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Sample records for catalytic membranes final

  1. Catalytic membrane program novation: High temperature catalytic membrane reactors. Final report

    SciTech Connect

    Kleiner, R.N.

    1998-08-28

    The original objective was to develop an energy-efficient hydrocarbon dehydrogenation process based on catalytic membrane reactors. Golden Technologies determined that the goals of this contract would be best served by novating the contract to an end user or other interested party which is better informed on the economic justification aspects of petrochemical refining processes to carry out the remaining work. In light of the Chevron results, the program objective was broadened to include development of inorganic membranes for applications in the chemical industry. The proposed membrane technologies shall offer the potential to improve chemical production processes via conversion increase and energy savings. The objective of this subcontract is to seek a party that would serve as a prime contractor to carry out the remaining tasks on the agreement and bring the agreement to a successful conclusion. Four tasks were defined to select the prime contractor. They were (1) prepare a request for proposal, (2) solicit companies as potential prime contractors as well as team members, (3) discuss modifications requested by the potential prime contractors, and (4) obtain, review and rank the proposals. The accomplishments on the tasks is described in detail in the following sections.

  2. Catalytic carbon membranes for hydrogen production. Final report

    SciTech Connect

    Damle, A.S.; Gangwal, S.K.

    1992-01-01

    Commercial carbon composite microfiltration membranes may be modified for gas separation applications by providing a gas separation layer with pores in the 1- to 10-nm range. Several organic polymeric precursors and techniques for depositing a suitable layer were investigated in this project. The in situ polymerization technique was found to be the most promising, and pure component permeation tests with membrane samples prepared with this technique indicated Knudsen diffusion behavior. The gas separation factors obtained by mixed-gas permeation tests were found to depend strongly on gas temperature and pressure indicating significant viscous flow at high-pressure conditions. The modified membranes were used to carry out simultaneous water gas shift reaction and product hydrogen separation. These tests indicated increasing CO conversions with increasing hydrogen separation. A simple process model was developed to simulate a catalytic membrane reactor. A number of simulations were carried out to identify operating conditions leading to product hydrogen concentrations over 90 percent. (VC)

  3. Catalytic membranes beckon

    SciTech Connect

    Caruana, C.M.

    1994-11-01

    Chemical engineers here and abroad are finding that the marriage of catalysts and membranes holds promise for faster and more specific reactions, although commercialization of this technology is several years away. Catalytic membrane reactors (CMRs) combine a heterogeneous catalyst and a permselective membrane. Reactions performed by CMRs provide higher yields--sometimes as much as 50% higher--because of better reaction selectivity--as opposed to separation selectivity. CMRs also can work at very high temperatures, using ceramic materials that would not be possible with organic membranes. Although the use of CMRs is not widespread presently, the development of new membranes--particularly porous ceramic and zeolite membranes--will increase the potential to improve yields of many catalytic processes. The paper discusses ongoing studies, metal and advanced materials for membranes, the need for continued research, hydrogen recovery from coal-derived gases, catalytic oxidation of sulfides, CMRs for water purification, and oxidative coupling of methane.

  4. Catalytic nanoporous membranes

    DOEpatents

    Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

    2013-08-27

    A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

  5. Catalytic nanoporous membranes

    DOEpatents

    Pellin, Michael J.; Hryn, John N.; Elam, Jeffrey W.

    2009-12-01

    A nanoporous catalytic membrane which displays several unique features including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity.

  6. Development of hollow fiber catalytic membrane reactors for high temperature gas cleanup. Final report, September 1989--March 1994

    SciTech Connect

    Ma, Yi Hua; Moser, W.R.; Pien, S.; Shelekhin, A.B.

    1994-07-01

    The objective of this project was to develop economically and technically viable catalytic membrane reactors for high temperature, high pressure gaseous contaminant control in Integrated Gasification Combined Cycle (IGCC) systems. These catalytic membrane reactors decompose H{sub 2}S and separate the reaction products. The reactors were designed to operate in the hostile process environment of the IGCC systems, and at temperatures ranging from 500 to 1000{degrees}C. Severe conditions encountered in the IGCC process (e.g., 900{degrees}C, containing of H{sub 2}S, CO{sub 2} and H{sub 2}O) make it impossible to use polymeric membranes in the process. A list of inorganic membranes that can be employed in the membrane reactor includes Pd metallic membranes, molecular-sieve glass membranes (PPG Industries), porous Vycor glass membranes and porous sol-gel derived membranes such as alumina, zirconia. Alumina and zirconia membranes, however, cannot withstand for a long time at high temperatures in the presence of water vapors. Palladium membranes are a very promising class of inorganic membranes for gas separations that is currently under development. In this project two different types of membranes were used in the design of the membrane reactor -- molecular-sieve glass membrane and Vycor glass porous membrane.

  7. Novel Catalytic Membrane Reactors

    SciTech Connect

    Stuart Nemser, PhD

    2010-10-01

    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  8. Catalytic Membrane Sensors

    SciTech Connect

    Boyle, T.J.; Brinker, C.J.; Gardner, T.J.; Hughes, R.C.; Sault, A.G.

    1998-12-01

    The proposed "catalytic membrane sensor" (CMS) was developed to generate a device which would selectively identify a specific reagent in a complex mixture of gases. This was to be accomplished by modifying an existing Hz sensor with a series of thin films. Through selectively sieving the desired component from a complex mixture and identifying it by decomposing it into Hz (and other by-products), a Hz sensor could then be used to detect the presence of the select component. The proposed "sandwich-type" modifications involved the deposition of a catalyst layered between two size selective sol-gel layers on a Pd/Ni resistive Hz sensor. The role of the catalyst was to convert organic materials to Hz and organic by-products. The role of the membraneo was to impart both chemical specificity by molecukir sieving of the analyte and converted product streams, as well as controlling access to the underlying Pd/Ni sensor. Ultimately, an array of these CMS elements encompassing different catalysts and membranes were to be developed which would enable improved selectivity and specificity from a compiex mixture of organic gases via pattern recognition methodologies. We have successfully generated a CMS device by a series of spin-coat deposited methods; however, it was determined that the high temperature required to activate the catalyst, destroys the sensor.

  9. High temperature catalytic membrane reactors

    SciTech Connect

    Not Available

    1990-03-01

    Current state-of-the-art inorganic oxide membranes offer the potential of being modified to yield catalytic properties. The resulting modules may be configured to simultaneously induce catalytic reactions with product concentration and separation in a single processing step. Processes utilizing such catalytically active membrane reactors have the potential for dramatically increasing yield reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity. Examples of commercial interest include hydrogenation, dehydrogenation, partial and selective oxidation, hydrations, hydrocarbon cracking, olefin metathesis, hydroformylation, and olefin polymerization. A large portion of the most significant reactions fall into the category of high temperature, gas phase chemical and petrochemical processes. Microporous oxide membranes are well suited for these applications. A program is proposed to investigate selected model reactions of commercial interest (i.e. dehydrogenation of ethylbenzene to styrene and dehydrogenation of butane to butadiene) using a high temperature catalytic membrane reactor. Membranes will be developed, reaction dynamics characterized, and production processes developed, culminating in laboratory-scale demonstration of technical and economic feasibility. As a result, the anticipated increased yield per reactor pass economic incentives are envisioned. First, a large decrease in the temperature required to obtain high yield should be possible because of the reduced driving force requirement. Significantly higher conversion per pass implies a reduced recycle ratio, as well as reduced reactor size. Both factors result in reduced capital costs, as well as savings in cost of reactants and energy.

  10. Novel Catalytic Membrane Reactors

    SciTech Connect

    2009-02-01

    This factsheet describes a research project that will focus on the development and application of nonporous high gas flux perfluoro membranes with high temperature rating and excellent chemical resistance.

  11. Dense ceramic catalytic membranes and membrane reactors for energy and environmental applications.

    PubMed

    Dong, Xueliang; Jin, Wanqin; Xu, Nanping; Li, Kang

    2011-10-21

    Catalytic membrane reactors which carry out separation and reaction in a single unit are expected to be a promising approach to achieve green and sustainable chemistry with less energy consumption and lower pollution. This article presents a review of the recent progress of dense ceramic catalytic membranes and membrane reactors, and their potential applications in energy and environmental areas. A basic knowledge of catalytic membranes and membrane reactors is first introduced briefly, followed by a short discussion on the membrane materials including their structures, composition and strategies for material development. The configuration of catalytic membranes, the design of membrane reaction processes and the high temperature sealing are also discussed. The performance of catalytic membrane reactors for energy and environmental applications are summarized and typical catalytic membrane reaction processes are presented and discussed. Finally, current challenges and difficulties related to the industrialization of dense ceramic membrane reactors are addressed and possible future research is also outlined.

  12. Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils. Final Report

    SciTech Connect

    George W. Huber; Upadhye, Aniruddha A.; Ford, David M.; Bhatia, Surita R.; Badger, Phillip C.

    2012-10-19

    This University of Massachusetts, Amherst project, "Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils" started on 1st February 2009 and finished on August 31st 2011. The project consisted following tasks: Task 1.0: Char Removal by Membrane Separation Technology The presence of char particles in the bio-oil causes problems in storage and end-use. Currently there is no well-established technology to remove char particles less than 10 micron in size. This study focused on the application of a liquid-phase microfiltration process to remove char particles from bio-oil down to slightly sub-micron levels. Tubular ceramic membranes of nominal pore sizes 0.5 and 0.8m were employed to carry out the microfiltration, which was conducted in the cross-flow mode at temperatures ranging from 38 to 45 C and at three different trans-membrane pressures varying from 1 to 3 bars. The results demonstrated the removal of the major quantity of char particles with a significant reduction in overall ash content of the bio-oil. The results clearly showed that the cake formation mechanism of fouling is predominant in this process. Task 2.0 Acid Removal by Membrane Separation Technology The feasibility of removing small organic acids from the aqueous fraction of fast pyrolysis bio-oils using nanofiltration (NF) and reverse osmosis (RO) membranes was studied. Experiments were carried out with a single solute solutions of acetic acid and glucose, binary solute solutions containing both acetic acid and glucose, and a model aqueous fraction of bio-oil (AFBO). Retention factors above 90% for glucose and below 0% for acetic acid were observed at feed pressures near 40 bar for single and binary solutions, so that their separation in the model AFBO was expected to be feasible. However, all of the membranes were irreversibly damaged when experiments were conducted with the model AFBO due to the presence of guaiacol in the feed solution. Experiments

  13. Enzyme catalytic membrane based on a hybrid mesoporous membrane.

    PubMed

    Fu, Wensheng; Yamaguchi, Akira; Kaneda, Hideaki; Teramae, Norio

    2008-02-21

    Immobilization of glucose oxidase (GOD) within a hybrid mesoporous membrane with 12 nm pore diameter was successfully achieved, resulting in catalytically high efficiency during flow of a glucose solution across the membrane.

