wastewater treatment or desalination is often the loss of membrane permeability due to biofouling initiated from protein adsorption and biofilm formation on the membrane surface. In this study, we developed a relatively simple and yet versatile approach to prepare polypropylene (PP) membrane with highly effective non-biofouling performance. Copolymer brushes were grafted to the surface of PP membrane through UV-induced polymerization of two oppositely charged monomers, i.e., [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TM) and 3-sulfopropyl methacrylate potassium salt (SA), with varying TM:SA molar ratios. Surface analysis with scanning electron microscope (SEM) clearly showed the grafted copolymer brushes on the membrane surfaces and that with X-ray photoelectron spectroscope (XPS) revealed a similar TM:SA ratio of the grafted copolymer brushes to that of the monomer solution used for the polymerization. Water contact angle measurements indicated that the hydrophilicity of the membrane surfaces was remarkably improved by the grafting of the TM/SA copolymer brushes, with the lowest water contact angle of 27 degrees being achieved at the TM:SA ratio of around 1:1. Experiments for antiprotein adsorption with bovine serum album (BSA) and lysozyme (LYZ) and antibiofilm formation with Escherichia coli (E. coli) demonstrated a great dependence of the membrane performance on the TM:SA ratios of the grafted copolymer brushes. It was found that the characteristics of the surface charges of the membrane surfaces played a very important role in the non-biofouling performance, and the membrane surface with balanced positive and negative charges showed the best non-biofouling performance for the proteins and bacteria tested in this study.

  5. Zirconium/PVA modified flat-sheet PVDF membrane as a cost-effective adsorptive and filtration material: A case study on decontamination of organic arsenic in aqueous solutions.

    PubMed

    Zhao, Dandan; Yu, Yang; Wang, Chenghong; Chen, J Paul

    2016-09-01

    Organic arsenic in waters has been a global concern in drinking water due to its higher toxicity to humans. In this study, a novel zirconium/polyvinyl alcohol (PVA) modified polyvinylidene fluoride (PVDF) membrane was applied to remove organic arsenic from water. The impregnation of zirconium ions within the modified membrane was attributed to the coordination reactions among the zirconium ions, ether and hydroxyl groups. The synthesized membrane worked better at the acidic conditions and achieved the optimal uptake for both monomethylarsonic (MMA) and dimethylarsinic (DMA) at pH 2.0. The adsorption isotherm study demonstrated that the adsorption of both organic arsenic species was controlled by the mono-layer adsorption process; the maximum adsorption capacities for MMA and DMA were 73.04 and 37.53mg/g at pH 2, and 29.78 and 19.03mg/g at pH 7.0, respectively. The presence of humic acid had a negligible impact on the uptake of organic arsenic, whereas varying impacts on the arsenic adsorption were observed due to the presence of coexisting anions such as fluoride, phosphate, carbonate and silicate. A single piece of membrane with a surface area of only 12.56cm(2) could treat 7.5-L MMA and 4.1-L DMA solution with an influent concentration of about 100μg/L to meet the WHO and USEPA standard of 10μg/L. Based on the XPS analyses, the ion exchange reaction between chloride ions on the membrane surface and organic arsenic species was responsible for the removal of both MMA and DMA. PMID:27267042

  6. An experimental investigation of strain rate, temperature and humidity effects on the mechanical behavior of a perfluorosulfonic acid membrane

    NASA Astrophysics Data System (ADS)

    Lu, Zongwen; Lugo, Melissa; Santare, Michael H.; Karlsson, Anette M.; Busby, F. Colin; Walsh, Peter

    2012-09-01

    The time-dependent hygro-thermal mechanical behavior of a perfluorosulfonic acid (PFSA) membrane (Nafion® 211 membrane) commonly used in Proton Exchange Membrane Fuel Cells (PEMFCs) is investigated at selected strain rates for a broad range of temperatures and humidities. Tensile tests and relaxation tests are conducted to determine Young's modulus and proportional limit stress as functions of strain rate, temperature and humidity. The results show that Young's modulus and proportional limit stress increase as the strain rate increases, and decrease as the temperature or humidity increases. The results also show that the mechanical response of Nafion® 211 membrane is more sensitive to typical changes in strain rate or temperature than to typical changes in humidity. In addition, two temperature/humidity cycles are conducted to determine the steady state swelling behavior of Nafion® 211 membrane as a function of temperature and humidity. The results show that the membrane swells with increasing temperature and humidity, and that there is little or no hygro-thermal history effect for the swelling strains.