  14. Catalytic membranes for fuel cells

    SciTech Connect

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2011-04-19

    A fuel cell of the present invention comprises a cathode and an anode, one or both of the anode and the cathode including a catalyst comprising a bundle of longitudinally aligned graphitic carbon nanotubes including a catalytically active transition metal incorporated longitudinally and atomically distributed throughout the graphitic carbon walls of said nanotubes. The nanotubes also include nitrogen atoms and/or ions chemically bonded to the graphitic carbon and to the transition metal. Preferably, the transition metal comprises at least one metal selected from the group consisting of Fe, Co, Ni, Mn, and Cr.

  15. Mesoporous catalysts, supports and catalytic membranes based on MCM-41. Final report for the period January 15,2000 - January 14, 2001

    SciTech Connect

    Haller, Gary L.

    2001-07-01

    The research had two objectives: to understand the effect of pore size on the chemistry and activity of active sites, and to investigate both the pore size and anchoring effect of Me-MCM-41 on Pt clusters (where Me is a metal incorporated in silica-based MCM-41). The focus is not on the effect of pore size on transport of reactants and products, but on how the local radius of curvature might affect the properties of a foreign ion embedded in a silicon wall that acts as a catalytic site or anchor for the catalytic site. The mesoporous molecular sieve, MCM-41, allows the variation of pore size with constant composition and pore geometry so these new materials allow this scientific question to be addressed for the first time. For the anchoring effect, concentration was on Sn-MCM-41 to prepare Pt/Sn-MCM-41 catalysts, by characterizing these and by testing them with probe reforming reactions (dehydrogenation, isomerization and aromatization). Although this is a final report on activity January 15, 2000 - January 14, 2001, this was a continuation of work initiated in the three-year grant period January 15, 1997 - January 14, 2000, so the summary of progress for these three years is appended for completeness.

  16. Catalytic carbon membranes for hydrogen production

    SciTech Connect

    Damle, A.S.; Gangwal, S.K.

    1992-01-01

    Commercial carbon composite microfiltration membranes may be modified for gas separation applications by providing a gas separation layer with pores in the 1- to 10-nm range. Several organic polymeric precursors and techniques for depositing a suitable layer were investigated in this project. The in situ polymerization technique was found to be the most promising, and pure component permeation tests with membrane samples prepared with this technique indicated Knudsen diffusion behavior. The gas separation factors obtained by mixed-gas permeation tests were found to depend strongly on gas temperature and pressure indicating significant viscous flow at high-pressure conditions. The modified membranes were used to carry out simultaneous water gas shift reaction and product hydrogen separation. These tests indicated increasing CO conversions with increasing hydrogen separation. A simple process model was developed to simulate a catalytic membrane reactor. A number of simulations were carried out to identify operating conditions leading to product hydrogen concentrations over 90 percent. (VC)

  17. Carbogenic molecular sieves for reaction and separation by design: A novel approach to shape selective super base, super acid and catalytic membranes. Final report

    SciTech Connect

    Foley, Henry C.

    2002-03-18

    This report details the findings of three years of research plus one year of a no-cost extension. Primary results are the work with supported nanoporous carbon membranes for separation and reaction as well as with cesium-nanoporous carbon catalysts. The work resulted in 17 plus 2 papers (2 are in progress) and partial or full support for five Ph.D. students. Two patents were filed based on this research.

  18. Lipase immobilized catalytically active membrane for synthesis of lauryl stearate in a pervaporation membrane reactor.

    PubMed

    Zhang, Weidong; Qing, Weihua; Ren, Zhongqi; Li, Wei; Chen, Jiangrong

    2014-11-01

    A composite catalytically active membrane immobilized with Candida rugosa lipase has been prepared by immersion phase inversion technique for enzymatic synthesis of lauryl stearate in a pervaporation membrane reactor. SEM images showed that a "sandwich-like" membrane structure with a porous lipase-PVA catalytic layer uniformly coated on a polyvinyl alcohol (PVA)/polyethersulfone (PES) bilayer was obtained. Optimum conditions for lipase immobilization in the catalytic layer were determined. The membrane was proved to exhibit superior thermal stability, pH stability and reusability than free lipase under similar conditions. In the case of pervaporation coupled synthesis of lauryl stearate, benefited from in-situ water removal by the membrane, a conversion enhancement of approximately 40% was achieved in comparison to the equilibrium conversion obtained in batch reactors. In addition to conversion enhancement, it was also found that excess water removal by the catalytically active membrane appears to improve activity of the lipase immobilized.

  19. Polymer and Membrane Design for Low Temperature Catalytic Reactions.

    PubMed

    Villalobos, Luis Francisco; Xie, Yihui; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2016-04-01

    Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane's ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Liberated PKA Catalytic Subunits Associate with the Membrane via Myristoylation to Preferentially Phosphorylate Membrane Substrates.

    PubMed

    Tillo, Shane E; Xiong, Wei-Hong; Takahashi, Maho; Miao, Sheng; Andrade, Adriana L; Fortin, Dale A; Yang, Guang; Qin, Maozhen; Smoody, Barbara F; Stork, Philip J S; Zhong, Haining

    2017-04-18

    Protein kinase A (PKA) has diverse functions in neurons. At rest, the subcellular localization of PKA is controlled by A-kinase anchoring proteins (AKAPs). However, the dynamics of PKA upon activation remain poorly understood. Here, we report that elevation of cyclic AMP (cAMP) in neuronal dendrites causes a significant percentage of the PKA catalytic subunit (PKA-C) molecules to be released from the regulatory subunit (PKA-R). Liberated PKA-C becomes associated with the membrane via N-terminal myristoylation. This membrane association does not require the interaction between PKA-R and AKAPs. It slows the mobility of PKA-C and enriches kinase activity on the membrane. Membrane-residing PKA substrates are preferentially phosphorylated compared to cytosolic substrates. Finally, the myristoylation of PKA-C is critical for normal synaptic function and plasticity. We propose that activation-dependent association of PKA-C renders the membrane a unique PKA-signaling compartment. Constrained mobility of PKA-C may synergize with AKAP anchoring to determine specific PKA function in neurons. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  1. Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

    DOEpatents

    Schwartz, Michael; White, James H.; Sammels, Anthony F.

    2000-01-01

    This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

  2. Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

    DOEpatents

    Schwartz, Michael; White, James H.; Sammells, Anthony F.

    2005-09-27

    This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

  3. Thin film porous membranes for catalytic sensors

    SciTech Connect

    Hughes, R.C.; Boyle, T.J.; Gardner, T.J.

    1997-06-01

    This paper reports on new and surprising experimental data for catalytic film gas sensing resistors coated with nanoporous sol-gel films to impart selectivity and durability to the sensor structure. This work is the result of attempts to build selectivity and reactivity to the surface of a sensor by modifying it with a series of sol-gel layers. The initial sol-gel SiO{sub 2} layer applied to the sensor surprisingly showed enhanced O{sub 2} interaction with H{sub 2} and reduced susceptibility to poisons such as H{sub 2}S.

  4. Catalytic membrane reactor for conversion of syngas to liquid hydrocarbons

    SciTech Connect

    Khassin, A.A.

    2005-07-01

    Plug-through catalytically-active contractor membranes can combine high permeability ({gt} 20 m Darcy), high mechanical strength ({gt} 20 kg cm{sup -2}) and high heat-conductivity ({gt} 4 W(mK){sup -1}). Therefore, it provides isothermicity and low pressure drop. The intense mass-transfer within transport pores, high specific area of these pores and small distances between two adjacent transport pores weaken the mass-transfer constraints. Using the PCM one can achieve high space time yield of hydrocarbons and high selectivity towards heavy hydrocarbons and olefins. These advantages allow supposing the effective usage of the PCM catalytic membrane reactors in Fischer-Tropsch synthesis. Also the same approach could be efficient for some other multiphase catalytic processes, like hydrogenation of the unsaturated fatty acids. 5 figs.

  5. Study on surface properties of gamma-alumina catalytic membrane

    SciTech Connect

    Mengchenu Lu; Guoxing Xiong; Bauser, H.

    1994-12-31

    In recent years, preparation and separation applications of gamma-alumina membranes have been extensively studied. In catalysis research field, this membrane can be used not only as a separating medium but also as a catalyst or catalyst support. In this paper, a gamma-alumina catalytic membrane was prepared by a sol-gel technique, then special attention was paid to its surface properties related to catalysis, its surface acidity, hydroxyl, microstructure and pore properties was studied by IR with pyridine adsorption, XRD and N{sub 2} adsorption at low temperature, 1-butanol dehydration as a probe reaction was used to study its reaction property.

  6. Catalytic membrane reactor for water and wastewater treatment

    NASA Astrophysics Data System (ADS)

    Heng, Samuel

    A double membrane reactor was fabricated and assessed for continuous treatment of water containing organic contaminants by ozonation. This innovative reactor consisted of a zeolite membrane prepared on the inner surface of a porous a-alumina support, which served as water selective extractor and active contactor, and a porous stainless membrane which was the ozone gas diffuser. The coupling of membrane separation and chemical oxidation was found to be highly beneficial to both processes. The total organic carbon (TOC) removal rate at the retentate was enhanced by up to 2.2 times, as compared to membrane ozonation. Simultaneously, clean water (< 2 mg C.L-1 ) was consistently produced on the permeate side, using a feed solution containing up to 1000 mg C.L-1, while the retentate was concentrated and treated. Most significantly, the addition of an adsorbing material, as a bed or a coated layer, onto the pores of the membrane support, was shown to further enhance TOC degradation, permeated TOC concentration, permeate flux, and moreover, ozone yield. The achievements of this project included: (1) The development of a novel low-temperature zeolite membrane activation method that generates consistently high quality membranes (i.e. high reproducibility and fewer defects). (2) The demonstration that gamma-alumina and gamma-alumina supported catalysts do not have significant activity and that the TOC removal enhancement usually observed during catalytic ozonation was due primarily to the contribution of adsorption and metal leaching. Thermogravimetric analysis (TGA) and elemental analysis (EA) of the spent catalyst showed that, during catalytic ozonation, oxygenated by-products of increased adsorbability were concentrated onto the gamma-alumina contactor, and were subsequently degraded. (3) The development of a method for coating high surface area gamma-alumina layers onto the grains of zeolite membrane support used as the active membrane contactor.

  7. Catalytic polyelectrolyte multilayers at the bipolar membrane interface.

    PubMed

    Abdu, Said; Sricharoen, Kittikun; Wong, John E; Muljadi, Eko S; Melin, Thomas; Wessling, Matthias

    2013-11-13

    Bipolar membranes are laminated anion and cation exchange membranes that split water at their interface very efficiently upon application of an electric field. This paper investigates the layer-by-layer (LbL) deposition of polyelectrolyte multilayers, as a tool to introduce molecularly thin catalyst groups at this interface of bipolar membranes. The bipolar membranes were prepared by first modifying an anion exchange membrane by consecutive dipping LbL assembly, then casting a thin highly charged intermediate layer followed by casting a cation exchange layer. The results reveal that polyelectrolytes of higher charge density coated on the anion exchange layer yield better performance. Several parameters of the LbL interface deposition were varied. Out of the investigated LbL assembly parameters, ionic strength and number of layers have shown the largest influence on catalytic activity as well as ionic selectivity. The membrane with two bilayers of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) and poly(ethyleneimine) (PEI), where the PEI was prepared in 0.5 M NaCl, gave rise to the best performance. Surprisingly, detailed data analysis at low electrical potential suggests that the interface layers of a bipolar membrane play a major role in its permselectivity. Previously, only the bulk thickness of the anion and cation exchange membrane was assumed to influence the bipolar membrane selectivity.

  8. Membranes for corrosive oxidations. Final CRADA report.

    SciTech Connect

    Snyder, S. W.; Energy Systems

    2010-02-01

    The objective of this project is to develop porous hydrophilic membranes that are highly resistant to oxidative and corrosive conditions and to deploy them for recovery and purification of high tonnage chemicals such as hydrogen peroxide and other oxychemicals. The research team patented a process for membrane-based separation of hydrogen peroxide (US Patent No. 5,662,878). The process is based on using a hydrophilic membrane to separate hydrogen peroxide from the organic working solution. To enable this process, a new method for producing hydrophilic membrane materials (Patent No.6,464,880) was reported. We investigated methods of producing these hydrophilic materials and evaluated separations performance in comparison to membrane stability. It was determined that at the required membrane flux, membrane stability was not sufficient to design a commercial process. This work was published (Hestekin et al., J. Membrane Science 2006). To meet the performance needs of the process, we developed a membrane contactor method to extract the hydrogen peroxide, then we surveyed several commercial and pre-commercial membrane materials. We identified pre-commercial hydrophilic membranes with the required selectivity, flux, and stability to meet the needs of the process. In addition, we invented a novel reaction/separations format that greatly increases the performance of the process. To test the performance of the membranes and the new formats we procured and integrated reactor/membrane separations unit that enables controlled mixing, flow, temperature control, pressure control, and sampling. The results were used to file a US non-provisional patent application (ANL-INV 03-12). Hydrogen peroxide is widely used in pulp and paper applications, environmental treatment, and other industries. Virtually all hydrogen peroxide production is now based on a process featuring catalytic hydrogenation followed by auto-oxidation of suitable organic carrier molecules. This process has several

  9. [Influence of UV-light on erythrocyte membrane structure and catalytic behaviour of membrane acetylcholine esterase].

    PubMed

    Volotovskiĭ, I D; Sheĭko, L M; Konev, S V

    1976-01-01

    UV-light is shown to induce the structural transitions in the erythrocyte membrane described by S-shape curves in plots of the structural response versus the irradiation dose. In contrast to the free acetylcholine esterase (AChE) UV-light acts on the membrane enzyme as a mixed inhibitor (simultaneous change in Vmax and Km). The modification of the environment structure of residual enzyme is suggested to be the main reason of this phenomenon. The effect is under the control of membrane integrity and disappears after its desintegration. Membrane AChE treated ultrasonically both prior to and after irradiation is inactivated without a Km change. The data obtained show the influence of erythrocyte membrane structure on the catalytic behaviour of membrane-bound AChE.

  10. Solid state proton and electron mediating membrane and use in catalytic membrane reactors

    DOEpatents

    White, James H.; Schwartz, Michael; Sammells, Anthony F.

    2000-01-01

    Mixed electron- and proton-conducting metal oxide materials are provided. These materials are useful in fabrication of membranes for use in catalytic membrane reactions, particularly for promoting dehydrogenation of hydrocarbons, oligomerization of hydrocarbons and for the decomposition of hydrogen-containing gases. Membrane materials are perovskite compounds of the formula: AB.sub.1-x B'.sub.x O.sub.3-y where A=Ca, Sr, or Ba; B=Ce, Tb, Pr or Th; B'=Ti, V, Cr, Mn, Fe, Co, Ni or Cu; 0.2

  11. Method for recovering catalytic elements from fuel cell membrane electrode assemblies

    DOEpatents

    Shore, Lawrence [Edison, NJ; Matlin, Ramail [Berkeley Heights, NJ; Heinz, Robert [Ludwigshafen, DE

    2012-06-26

    A method for recovering catalytic elements from a fuel cell membrane electrode assembly is provided. The method includes converting the membrane electrode assembly into a particulate material, wetting the particulate material, forming a slurry comprising the wetted particulate material and an acid leachate adapted to dissolve at least one of the catalytic elements into a soluble catalytic element salt, separating the slurry into a depleted particulate material and a supernatant containing the catalytic element salt, and washing the depleted particulate material to remove any catalytic element salt retained within pores in the depleted particulate material.

  12. Solid state proton and electron mediating membrane and use in catalytic membrane reactors

    DOEpatents

    White, James H.; Schwartz, Michael; Sammells, Anthony F.

    1998-01-01

    This invention provides catalytic proton and electron mediating membranes useful in catalytic reactors. The membranes have an oxidation and a reduction surface and comprise a single-phase mixed metal oxide material of the formula: AB.sub.1-x B'.sub.x O.sub.3-y wherein A is selected from Ca, Sr or Ba ions; B is selected from Ce, Tb, Pr, or Th ions; B' is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Ga, or In ions, or combinations thereof; and x is greater than or equal to 0.02 and less than or equal to 0.5. The membranes can further comprise a catalyst on either the oxidation or reduction surface, or both. Membranes include those which are fabricated-by combining powders of metal oxides or metal carbonates of metal A ion, metal B ion and metal B' ion such that the stoichiometric ratio A:B:B' is 1:1-x:x where 0.2.ltoreq..times.0.5, repeatedly calcining and milling the combined powders until a single-phase material is obtained and pressing and sintering the singlephase material to obtain a membrane.

  13. Solid state proton and electron mediating membrane and use in catalytic membrane reactors

    DOEpatents

    White, J.H.; Schwartz, M.; Sammells, A.F.

    1998-10-13

    This invention provides catalytic proton and electron mediating membranes useful in catalytic reactors. The membranes have an oxidation and a reduction surface and comprise a single-phase mixed metal oxide material of the formula: AB{sub 1{minus}x}B{prime}{sub x}O{sub 3{minus}y} wherein A is selected from Ca, Sr or Ba ions; B is selected from Ce, Tb, Pr, or Th ions; B{prime} is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Ga, or In ions, or combinations thereof; and x is greater than or equal to 0.02 and less than or equal to 0.5. The membranes can further comprise a catalyst on either the oxidation or reduction surface, or both. Membranes include those which are fabricated by combining powders of metal oxides or metal carbonates of metal A ion, metal B ion and metal B{prime} ion such that the stoichiometric ratio A:B:B{prime} is 1:1{minus}x:x where 0.2{<=}{times}0.5, repeatedly calcining and milling the combined powders until a single-phase material is obtained and pressing and sintering the single phase material to obtain a membrane. 6 figs.

  14. Cryogenic methane separation/catalytic hydrogasification process analysis. Final report

    SciTech Connect

    Cassano, A.A.; Hilton, M.F.; Li, T.C.; Tsao, T.R.

    1980-02-14

    The objective of this program was to recommend the most attractive combinations of acid gas removal methane separation systems for the Exxon Catalytic Coal Gasification (CCG) and the Rockwell Hydrogasification process currently undergoing development supported by DOE. The program was comprised of the following tasks. Screening to define the most promising integration scheme for each gasification process; development of a process flowsheet, heat and material balance, P and ID, equipment specification, utility summary, and plot plan for the process combination selected; and preparation of detailed economic and final report. The results of the study are documented in this report. The evaluations were performed using data supplied by the prime coal gasification contractors and the vendors of proprietary acid gas removal processes. This information, combined with Air Products' in-house capabilities in acid gas and cryogenic separation processses, was used to develop process designs and cost estimates for each integrated system. The design based and economic criteria employed in the study are described.

  15. Solid state proton and electron mediating membrane and use in catalytic membrane reactors

    DOEpatents

    White, James H.; Schwartz, Michael; Sammells, Anthony F.

    2001-01-01

    Mixed electron- and proton-conducting metal oxide materials are provided. These materials are useful in fabrication of membranes for use in catalytic membrane reactions, particularly for promoting dehydrogenation of hydrocarbons, oligomerization of hydrocarbons and for the decomposition of hydrogen-containing gases. Membrane materials are perovskite compounds of the formula: AB.sub.1-x B'.sub.x O.sub.3-y where A=Ca, Sr, or Ba; B=Ce, Tb, Pr or Th; B'=Ti, V, Cr, Mn, Fe, Co, Ni or Cu; 0.2.ltoreq.x.ltoreq.0.5, and y is a number sufficient to neutralize the charge in the mixed metal oxide material.

  16. Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium nanoparticles.

    PubMed

    Jia, Zhiqian; Sun, Huijie; Du, Zhenxia; Lei, Zhigang

    2014-02-01

    Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium (Pd) nanoparticles was studied for the first time. The effects of Pd loading, dye concentration and reuse repetitions of membranes were investigated. In reduction, the dye concentration decreased whereas the pH rose gradually. An optimal Pd loading was found. The catalytic membranes were able to be reused more than 3 times.