  7. Solid-phase Extraction and Purification of Membrane Proteins Using a UV-modified PMMA Microfluidic Bioaffinity μSPE Device

    PubMed Central

    Battle, Katrina N.; Jackson, Joshua M.; Witek, Małgorzata A.; Hupert, Mateusz L.; Hunsucker, Sally A.; Armistead, Paul M.; Soper, Steven A.

    2014-01-01

    We present a novel microfluidic solid-phase extraction (μSPE) device for the affinity enrichment of biotinylated membrane proteins from whole cell lysates. The device offers features that address challenges currently associated with the extraction and purification of membrane proteins from whole cell lysates, including the ability to release the enriched membrane protein fraction from the extraction surface so that they are available for downstream processing. The extraction bed was fabricated in PMMA using hot embossing and was comprised of 3,600 micropillars. Activation of the PMMA micropillars by UV/O3 treatment permitted generation of surface-confined carboxylic acid groups and the covalent attachment of NeutrAvidin onto the μSPE device surfaces, which was used to affinity select biotinylated MCF-7 membrane proteins directly from whole cell lysates. The inclusion of a disulfide linker within the biotin moiety permitted release of the isolated membrane proteins via DTT incubation. Very low levels (~20 fmol) of membrane proteins could be isolated and recovered with ~89% efficiency with a bed capacity of 1.7 pmol. Western blotting indicated no traces of cytosolic proteins in the membrane protein fraction as compared to significant contamination using a commercial detergent-based method. We highlight future avenues for enhanced extraction efficiency and increased dynamic range of the μSPE device using computational simulations of different micropillar geometries to guide future device designs. PMID:24487280

  8. An ultrathin self-humidifying membrane for PEM fuel cell application: fabrication, characterization, and experimental analysis.

    PubMed

    Zhu, Xiaobing; Zhang, Huamin; Zhang, Yu; Liang, Yongmin; Wang, Xiaoli; Yi, Baolian

    2006-07-27

    An ultrathin poly(tetrafluoroethylene) (PTFE)-reinforced multilayer self-humidifying composite membrane (20 microm, thick) is developed. The membrane is composed of Nafion-impregnated porous PTFE composite as the central layer, and SiO2 supported nanosized Pt particles (Pt-SiO2) imbedded into the Nafion as the two side layers. The proton exchange membrane (PEM) fuel cell employing the self-humidifying membrane (Pt-SiO2/NP) turns out a peak power density of 1.40 W cm(-2) and an open circuit voltage (OCV) of 1.032 V under dry H2/O2 condition. The excellent performance is attributed to the combined result of both the accelerated water back-diffusion in the thin membrane and the adsorbing/releasing water properties of the Pt-SiO2 catalyst in the side layers. Moreover, the inclusion of the hygroscopic Pt-SiO2 catalyst inside the membrane results in an enhanced anode self-humidification capability and also the decreased cathode polarization (accordingly an improved cell OCV). Several techniques, such as transmission electronic microscopy, scanning electronic microscopy, energy dispersive spectroscopy, thermal analysis and electrochemical impedance spectroscopy etc., are employed to characterize the Pt-SiO2/NP membrane. The results are discussed in comparison with the plain Nafion/PTFE membrane (NP). It is established that the reverse net water drag (from the cathode to the anode) across the Pt-SiO2/NP membrane reaches 0.16 H2O/H+. This implies a good hydration of the Pt-SiO2/NP membrane and thus ensures an excellent PEM fuel cell performance under self-humidification operation.