  17. Oxygen transport membrane system and method for transferring heat to catalytic/process reactors

    DOEpatents

    Kelly, Sean M.; Kromer, Brian R.; Litwin, Michael M.; Rosen, Lee J.; Christie, Gervase Maxwell; Wilson, Jamie R.; Kosowski, Lawrence W.; Robinson, Charles

    2016-01-19

    A method and apparatus for producing heat used in a synthesis gas production process is provided. The disclosed method and apparatus include a plurality of tubular oxygen transport membrane elements adapted to separate oxygen from an oxygen containing stream contacting the retentate side of the membrane elements. The permeated oxygen is combusted with a hydrogen containing synthesis gas stream contacting the permeate side of the tubular oxygen transport membrane elements thereby generating a reaction product stream and radiant heat. The present method and apparatus also includes at least one catalytic reactor containing a catalyst to promote the steam reforming reaction wherein the catalytic reactor is surrounded by the plurality of tubular oxygen transport membrane elements. The view factor between the catalytic reactor and the plurality of tubular oxygen transport membrane elements radiating heat to the catalytic reactor is greater than or equal to 0.5

  18. Oxygen transport membrane system and method for transferring heat to catalytic/process reactors

    DOEpatents

    Kelly, Sean M; Kromer, Brian R; Litwin, Michael M; Rosen, Lee J; Christie, Gervase Maxwell; Wilson, Jamie R; Kosowski, Lawrence W; Robinson, Charles

    2014-01-07

    A method and apparatus for producing heat used in a synthesis gas production is provided. The disclosed method and apparatus include a plurality of tubular oxygen transport membrane elements adapted to separate oxygen from an oxygen containing stream contacting the retentate side of the membrane elements. The permeated oxygen is combusted with a hydrogen containing synthesis gas stream contacting the permeate side of the tubular oxygen transport membrane elements thereby generating a reaction product stream and radiant heat. The present method and apparatus also includes at least one catalytic reactor containing a catalyst to promote the stream reforming reaction wherein the catalytic reactor is surrounded by the plurality of tubular oxygen transport membrane elements. The view factor between the catalytic reactor and the plurality of tubular oxygen transport membrane elements radiating heat to the catalytic reactor is greater than or equal to 0.5.

  19. Ceramic membranes for catalytic membrane reactors with high ionic conductivities and low expansion properties

    DOEpatents

    Mackay, Richard; Sammells, Anthony F.

    2000-01-01

    Ceramics of the composition: Ln.sub.x Sr.sub.2-x-y Ca.sub.y B.sub.z M.sub.2-z O.sub.5+.delta. where Ln is an element selected from the fblock lanthanide elements and yttrium or mixtures thereof; B is an element selected from Al, Ga, In or mixtures thereof; M is a d-block transition element of mixtures thereof; 0.01.ltoreq.x.ltoreq.1.0; 0.01.ltoreq.y.ltoreq.0.7; 0.01.ltoreq.z.ltoreq.1.0 and .delta. is a number that varies to maintain charge neutrality are provided. These ceramics are useful in ceramic membranes and exhibit high ionic conductivity, high chemical stability under catalytic membrane reactor conditions and low coefficients of expansion. The materials of the invention are particularly useful in producing synthesis gas.

  20. A mesoporous catalytic membrane architecture for lithium-oxygen battery systems.

    PubMed

    Ryu, Won-Hee; Gittleson, Forrest S; Schwab, Mark; Goh, Tenghooi; Taylor, André D

    2015-01-14

    Controlling the mesoscale geometric configuration of catalysts on the oxygen electrode is an effective strategy to achieve high reversibility and efficiency in Li-O2 batteries. Here we introduce a new Li-O2 cell architecture that employs a catalytic polymer-based membrane between the oxygen electrode and the separator. The catalytic membrane was prepared by immobilization of Pd nanoparticles on a polyacrylonitrile (PAN) nanofiber membrane and is adjacent to a carbon nanotube electrode loaded with Ru nanoparticles. During oxide product formation, the insulating PAN polymer scaffold restricts direct electron transfer to the Pd catalyst particles and prevents the direct blockage of Pd catalytic sites. The modified Li-O2 battery with a catalytic membrane showed a stable cyclability for 60 cycles with a capacity of 1000 mAh/g and a reduced degree of polarization (∼ 0.3 V) compared to cells without a catalytic membrane. We demonstrate the effects of a catalytic membrane on the reaction characteristics associated with morphological and structural features of the discharge products via detailed ex situ characterization.

  1. Preparation of amino-functionalized regenerated cellulose membranes with high catalytic activity.

    PubMed

    Wang, Wei; Bai, Qian; Liang, Tao; Bai, Huiyu; Liu, Xiaoya

    2017-09-01

    The modification of regenerated cellulose (RC) membranes was carried out by using silane coupling agents presenting primary and secondary amino-groups. The grafting of the amino groups onto the modified cellulose molecule was confirmed by X-ray photoelectron spectroscopies and (13)C nuclear magnetic resonance spectroscopic analyses. The crystallinity of the cellulose membranes (CM) decreased after chemical modification as indicated by the X-ray diffraction results. Moreover, a denser structure was observed at the surface and cross section of the modified membranes by SEM images. The contact angle measurements showed that the silane coupling treatment enhanced the hydrophobicity of the obtained materials. Then the catalytic properties of two types of modified membranes were studied in a batch process by evaluating their catalytic performance in a Knoevenagel condensation. The results indicated that the cellulose membrane grafted with many secondary amines exhibited a better catalytic activity compared to the one grafted only by primary amines. In addition, the compact structure of the modified membranes permitted their application in a pervaporation catalytic membrane reactor. Therefore, functional CM that prepared in this paper represented a promising material in the field of industrial catalysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Esterification of acidified oil with methanol by SPES/PES catalytic membrane.

    PubMed

    Shi, Wenying; He, Benqiao; Li, Jianxin

    2011-05-01

    A sulfonated polyethersulfone (SPES)/polyethersulfone (PES) blend catalytic membrane was prepared and used as a heterogeneous catalyst in the esterification of the acidified oil (acid value 153 mg KOH/g) with methanol for producing biodiesel. The results showed that the free fatty acids conversion reached 97.6% using SPES/PES catalytic membrane under the optimal esterification conditions. Meanwhile, the SPES/PES membrane with 20.3% degree of sulfonation showed a good catalytic stability. A pseudo-homogeneous kinetic model was established. The results indicated that the reaction rate constant increased with increasing methanol/acidified oil molar ratio, the loading of catalytic membrane and reaction temperature. The reaction order was 2 and the activation energy decreased from 74.65 to 21.07 kJ/mol with increasing catalytic membrane loading from 0 to 0.135 meq/g(oil). It implies that the esterification is not diffusively controlled but kinetically controlled. The predicted results were in good agreement with the experimental data. Copyright © 2010 Elsevier Ltd. All rights reserved.

  3. Direct catalytic decomposition of nitric oxide. Final report

    SciTech Connect

    Flytzani-Stephanopoulos, M.; Sarofim, A.F.; Zhang, Yanping

    1995-06-15

    This project investigated a suitable catalyst system for the direct NO decomposition for post-combustion NO{sub x} control. The studied process does not use a reductant, such as ammonia in the case of Selective Catalytic Reduction (SCR) process for catalytic reduction of NO{sub x} to nitrogen. This is a simplified process basically involving passing the flue gas through a catalytic converter, thus avoiding problems generally associated with the commercial SCR process, namely high operating cost, ammonia slip, and potential N{sub 2}O emissions. The main results from this research project are summarized in the following: Cu-ZSM-5 and M/Cu-ZSM-5 were synthesized by incorporating metal cations into ZSM-5 zeolite supports by optimized ion exchange procedures. It was found that (1) the catalytic activity of Cu-ZSM-5 only increased with copper loading when the Cu-ZSM-5 was prepared in an aqueous copper acetate solution with pH lower than 5.74; (2) high pH of the solution led not only to ion-exchanged Cu{sup 2+}, but also copper deposition on the zeolite surface forming inactive CuO particles as identified by STEM/EDX and XRD; (3) the sequence of metal ion exchange first, followed by copper ion exchange to synthesize M/Cu-ZSM-5, where M represents any metal ion but copper, was important for the cocation to show promotion effects; and (4) air-calcination of M-ZSM was effective in keeping M cations in the zeolite during subsequent copper ion exchange. Positive alkaline and rare earth metal cocation effects on the Cu-ZSM-5 were identified in oxygen-containing gas mixtures in the high temperature region (450--600C). Cerium ion promoted the Cu-ZSM-5 activity in the low temperature range (< 450C) in oxygen-free gas mixture, while alkaline earth and transition metal cocations improved the NO conversion to N{sub 2} in high temperature region.

  4. Final Report, "Molecular Design of Hydrocarbon Oxidation Catalytic Processes"

    SciTech Connect

    Professor Francisco Zaera

    2007-08-09

    production of small amounts of ethylene and water, most likely via the concerted decomposition or disproportionation of the adsorbed molecular species. The bulk of the 2-iodoethanol decomposes at about 150 K via an initial carbon-iodine scission to form –O(H)CH2CH2– (~80%) and 2-hydroxyethyl (~20%) intermediates. Two competing reactions are involved with the subsequent conversion of the 2-hydroxyethyl species around 160 K, a reductive elimination with surface hydrogen to yield ethanol, and a β-H elimination to surface vinyl alcohol. The –O(H)CH2CH2–, on the other hand, dehydrogenates to a –OCH2CH2– oxametallacycle species about the same temperature. Both 2-hydroxyethyl and oxametallacycle species tautomerize to acetaldehyde, around 210 K and above 250 K, respectively, and some of that acetaldehyde desorbs while the rest decomposes to hydrogen and carbon monoxide. We contend that a better understanding of the surface chemistry of oxygen-containing surfaces can lead to better selectivities in catalysis. This is arguably the most important issue in the field of catalysis in the near future, and one that impacts several technologies of interest to DOE such as the manufacturing of speciality chemicals and the control and removal of pollutants. Additional work was performed on the characterization of the chemistry of methyl and methylene adsorbed species on oxygen-treated nickel surfaces. Complex chemistry was observed involving not only hydrogenation and dehydrogenation steps, but also C-C couplings and methylene insertions to produce heavier hydrocarbons, and oxygen insertion reactions that yield oxygenates. Finally, a dual titration technique employing xenon and a chemically sensitive probe was developed to identify minority catalytic sites on oxide surfaces. In the case of oxygen-treated Ni(110) single crystals, it was found that both hydrogen transfer with adsorbed water or ammonia and certain hydrocarbon hydrogenation reactions take place at the end of the

  5. Catalytic membranes for CO oxidation in fuel cells

    DOEpatents

    Sandi-Tapia, Giselle; Carrado Gregar, Kathleen; Kizilel, Riza

    2010-06-08

    A hydrogen permeable membrane, which includes a polymer stable at temperatures of about 200 C having clay impregnated with Pt or Au or Ru or Pd particles or mixtures thereof with average diameters of less than about 10 nanometers (nms) is disclosed. The membranes are useful in fuel cells or any device which requires hydrogen to be separated from carbon monoxide.