  9. Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells.

    PubMed

    Liu, Xiaoteng; Christensen, Paul A; Kelly, Stephen M; Rocher, Vincent; Scott, Keith

    2013-12-05

    Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved.

  10. 2H nuclear magnetic resonance study of deuterated water dynamics in perfluorosulfonic acid ionomer Nafion

    NASA Astrophysics Data System (ADS)

    Han, Jun Hee; Lee, Kyu Won; Lee, Cheol Eui

    2016-11-01

    We have employed deuteron nuclear magnetic resonance (NMR) spectroscopy in order to study the dynamics of the deuterated water (D2O) molecules introduced into a perfluorosulfonic acid ionomer Nafion (NR-211) film. According to the 2H NMR spectral analysis, the deuterated water molecules at low temperatures occupied either relatively rigid or mobile sites up to the temperature TM=240 K where all the deuterated water molecules became mobile. The temperature-dependent NMR linewidths sensitively reflected the motional narrowing of the rigid and mobile sites, and the NMR chemical shift reflected significant changes in the hydrogen bonds of the deuterated water. While a slow- to fast-limit motional transition was manifested at TM in the laboratory-frame NMR spin-lattice relaxation, the rotating-frame spin-lattice relaxation indicated no bulk liquid water state down to 200 K.

  11. Signal stability of Nafion-coated thin mercury film electrodes for stripping voltammetry.

    PubMed

    Hoyer, B; Jensen, N

    1994-03-01

    The signal stability of the Nafion-coated thin mercury film electrode (NCTMFE) was studied by using cadmium and lead as test analytes and differential pulse anodic stripping voltammetry as detection method. In particular, the effect of the casting solvent and the curing procedure employed in the preparation of the polymer film was examined. Best results were obtained with N,N-dimethylacetamide as casting solvent and a two-step curing procedure in which the polymer was evaporated to dryness at 55 degrees and cured at 105 degrees with a hot-air gun. Mercury plating was performed ex situ. An NCTMFE prepared in this manner has a better signal stability than ex situ-plated as well as in situ-plated conventional mercury film electrodes. PMID:18965949

  12. Synthesis and characterization of carbon nanotubes supported platinum nanocatalyst for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Lin, J. F.; Kamavaram, V.; Kannan, A. M.

    Multi-walled carbon nanotubes (MWCNTs) were used as catalyst support for depositing platinum nanoparticles by a wet chemistry route. MWCNTs were initially surface modified by citric acid to introduce functional groups which act as anchors for metallic clusters. A two-phase (water-toluene) method was used to transfer PtCl 6 2- from aqueous to organic phase and the subsequent sodium formate solution reduction step yielded Pt nanoparticles on MWCNTs. High-resolution TEM images showed that the platinum particles in the size range of 1-3 nm are homogeneously distributed on the surface of MWCNTs. The Pt/MWCNTs nanocatalyst was evaluated in the proton exchange membrane (PEM) single cell using H 2/O 2 at 80 °C with Nafion-212 electrolyte. The single PEM fuel cell exhibited a peak power density of about 1100 mW cm -2 with a total catalyst loading of 0.6 mg Pt cm -2 (anode: 0.2 mg Pt cm -2 and cathode: 0.4 mg Pt cm -2). The durability of Pt/MWCNTs nanocatalyst was evaluated for 100 h at 80 °C at ambient pressure and the performance (current density at 0.4 V) remained stable throughout. The electrochemically active surface area (64 m 2 g -1) as estimated by cyclic voltammetry (CV) was also similar before and after the durability test.

  13. Hydrophobicity effects in iron polypyridyl complex electrocatalysis within Nafion thin-film electrodes.

    PubMed

    Azad, Uday Pratap; Yadav, Dharmendra Kumar; Ganesan, Vellaichamy; Marken, Frank

    2016-08-17

    Four polypyridyl redox catalysts Fe(bp)3(2+), Fe(ph)3(2+), Fe(dm)3(2+), and Fe(tm)3(2+) (with bp, ph, dm, and tm representing 2,2'-bipyridine, 1,10-phenanthroline, 4,4'-dimethyl-2,2'-bipyridine, and 3,4,7,8-tetramethyl-1,10-phenanthroline, respectively) are investigated for the electrocatalytic oxidation of three analytes (nitrite, arsenite, and isoniazid). The poly-pyridyl iron complex is exchanged into a Nafion film immobilized on a glassy carbon electrode, which is then immersed in 0.1 M Na2SO4. Cyclic voltammetry is employed for the evaluation of the mechanism and estimation of kinetic parameters. The electrocatalytic behaviour going from low to high substrate concentration is consistent with the Albery-Hillman cases of "LEty" switching to "LEk" (changing from the first order in the substrate to half order in the substrate), denoting a process that occurs in a reaction zone close to the electrode surface with diffusion of charge (from the electrode surface into the film) and of anionic or neutral analyte (from the Nafion-solution interface into the film). The relative hydrophobicity of the iron polypyridyl catalyst within the film is shown to affect both the diffusion of charge/electrons and analyte within the film with Fe(tm)3(2+) providing the mildest catalyst. All three analytes, nitrite, isoniazid, and arsenite, exhibit linear calibration ranges beneficial for analytical applications in the micro-molar to the milli-molar range. PMID:27498920

  14. Hydrophobicity effects in iron polypyridyl complex electrocatalysis within Nafion thin-film electrodes.

    PubMed

    Azad, Uday Pratap; Yadav, Dharmendra Kumar; Ganesan, Vellaichamy; Marken, Frank

    2016-08-17

    Four polypyridyl redox catalysts Fe(bp)3(2+), Fe(ph)3(2+), Fe(dm)3(2+), and Fe(tm)3(2+) (with bp, ph, dm, and tm representing 2,2'-bipyridine, 1,10-phenanthroline, 4,4'-dimethyl-2,2'-bipyridine, and 3,4,7,8-tetramethyl-1,10-phenanthroline, respectively) are investigated for the electrocatalytic oxidation of three analytes (nitrite, arsenite, and isoniazid). The poly-pyridyl iron complex is exchanged into a Nafion film immobilized on a glassy carbon electrode, which is then immersed in 0.1 M Na2SO4. Cyclic voltammetry is employed for the evaluation of the mechanism and estimation of kinetic parameters. The electrocatalytic behaviour going from low to high substrate concentration is consistent with the Albery-Hillman cases of "LEty" switching to "LEk" (changing from the first order in the substrate to half order in the substrate), denoting a process that occurs in a reaction zone close to the electrode surface with diffusion of charge (from the electrode surface into the film) and of anionic or neutral analyte (from the Nafion-solution interface into the film). The relative hydrophobicity of the iron polypyridyl catalyst within the film is shown to affect both the diffusion of charge/electrons and analyte within the film with Fe(tm)3(2+) providing the mildest catalyst. All three analytes, nitrite, isoniazid, and arsenite, exhibit linear calibration ranges beneficial for analytical applications in the micro-molar to the milli-molar range.