  6. Membrane Guanylate Cyclase catalytic Subdomain: Structure and Linkage with Calcium Sensors and Bicarbonate.

    PubMed

    Ravichandran, Sarangan; Duda, Teresa; Pertzev, Alexandre; Sharma, Rameshwar K

    2017-01-01

    Membrane guanylate cyclase (MGC) is a ubiquitous multi-switching cyclic GMP generating signaling machine linked with countless physiological processes. In mammals it is encoded by seven distinct homologous genes. It is a single transmembrane spanning multi-modular protein; composed of integrated blocks and existing in homo-dimeric form. Its core catalytic domain (CCD) module is a common transduction center where all incoming signals are translated into the production of cyclic GMP, a cellular signal second messenger. Crystal structure of the MGC's CCD does not exist and its precise identity is ill-defined. Here, we define it at a sub-molecular level for the phototransduction-linked MGC, the rod outer segment guanylate cyclase type 1, ROS-GC1. (1) The CCD is a conserved 145-residue structural unit, represented by the segment V(820)-P(964). (2) It exists as a homo-dimer and contains seven conserved catalytic elements (CEs) wedged into seven conserved motifs. (3) It also contains a conserved 21-residue neurocalcin δ-modulated structural domain, V(836)-L(857). (4) Site-directed mutagenesis documents that each of the seven CEs governs the cyclase's catalytic activity. (5) In contrast to the soluble and the bacterium MGC which use Mn(2+)-GTP substrate for catalysis, MGC CCD uses the natural Mg(2+)-GTP substrate. (6) Strikingly, the MGC CCD requires anchoring by the Transmembrane Domain (TMD) to exhibit its major (∼92%) catalytic activity; in isolated form the activity is only marginal. This feature is not linked with any unique sequence of the TMD; there is minimal conservation in TMD. Finally, (7) the seven CEs control each of four phototransduction pathways- -two Ca(2+)-sensor GCAPs-, one Ca(2+)-sensor, S100B-, and one bicarbonate-modulated. The findings disclose that the CCD of ROS-GC1 has built-in regulatory elements that control its signal translational activity. Due to conservation of these regulatory elements, it is proposed that these elements also control the

  7. Membrane Guanylate Cyclase catalytic Subdomain: Structure and Linkage with Calcium Sensors and Bicarbonate

    PubMed Central

    Ravichandran, Sarangan; Duda, Teresa; Pertzev, Alexandre; Sharma, Rameshwar K.

    2017-01-01

    Membrane guanylate cyclase (MGC) is a ubiquitous multi-switching cyclic GMP generating signaling machine linked with countless physiological processes. In mammals it is encoded by seven distinct homologous genes. It is a single transmembrane spanning multi-modular protein; composed of integrated blocks and existing in homo-dimeric form. Its core catalytic domain (CCD) module is a common transduction center where all incoming signals are translated into the production of cyclic GMP, a cellular signal second messenger. Crystal structure of the MGC’s CCD does not exist and its precise identity is ill-defined. Here, we define it at a sub-molecular level for the phototransduction-linked MGC, the rod outer segment guanylate cyclase type 1, ROS-GC1. (1) The CCD is a conserved 145-residue structural unit, represented by the segment V820-P964. (2) It exists as a homo-dimer and contains seven conserved catalytic elements (CEs) wedged into seven conserved motifs. (3) It also contains a conserved 21-residue neurocalcin δ-modulated structural domain, V836-L857. (4) Site-directed mutagenesis documents that each of the seven CEs governs the cyclase’s catalytic activity. (5) In contrast to the soluble and the bacterium MGC which use Mn2+-GTP substrate for catalysis, MGC CCD uses the natural Mg2+-GTP substrate. (6) Strikingly, the MGC CCD requires anchoring by the Transmembrane Domain (TMD) to exhibit its major (∼92%) catalytic activity; in isolated form the activity is only marginal. This feature is not linked with any unique sequence of the TMD; there is minimal conservation in TMD. Finally, (7) the seven CEs control each of four phototransduction pathways- -two Ca2+-sensor GCAPs-, one Ca2+-sensor, S100B-, and one bicarbonate-modulated. The findings disclose that the CCD of ROS-GC1 has built-in regulatory elements that control its signal translational activity. Due to conservation of these regulatory elements, it is proposed that these elements also control the

  8. Development of hollow-fiber catalytic-membrane reactors for high-temperature gas cleanup

    SciTech Connect

    Ma, Yi H.; Moser, M.R.; Pien, S.M.

    1992-12-01

    The project consist of the following main activities: (1) Design of catalytic hollow fiber membrane reactors. Single and multiple hollow-fiber membranes were studied in reactor/permeation cells made from stainless steel or quartz tubes. Modification of the hollow fiber membrane with catalysts was performed by aqueous impregnation, vapor deposition, and utilization of packed-bed reactors. (2) Investigation of gas separations and catalytic reactions in membrane reactors. Permeation of pure gases and gas mixtures was studied as a function of temperature. Pure component catalytic studies on the decomposition of H{sub 2}S was typically studied using 10% H{sub 2}S diluted in He. The H{sub 2}S and H{sub 2} concentrations were measured in both the tube and shell sides of the membrane reactor to determine the degree of chemical equilibrium shift. (3) Process development of the cleanup system using a simulated gas stream with a composition similar to that from an IGCC system. Catalytic studies using the IGCC gas composition will be performed according to the procedure used in the H{sub 2}S experiments. The conditions for optimum conversion in a gas mixture will be investigated.

  9. Development of hollow-fiber catalytic-membrane reactors for high-temperature gas cleanup

    SciTech Connect

    Ma, Yi H.; Moser, M.R.; Pien, S.M.

    1992-01-01

    The project consist of the following main activities: (1) Design of catalytic hollow fiber membrane reactors. Single and multiple hollow-fiber membranes were studied in reactor/permeation cells made from stainless steel or quartz tubes. Modification of the hollow fiber membrane with catalysts was performed by aqueous impregnation, vapor deposition, and utilization of packed-bed reactors. (2) Investigation of gas separations and catalytic reactions in membrane reactors. Permeation of pure gases and gas mixtures was studied as a function of temperature. Pure component catalytic studies on the decomposition of H[sub 2]S was typically studied using 10% H[sub 2]S diluted in He. The H[sub 2]S and H[sub 2] concentrations were measured in both the tube and shell sides of the membrane reactor to determine the degree of chemical equilibrium shift. (3) Process development of the cleanup system using a simulated gas stream with a composition similar to that from an IGCC system. Catalytic studies using the IGCC gas composition will be performed according to the procedure used in the H[sub 2]S experiments. The conditions for optimum conversion in a gas mixture will be investigated.

  10. Catalytic photoinduced electron transport across a lipid bilayer mediated by a membrane-soluble electron relay.

    PubMed

    Limburg, B; Bouwman, E; Bonnet, S

    2015-12-14

    Unidirectional photocatalytic electron transfer from a hydrophilic electron donor encapsulated in the interior of a liposome, to a hydrophilic electron acceptor on the other side of the membrane, has been achieved using the simple membrane-soluble electron relay 1-methoxy-N-methylphenazinium (MMP(+)). The total amount of photoproduct (>140 nmol) exceeds the number of moles of MMP(+) present (125 nmol), thus showing that the transport of electrons is catalytic.

  11. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    SciTech Connect

    Vicic, David A.

    2014-05-01

    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  12. Mn oxide coated catalytic membranes for a hybrid ozonation-membrane filtration: comparison of Ti, Fe and Mn oxide coated membranes for water quality.

    PubMed

    Byun, S; Davies, S H; Alpatova, A L; Corneal, L M; Baumann, M J; Tarabara, V V; Masten, S J

    2011-01-01

    In this study the performance of catalytic membranes in a hybrid ozonation-ceramic membrane filtration system was investigated. The catalytic membranes were produced by coating commercial ceramic ultrafiltration membranes with manganese or iron oxide nanoparticles using a layer-by-layer self-assembly technique. A commercial membrane with a titanium oxide filtration layer was also evaluated. The performance of the coated and uncoated membranes was evaluated using water from a borderline eutrophic lake. The permeate flux and removal of the organic matter was found to depend on the type of the metal oxide present on the membrane surface. The performance of the manganese oxide coated membrane was superior to that of the other membranes tested, showing the fastest recovery in permeate flux when ozone was applied and the greatest reduction in the total organic carbon (TOC) in the permeate. The removal of trihalomethanes (THMs) and haloacetic acids (HAAs) precursors using the membrane coated 20 times with manganese oxide nanoparticles was significantly better than that for the membranes coated with 30 or 40 times with manganese oxide nanoparticles or 40 times with iron oxide nanoparticles. Copyright © 2010 Elsevier Ltd. All rights reserved.

  13. One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters.

    PubMed

    Kim, Seok-Jhin; Tan, Shuai; Taborga Claure, Micaela; Briones Gil, Laura; More, Karren L; Liu, Yujun; Moore, Jason S; Dixit, Ravindra S; Pendergast, John G; Sholl, David S; Jones, Christopher W; Nair, Sankar

    2016-09-21

    Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

  14. Long life catalytic membrane reactors for spontaneous conversion of natural gas to synthesis gas

    SciTech Connect

    Schwartz, M., White, J., Deych, S., Millard, J., Myers, M., Sammells, A.

    1997-10-01

    This program is focusing on the development of mixed ionic and electronic conducting materials based on the brown millerite structure for use in catalytic membrane reactors (CMRs). These CMRs are being evaluated for promoting the spontaneous and highly selective oxidative reforming of carbon dioxide / natural gas mixtures to synthesis gas.

  15. Non-catalytic steam hydrolysis of fats. Final report

    SciTech Connect

    Deibert, M.C.

    1992-08-28

    Hydrolysis of fats and oils produces fatty acid and glycerol. The catalyzed, liquid phase Colgate-Emry process, state-of-the-art, produces impure products that require extensive energy investment for their purification to commercial grade. Non-catalytic steam hydrolysis may produce products more easily purified. A bench-scale hydrolyzer was designed and constructed to contact descending liquid fat or oil with rising superheated steam. Each of the five stages in the reactor was designed similar to a distillation column stage to promote intimate liquid-gas contact. Degree of hydrolysis achieved in continuous tests using tallow feed were 15% at 280C and 35% at 300C at a tallow-to-steam mass feed ratio of 4.2. At a feed ratio of 9.2, the degree of hydrolysis was 21% at 300C. Decomposition was strongly evident at 325C but not at lower temperatures. Soybean oil rapidly polymerized under reaction conditions. Batch tests at 320C produced degrees of hydrolyses of between 44% and 63% using tallow and palm oil feeds. Over 95% fatty acids were present in a clean, readily separated organic portion of the overhead product from most tests. The test reactor had serious hydraulic resistance to liquid down-flow which limited operation to very long liquid residence times. These times are in excess of those that tallow and palm oil are stable at the reaction temperature. Little glycerol and extensive light organics were produced indicating that unexplained competing reactions to hydrolysis occurred in the experimental system. Further tests using an improved reactor will be required.

  16. Modification of tubular ceramic membranes with carbon nanotubes using catalytic chemical vapor deposition.

    PubMed

    Tran, Duc Trung; Thieffry, Guillemette; Jacob, Matthieu; Batiot-Dupeyrat, Catherine; Teychene, Benoit

    2015-01-01

    In this study, carbon nanotubes (CNTs) were successfully grown on tubular ceramic membranes using the catalytic chemical vapor deposition (CCVD) method. CNTs were synthesized at 650°C for 3-6 h under a 120 mL min(-1) flow of C2H6 on ceramic membranes impregnated with iron salt. The synthesis procedure was beforehand optimized in terms of catalyst amount, impregnation duration and reaction temperature, using small pieces of tubular ceramic membranes. The yield, size and structure of the CNTs produced were characterized using thermogravimetric analysis and microscopic imaging techniques. Afterwards, preliminary filtration tests with alginate and phenol were performed on two modified tubular membranes. The results indicate that the addition of CNTs on the membrane material increased the permeability of ceramic membrane and its ability to reject alginate and adsorb phenol, yet decreased its fouling resistance.

  17. Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection.

    PubMed

    Sergeyeva, T A; Slinchenko, O A; Gorbach, L A; Matyushov, V F; Brovko, O O; Piletsky, S A; Sergeeva, L M; Elska, G V

    2010-02-05

    Portable biomimetic sensor devices for the express control of phenols content in water were developed. The synthetic binding sites mimicking active site of the enzyme tyrosinase were formed in the structure of free-standing molecularly imprinted polymer membranes. Molecularly imprinted polymer membranes with the catalytic activity were obtained by co-polymerization of the complex Cu(II)-catechol-urocanic acid ethyl ester with (tri)ethyleneglycoldimethacrylate, and oligourethaneacrylate. Addition of the elastic component oligourethaneacrylate provided formation of the highly cross-linked polymer with the catalytic activity in a form of thin, flexible, and mechanically stable membrane. High accessibility of the artificial catalytic sites for the interaction with the analyzed phenol molecules was achieved due to addition of linear polymer (polyethyleneglycol Mw 20,000) to the initial monomer mixture before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) were formed. The cross-linked component of the semi-IPN was represented by the highly cross-linked catalytic molecularly imprinted polymer, while the linear one was represented by polyethyleneglycol Mw 20,000. Extraction of the linear polymer from the fully formed semi-IPN resulted in formation of large pores in the membranes' structure. Concentration of phenols in the analyzed samples was detected using universal portable device oxymeter with the oxygen electrode in a close contact with the catalytic molecularly imprinted polymer membrane as a transducer. The detection limit of phenols detection using the developed sensor system based on polymers-biomimics with the optimized composition comprised 0.063 mM, while the linear range of the sensor comprised 0.063-1 mM. The working characteristics of the portable sensor devices were investigated. Storage stability of sensor systems at room temperature comprised 12 months (87%). As compared to traditional methods of phenols

  18. Production of an ion-exchange membrane-catalytic electrode bonded material for electrolytic cells

    NASA Technical Reports Server (NTRS)

    Takenaka, H.; Torikai, E.

    1986-01-01

    A good bond is achieved by placing a metal salt in solution on one side of a membrane and a reducing agent on the other side so that the reducing agent penetrates the membrane and reduces the metal. Thus, a solution containing Pt, Rh, etc., is placed on one side of the membrane and a reducing agent such as NaBH, is placed on the other side. The bonded metal layer obtained is superior in catalytic activity and is suitable as an electrode in a cell such as for solid polymer electrolyte water electrolysis.

  19. Catalytic partial oxidation coupled with membrane purification to improve resource and energy efficiency in syngas production.

    PubMed

    Iaquaniello, G; Salladini, A; Palo, E; Centi, G

    2015-02-01

    Catalytic partial oxidation coupled with membrane purification is a new process scheme to improve resource and energy efficiency in a well-established and large scale-process like syngas production. Experimentation in a semi industrial-scale unit (20 Nm(3)  h(-1) production) shows that a novel syngas production scheme based on a pre-reforming stage followed by a membrane for hydrogen separation, a catalytic partial oxidation step, and a further step of syngas purification by membrane allows the oxygen-to-carbon ratio to be decreased while maintaining levels of feed conversion. For a total feed conversion of 40 %, for example, the integrated novel architecture reduces oxygen consumption by over 50 %, with thus a corresponding improvement in resource efficiency and an improved energy efficiency and economics, these factors largely depending on the air separation stage used to produce pure oxygen.

  20. Block copolymer hollow fiber membranes with catalytic activity and pH-response.

    PubMed

    Hilke, Roland; Pradeep, Neelakanda; Madhavan, Poornima; Vainio, Ulla; Behzad, Ali Reza; Sougrat, Rachid; Nunes, Suzana P; Peinemann, Klaus-Viktor

    2013-08-14

    We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes.

  1. Development of hollow fiber catalytic membrane reactors for high temperature gas cleanup

    SciTech Connect

    Ma, Y.H.; Moser, W.R.; Pien, S.; Shelekhin, A.B.

    1994-10-01

    The technology employed in the Integrated Gasification Combined Cycle (IGCC) permits burning coals with a wide range of sulfur concentrations. Emissions from the process should be reduced by an order of magnitude below stringent federal air quality regulations for coal-fired plants. The maximum thermal efficiency of this type of process can be achieved by removing sulfur and particulates from the high temperature gas. The objective of this project was to develop economically and technically viable catalytic membrane reactors for high temperature, high pressure gaseous contaminant control in IGCC systems. These catalytic membrane reactors were used to decompose H{sub 2}S and separate the reaction products. The reactors were designed to operate in the hostile process environment of the IGCC systems, and at temperatures ranging from 500 to 1,000. Feasibility of the membrane reactor process for decomposition of hydrogen sulfide was demonstrated; permeability and selectivity of molecular-sieve and Vycor glass membranes were studied at temperatures up to 1,000 C; experimental study of hydrogen sulfide in the membrane reactor was completed; and a generalized mathematical model was developed for the simulation of the high temperature membrane reactor.

  2. A hybrid process combining homogeneous catalytic ozonation and membrane distillation for wastewater treatment.

    PubMed

    Zhang, Yong; Zhao, Peng; Li, Jie; Hou, Deyin; Wang, Jun; Liu, Huijuan

    2016-10-01

    A novel catalytic ozonation membrane reactor (COMR) coupling homogeneous catalytic ozonation and direct contact membrane distillation (DCMD) was developed for refractory saline organic pollutant treatment from wastewater. An ozonation process took place in the reactor to degrade organic pollutants, whilst the DCMD process was used to recover ionic catalysts and produce clean water. It was found that 98.6% total organic carbon (TOC) and almost 100% salt were removed and almost 100% metal ion catalyst was recovered. TOC in the permeate water was less than 16 mg/L after 5 h operation, which was considered satisfactory as the TOC in the potassium hydrogen phthalate (KHP) feed water was as high as 1000 mg/L. Meanwhile, the membrane distillation flux in the COMR process was 49.8% higher than that in DCMD process alone after 60 h operation. Further, scanning electron microscope images showed less amount and smaller size of contaminants on the membrane surface, which indicated the mitigation of membrane fouling. The tensile strength and FT-IR spectra tests did not reveal obvious changes for the polyvinylidene fluoride membrane after 60 h operation, which indicated the good durability. This novel COMR hybrid process exhibited promising application prospects for saline organic wastewater treatment.

  3. A self-catalytic mixed-conducting membrane reactor for effective production of hydrogen from methane

    NASA Astrophysics Data System (ADS)

    Dong, Xueliang; Liu, Zhengkun; Jin, Wanqin; Xu, Nanping

    A supported mixed-conducting LNCO membrane with a pore-gradient structure LNO support was successfully prepared via a dry pressing and co-sintering route. The match of sintering behaviors between membrane and support was realized by the preparation of an ABB‧B‧‧B‧BA-type membrane. A scanning electron microscopy (SEM) test demonstrated that the surface of the supported membrane was dense and crack-free and the pore-gradient structure of the support can be observed clearly. The oxygen flux of the supported membrane was about 5.6 times that of the symmetric LNCO membrane. A self-catalytic mixed-conducting membrane reactor was constructed using the prepared membrane for hydrogen production from methane. It was found that this membrane reactor exhibited high performance and good stability for hydrogen production. At 1123 K, the CH 4 conversion, hydrogen selectivity and hydrogen production remained at about 60%, 89% and 8.0 ml(STP) cm -2 min -1, respectively, for more than 120 h.

  4. [Nitric Oxide Removal with a Fe-TiO₂/PSF Hybrid Catalytic Membrane Bioreactor].

    PubMed

    Li, Bao-ren; Chen, Zhou-yang; Wang, Jian-bin; Zhang, Zai-li; Fan, Qing-juan; Wei, Zai-shan

    2016-03-15

    The Fe-doped titanium dioxide (Fe-TiO₂) was prepared by the sol-gel method and was loaded on polysulfone (PSF) hollow fiber membrane. A novel Fe-TiO₂/PSF hybrid catalytic membrane biofilm reactor (HCMBfR) was investigated for nitric oxide removal, to further improve the elimination capacity. HCMBfR exhibited a good stability in the 180-day operation period, the NO removal efficiency was up to 93.2% and the maximum elimination capacity reached 167.1 g · (m³ · h)⁻1. The additional use of the biofilm to wet Fe-TiO₂/PSF membrane catalysis reactor led to the enhancement of NO removal efficiency from 59. 5% to 66% . The NO removal efficiency in the intimate coupling of Fe-TiO₂/PSF hybrid catalytic membrane and biofilm reactor ( HCMBfR) increased from 1.4% to 13% as compared to that of the membrane biofilm reactor (MBfR) only. The optimal illumination intensity, gas residence time, pH and nC/nN were 670 lx, 9 a, 6.8-7.2 and 3.7, respectively.