  15. Proton Exchange Membranes for Fuel Cells

    SciTech Connect

    Devanathan, Ramaswami

    2010-11-01

    Proton exchange membrane, also known as polymer electrolyte membrane, fuel cells (PEMFCs) offer the promise of efficient conversion of chemical energy of fuel, such as hydrogen or methanol, into electricity with minimal pollution. Their widespread use to power zero-emission automobiles as part of a hydrogen economy can contribute to enhanced energy security and reduction in greenhouse gas emissions. However, the commercial viability of PEMFC technology is hindered by high cost associated with the membrane electrode assembly (MEA) and poor membrane durability under prolonged operation at elevated temperature. Membranes for automotive fuel cell applications need to perform well over a period comparable to the life of an automotive engine and under heavy load cycling including start-stop cycling under sub-freezing conditions. The combination of elevated temperature, changes in humidity levels, physical stresses and harsh chemical environment contribute to membrane degradation. Perfluorinated sulfonic acid (PFSA)-based membranes, such as Nafion®, have been the mainstay of PEMFC technology. Their limitations, in terms of cost and poor conductivity at low hydration, have led to continuing research into membranes that have good proton conductivity at elevated temperatures above 120 °C and under low humidity conditions. Such membranes have the potential to avoid catalyst poisoning, simplify fuel cell design and reduce the cost of fuel cells. Hydrocarbon-based membranes are being developed as alternatives to PFSA membranes, but concerns about chemical and mechanical stability and durability remain. Novel anhydrous membranes based on polymer gels infused with protic ionic liquids have also been recently proposed, but considerable fundamental research is needed to understand proton transport in novel membranes and evaluate durability under fuel cell operating conditions. In order to advance this promising technology, it is essential to rationally design the next generation

  16. Electrically driven ion separations and nanofiltration through membranes coated with polyelectrolyte multilayers

    NASA Astrophysics Data System (ADS)

    White, Nicholas

    Polyelectrolyte multilayer (PEM) films deposited using the layer-by-layer (LBL) method are attractive for their simple deposition, tailorable nature, scalability, and charge or size-based selectivity for solutes. This dissertation explores ion separations in electrodialysis (ED) and solute removal through nanofiltration with PEMs deposited on polymer membranes. ED membranes typically exhibit modest selectivities between monovalent and divalent ions. In contrast, this work shows that K+/Mg 2+ ED selectivities reach values >1000 when using Nafion 115 cation-exchange membranes coated with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For comparison, the corresponding K+ /Mg2+ selectivity of bare Nafion 115 is <2. However, water-splitting at strongly overlimiting current densities may lead to a local pH increase close to the membrane surface and alter film permeability or allow passage of Mg(OH)x species to decrease selectivity. When the source phase contains high salt concentrations, the K+ transference number approaches unity and the K+/Mg2+ selectivity is >20,000, presumably because the applied current is below the limiting value for K+ and H+ transport is negligible at this high K+ concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions. The high ED selectivities of (PAH/PSS)5PAH-coated Nafion membranes translate to separations with Li+/Co2+ and K +/La3+. Even with adsorption of only 3 polyelectrolyte layers, Nafion membranes exhibit a Li+/Co2+ selectivity >23. However, the resistance to monovalent-ion passage does not decrease significantly with fewer polyelectrolyte layers. At overlimiting currents, hydroxides from water splitting form insoluble metal hydroxides to foul the membrane. With 0.1 M source-phase salt concentrations, transference numbers for monovalent cations approach unity and selectivities are >5000

  17. Intermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applications

    NASA Astrophysics Data System (ADS)

    Liang, Yu; Gong, Chenliang; Qi, Zhigang; Li, Hui; Wu, Zhongying; Zhang, Yakui; Zhang, Shujiang; Li, Yanfeng

    2015-06-01

    A series of novel ionic cross-linking sulfonated poly(ether ether ketone) (SPEEK) membranes containing the diazafluorene functional group are synthesized to reduce the swelling ratio and methanol permeability for direct methanol fuel cell (DMFC) applications. The ionic cross-linking is realized by the interaction between sulfonic acid groups and pyridyl in diazafluorene. The prepared membranes exhibit good mechanical properties, adequate thermal stability, good oxidative stability, appropriate water uptake and low swelling ratio. Moreover, the ionic cross-linked membranes exhibit lower methanol permeability in the range between 0.56 × 10-7 cm2 s-1 and 1.8 × 10-7 cm2 s-1, which is lower than Nafion 117, and they exhibit higher selectivity than Nafion 117 at 30 °C on the basis of applicable proton conductivity.

  18. Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes.

    PubMed

    Li, Zhiyang; Leung, Calvin; Gao, Fan; Gu, Zhiyong

    2015-01-01

    In this paper, vertically aligned Pt nanowire arrays (PtNWA) with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H₂O₂) detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO) template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with dif