  5. Conversion of elemental mercury with a novel membrane catalytic system at low temperature.

    PubMed

    Guo, Yongfu; Yan, Naiqiang; Yang, Shijian; Liu, Ping; Wang, Juan; Qu, Zan; Jia, Jinping

    2012-04-30

    A unique assembly, which integrated membrane delivery for oxidants with catalytic oxidation (MDCOs), was employed to convert elemental mercury (Hg(0)) to its oxidized form at low temperature (around 150 °C). MnO(x) was used as the main catalytic component in MDCOs with Mo and/or Ru to improve the catalytic activity. The MDCOs was proved to be very effective for the conversion of Hg(0) compared with the traditional catalytic oxidation mode (TCO). The analysis of speciation for Hg after catalytic oxidation showed that there was mainly mercury (II) chloride. The addition of transition metals of Mo and Ru obviously improved the conversion of Hg(0) to Hg(2+) and enhanced the activity of the MDCOs at low temperature, and the conversion efficiency of Hg(0) reached 95% with Mo-Ru-Mn catalyst and 8 ppmv HCl. The inhibition of SO(2) to Hg(0) conversion in the MDCOs was insignificant. The Hg(0) removal exceeded 80% even if the concentration of SO(2) reached 1000 ppmv. The results also indicated that the Deacon reaction with the yield of Cl(2) were significantly improved after modified, and MDCOs with Mo-Ru-Mn catalyst can work efficiently at low temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Ag Nanoparticle/Polydopamine-Coated Inverse Opals as Highly Efficient Catalytic Membranes.

    PubMed

    Choi, Gwan H; Rhee, Do Kyung; Park, A Reum; Oh, Min Jun; Hong, Sunghwan; Richardson, Joseph J; Guo, Junling; Caruso, Frank; Yoo, Pil J

    2016-02-10

    Polymeric three-dimensional inverse-opal (IO) structures provide unique structural properties useful for various applications ranging from optics to separation technologies. Despite vast needs for IO functionalization to impart additional chemical properties, this task has been seriously challenged by the intrinsic limitation of polymeric porous materials that do not allow for the easy penetration of waterborne moieties or precursors. To overcome this restriction, we present a robust and straightforward method of employing a dipping-based surface modification with polydopamine (PDA) inside the IO structures, and demonstrate their application to catalytic membranes via synthetic incorporation of Ag nanoparticles. The PDA coating offers simultaneous advantages of achieving the improved hydrophilicity required for the facilitated infiltration of aqueous precursors and successful creation of nucleation sites for a reduction of growth of the Ag nanoparticles. The resulting Ag nanoparticle-incorporated IO structures are utilized as catalytic membranes for the reduction of 4-nitrophenol to its amino derivatives in the presence of NaBH4. Synergistically combined characteristics of high reactivity of Ag nanoparticles along with a greatly enhanced internal surface area of IO structures enable the implementation of remarkably improved catalytic performance, exhibiting a good conversion efficiency greater than 99% while minimizing loss in the membrane permeability.

  7. Hollow microgel based ultrathin thermoresponsive membranes for separation, synthesis, and catalytic applications.

    PubMed

    Tripathi, Bijay Prakash; Dubey, Nidhi Chandrama; Stamm, Manfred

    2014-10-22

    Thermoresponsive core-shell microgels with degradable core are synthesized via surfactant based free radical polymerization using N,N'-(1,2-dihydroxy-ethylene)bis(acrylamide) (DHEA) as a cross-linker for core preparation. The 1,2-glycol bond present in DHEA is susceptible to NaIO4 solution, and thus, the structure can be cleaved off resulting in hollow microgel. Ultrathin membranes are prepared by suction filtration of a dilute suspension of core-shell microgels over a sacrificial layer of Cd(OH)2 nanostrand coated on track etched membrane. After removal of the degraded cores from microgels, the membranes are cross-linked with glutaraldehyde and the nanostrands are removed by passing a 10 mM HCl solution. The prepared membranes are thoroughly characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), dynamic light scattering (DLS), and dynamic contact angle for morphology, thermoresponsive, and hydrophilic properties, respectively. The prepared membranes showed thermoresponsive permeation behavior and remarkable separation performance for low molecular weight dyes and lysozyme protein. These membranes are also used to synthesize gold nanoparticles and immobilize lactate dehydrogenase enzyme for catalytic and biocatalytic application. The results for water permeation, solute rejection, and ability to immobilize gold nanoparticles and enzymes showed its wide range of applicability. Furthermore, the synthesis of hollow microgel is simple and environmentally friendly, and the membrane preparation is easy, scalable, and other microgel systems can also be used. These responsive membranes constitute a significant contribution to advanced separation technology.

  8. Metal nanoparticles in catalytic polymer membranes and ion-exchange systems for advanced purification of water from molecular oxygen

    NASA Astrophysics Data System (ADS)

    Volkov, V. V.; Kravchenko, T. A.; Roldughin, Vyacheslav I.

    2013-05-01

    Methods of synthesis of metal nanoparticles and metal/polymer nanocomposites including ion-exchange materials are considered. The effect of the composition and size of nanoparticles on their catalytic activity is analyzed. Attention is focused on the composites used in catalytic processes, namely, catalytic membranes and ion-exchange systems. The problems associated with the removal of dissolved oxygen from water by means of such composites are discussed. The bibliography includes 225 references.

  9. Conversion of elemental mercury with a novel membrane delivery catalytic oxidation system (MDCOs).

    PubMed

    Guo, Yongfu; Yan, Naiqiang; Yang, Shijian; Qu, Zan; Wu, Zhongbiao; Liu, Yue; Liu, Ping; Jia, Jinping

    2011-01-15

    In order to overcome the shortcomings of the traditional catalytic oxidation (TCO) mode for the conversion of the trace level of elemental mercury (Hg(0)) in flue gas, we put forward a novel and unique assembly that integrated membrane delivery with catalytic oxidation systems (MDCOs), which combined the controlled delivery of oxidants with the catalytic oxidation of Hg(0). The results show that the demanded HCl for Hg(0) conversion in the MDCOs was less than 5% of that in the TCO mode, and over 90% of Hg(0) removal efficiency can be obtained in the MDCOs with less than 0.5 mg m(-3) of HCl escaped. Meanwhile, the inhibition of SO(2) to Hg(0) catalytic conversion in the MDCOs was also less significant than in the TCO. The MDCOs have high retainability for HCl, which is quite favorable to Hg(0) conversion and HCl utilization. The reaction mechanism on mercury conversion in the MDCOs is discussed. The MDCOs appear to be a promising method for emission control of elemental mercury.

  10. The catalytic function of cytochrome P450 is entwined with its membrane-bound nature.

    PubMed

    Barnaba, Carlo; Gentry, Katherine; Sumangala, Nirupama; Ramamoorthy, Ayyalusamy

    2017-01-01

    Cytochrome P450, a family of monooxygenase enzymes, is organized as a catalytic metabolon, which requires enzymatic partners as well as environmental factors that tune its complex dynamic. P450 and its reducing counterparts-cytochrome P450-reductase and cytochrome b 5 -are membrane-bound proteins located in the cytosolic side of the endoplasmic reticulum. They are believed to dynamically associate to form functional complexes. Increasing experimental evidence signifies the role(s) played by both protein-protein and protein-lipid interactions in P450 catalytic function and efficiency. However, the biophysical challenges posed by their membrane-bound nature have severely limited high-resolution understanding of the molecular interfaces of these interactions. In this article, we provide an overview of the current knowledge on cytochrome P450, highlighting the environmental factors that are entwined with its metabolic function. Recent advances in structural biophysics are also discussed, setting up the bases for a new paradigm in the study of this important class of membrane-bound enzymes.

  11. Catalytic membranes prepared using layer-by-layer adsorption of polyelectrolyte/metal nanoparticle films in porous supports.

    PubMed

    Dotzauer, David M; Dai, Jinhua; Sun, Lei; Bruening, Merlin L

    2006-10-01

    Layer-by-layer adsorption of polyelectrolytes and gold nanoparticles within porous supports provides a convenient method for forming catalytic membranes. The polyelectrolyte film effectively immobilizes the gold nanoparticles without inhibiting access to catalytic sites, as shown by the similar rate constants for nanoparticle-catalyzed 4-nitrophenol reduction in solution and in membranes. Modified alumina membranes reduce >99% of 0.4 mM 4-nitrophenol at linear flow rates of 0.98 cm/s, and the modification process is also applicable to track-etched polycarbonate supports.

  12. Improving carbon tolerance of Ni-YSZ catalytic porous membrane by palladium addition for low temperature steam methane reforming

    NASA Astrophysics Data System (ADS)

    Lee, Sang Moon; Won, Jong Min; Kim, Geo Jong; Lee, Seung Hyun; Kim, Sung Su; Hong, Sung Chang

    2017-10-01

    Palladium was added on the Ni-YSZ catalytic porous membrane by wet impregnation and electroless plating methods. Its surface morphology characteristics and carbon deposition properties for the low temperature steam methane reforming were investigated. The addition of palladium could obviously be enhanced the catalytic activity as well as carbon tolerance of the Ni-YSZ porous membrane. The porous membranes were evaluated by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR), CH4 temperature-programmed reduction (CH4-TPR), and O2 temperature-programmed oxidation (O2-TPO). It was found that the Pd-Ni-YSZ catalytic porous membrane showed the superior stability as well as the deposition of carbon on the surface during carbon dissociation adsorption at 650 °C was also suppressed.

  13. Methane steam reforming analysis in a palladium-based catalytic membrane reactor

    SciTech Connect

    Barbieri, G.; Violante, V.; Maio, F.P. di; Criscuoli, A.; Drioli, E. |

    1997-08-01

    The methane steam reforming in a catalytic membrane reactor has been studied. A previous theoretical study of this reaction has been carried out. In the model a global kinetic rate as a function of three reactions over nickel catalyst as proposed by Xu and Froment has been considered. It has been shown that the counterflow configuration has, at high temperature (500 C), a marginal advantage on parallel flow and, also, that the space velocity cannot be considered a design variable for membrane reactors. A laboratory plant was realized utilizing membranes of Pd and Pd/Ag supported on Al{sub 2}O{sub 3}. The Pd membranes utilized have been prepared using the co-condensation technique and the electroless plating method. A comparison of the overall membrane performance has also been carried out. The experiments were aimed to study the effects of several parameters such as temperature, feed flow rate, and feed molar ratio on the methane conversion. The experimental results have been compared with the data predicted by the previously developed theoretical model.

  14. Instantaneous Click Chemistry by a Copper-Containing Polymeric-Membrane-Installed Microflow Catalytic Reactor.

    PubMed

    Yamada, Yoichi M A; Ohno, Aya; Sato, Takuma; Uozumi, Yasuhiro

    2015-11-23

    The copper(I)-catalyzed Huisgen cycloaddition (azide-alkyne cycloaddition) is an important reaction in click chemistry that ideally proceeds instantaneously. An instantaneous Huisgen cycloaddition has been developed that uses a novel catalytic dinuclear copper complex-containing polymeric membrane-installed microflow device. A polymeric membranous copper catalyst was prepared from poly(4-vinylpyridine), copper(II) sulfate, sodium chloride, and sodium ascorbate at the interface of two laminar flows inside microchannels. Elucidation of the structure by XANES, EXAFS, and elemental analysis, as well as second-order Møller-Plesset perturbation theory (MP2) calculations and density functional theory (DFT) calculations assigned the local structure near Cu as a μ-chloro dinuclear Cu(I) complex. The microflow device promotes the instantaneous click reaction of a variety of alkynes and organic azides to afford the corresponding triazoles in quantitative yield.

  15. Simple fabrication of a Pd-P film on a polymer membrane and its catalytic applications.

    PubMed

    Byeon, Jeong Hoon; Kim, Young-Woo

    2011-08-01

    Composites were prepared by a surface activation by aerosol deposition of Pd nanoparticles (Pd nano seeds) on a poly(tetrafluoroethylene) membrane and subsequent Pd-P film formation by electroless deposition. Activation of the membrane processed by an ambient Pd spark discharge and subsequent fixation of the spark produced Pd nano seeds. Characterizations for electroless Pd-P films indicated that P entered into the crystal lattice of Pd and formed an alloy. The fabricated composites were applied to catalytic applications of formic acid oxidation (FAO) and toluene conversion (TC). The composite catalysts from the simple activation had more stable performances of FAO and TC than those from the conventional Sn-Pd activation, and their better performances might have originated from better purity due to the simple activation that only introduced pure Pd nano seeds.

  16. Catalytic Membrane Reactor Immobilized with Alloy Nanoparticle-Loaded Protein Fibrils for Continuous Reduction of 4-Nitrophenol.

    PubMed

    Huang, Renliang; Zhu, Hongxiu; Su, Rongxin; Qi, Wei; He, Zhimin

    2016-10-18

    A catalytic membrane reactor, which contains a membrane matrix and a catalytic film of alloy nanoparticle-loaded β-lactoglobulin fibrils (NPs@β-LGF), was developed for the continuous-flow reduction of 4-nitrophenol (4-NP). The Cu-Ag and Cu-Ag-Au alloy NPs were synthesized using β-LGF as a scaffold and stabilizing agent. In this process, the Cu nanoclusters were formed in the initial stage and were able to promote the synthesis of Ag(0), which acts as a reducing agent for the rapid formation of Au(0). Furthermore, a catalytic membrane reactor was constructed by depositing the NPs@β-LGFs on a membrane matrix. The catalytic activity of the Cu-Ag-Au alloy NPs was higher than that of the Cu-Ag alloy NPs, using the reduction of 4-NP to 4-AP as a model reaction. The observed rate constant in the continuous-flow system is also higher than that in the batch system. In addition, these catalytic membrane reactors had good operating stability and antibacterial activity.

  17. Comparative catalytic activity of PET track-etched membranes with embedded silver and gold nanotubes

    NASA Astrophysics Data System (ADS)

    Mashentseva, Anastassiya; Borgekov, Daryn; Kislitsin, Sergey; Zdorovets, Maxim; Migunova, Anastassiya

    2015-12-01

    Irradiated by heavy ions nanoporous polyethylene terephthalate track-etched membranes (PET TeMs) after +15Kr84 ions bombardment (1.75 MeV/nucl with the ion fluency of 1 × 109 cm-2) and sequential etching was applied in this research as a template for development of composites with catalytically enriched properties. A highly ordered silver and gold nanotubes arrays were embedded in 100 nm pores of PET TeMs via electroless deposition technique at 4 °C during 1 h. All ;as-prepared; composites were examined for catalytic activity using reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride as a common reaction to test metallic nanostructures catalysts. The effect of temperature on the catalytic activity was investigated in range of 292-313 K and activation energy were calculated. Kapp of Ag/PET composites linearly increase with an increase of the temperature thus normal Arrhenius behavior have been seen and the activation energy was calculated to be 42.13 kJ/mol. Au/PET composites exhibit not only more powerful catalytic activity but also non-linear dependence of rate constant from temperature. Kapp increased with increasing temperature throughout the 292-308 K temperature range; the reaction had an activation energy 65.32 kJ/mol. In range 311-313 K rate constant dramatically decreased and the apparent activation energy at this temperature rang was -91.44 kJ/mol due some structural changes, i.e. agglomeration of Au nanoparticles on the surface of composite.

  18. Synthesis and Catalytic Performance of Hierarchically Porous MIL-100(Fe)@polyHIPE Hybrid Membranes.

    PubMed

    Kovačič, Sebastijan; Mazaj, Matjaž; Ješelnik, Marjan; Pahovnik, David; Žagar, Ema; Slugovc, Christian; Logar, Nataša Zabukovec

    2015-09-01

    Metal-organic frameworks (MOFs) nanoparticles in combination with a nonionic surfactant (Pluronic L-121) are used to stabilize dicyclopentadiene (DCPD)-in-water high internal phase emulsions (HIPEs). The resulting HIPEs containing the MIL-100(Fe) nanoparticles (MIL: Materials of Institut Lavoisier) at the interface between the oil- and the water-phases are then cured, and 100 μm thick, fully open, hierarchically porous hybrid membranes are obtained. The properties of the MIL-100(Fe)@pDCPD polyHIPE membranes are characterized and it is found that up to 14 wt% of the MIL-100(Fe) nanoparticles are incorporated in the hybrid material resulting in an increase of the microporosity up to 130 m(2) g(-1). Hybrid membranes show an appealing catalytic activity in Friedel-Crafts alkylation in a batch mode as well as in a flow-through mode, thereby demonstrating the preserved accessibility of Lewis acidic sites in the MOF nanostructures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Gas separations using ceramic membranes. Final report, September 1988--February 1993

    SciTech Connect

    Lin, C.L.; Wu, J.C.S.; Gallaher, G.R.; Smith, G.W.; Flowers, D.L.; Gerdes, T.E.; Liu, P.K.T.

    1993-02-01

    This study covers a comprehensive evaluation of existing ceramic membranes for high temperature gas separations. Methodology has been established for microporous characterization stability and gas separation efficiency. A mathematical model was developed to predict gas separations with existing membranes. Silica and zeolitic modifications of existing membranes were pursued to enhance its separation efficiency. Some of which demonstrate unique separations properties. Use of the dense-silica membranes for hydrogen enrichment was identified as a promising candidate for future development. In addition, the decomposition of trace ammonia contaminant via a catalytic membrane reactor appears feasible. A further economic analysis is required to assess its commercial viability.

  20. Removal of Perchlorate from Water and Wastewater by Catalytic Hydrogen Gas Membrane Systems

    DTIC Science & Technology

    2007-01-01

    ClO2 -) and chlorate (ClO3-) appeared. The total chlorine concentration, i.e.,, the sum of all chlorine-containing species, decreased with reaction...catalytic membrane can be described by: )C(rJ dt dC d −= , Time (hr) 0 2 4 6 8 C on ce nt ra tio n (p pb ) 0 200 400 600 800 1000 ClO2 - Cl- ClO3...H H H H O O- Cl O H H H H H H ClO3- H2O H H H H H H ClO2 - HOH H2O H2O H H H H H H O Cl- 2HOH H H H H H H O Cl- O H2O H H H H H H O Cl- H H H

  1. A conceptual design of catalytic gasification fuel cell hybrid power plant with oxygen transfer membrane

    NASA Astrophysics Data System (ADS)

    Shi, Wangying; Han, Minfang

    2017-09-01

    A hybrid power generation system integrating catalytic gasification, solid oxide fuel cell (SOFC), oxygen transfer membrane (OTM) and gas turbine (GT) is established and system energy analysis is performed. In this work, the catalytic gasifier uses steam, recycled anode off-gas and pure oxygen from OTM system to gasify coal, and heated by hot cathode off-gas at the same time. A zero-dimension SOFC model is applied and verified by fitting experimental data. Thermodynamic analysis is performed to investigate the integrated system performance, and system sensitivities on anode off-gas back flow ratio, SOFC fuel utilization, temperature and pressure are discussed. Main conclusions are as follows: (1) System overall electricity efficiency reaches 60.7%(HHV) while the gasifier operates at 700 °C and SOFC at 850 °C with system pressure at 3.04 bar; (2) oxygen enriched combustion simplify the carbon-dioxide capture process, which derives CO2 of 99.2% purity, but results in a penalty of 6.7% on system electricity efficiency; (3) with SOFC fuel utilization or temperature increasing, the power output of SOFC increases while GT power output decreases, and increasing system pressure can improve both the performance of SOFC and GT.

  2. Catalytic conversion of light alkanes. Final report, January 1, 1990--October 31, 1994

    SciTech Connect

    1998-12-31

    During the course of the first three years of the Cooperative Agreement (Phase I-III), we uncovered a family of metal perhaloporphyrin complexes which had unprecedented activity for the selective air-oxidation of fight alkanes to alcohols. The reactivity of fight hydrocarbon substrates with air or oxygen was in the order: isobutane>propane>ethane>methane, in accord with their homolytic bond dissociation energies. Isobutane was so reactive that the proof-of concept stage of a process for producing tert-butyl alcohol from isobutane was begun (Phase V). It was proposed that as more active catalytic systems were developed (Phases IV, VI), propane, then ethane and finally methane oxidations will move into this stage (Phases VII through IX). As of this writing, however, the program has been terminated during the later stages of Phases V and VI so that further work is not anticipated. We made excellent progress during 1994 in generating a class of less costly new materials which have the potential for high catalytic activity. New routes were developed for replacing costly perfluorophenyl groups in the meso-position of metalloporphyrin catalysts with far less expensive and lower molecular weight perfluoromethyl groups.

  3. The final catalytic step of cytochrome p450 aromatase: a density functional theory study.

    PubMed

    Hackett, John C; Brueggemeier, Robert W; Hadad, Christopher M

    2005-04-13

    B3LYP density functional theory calculations are used to unravel the mysterious third step of aromatase catalysis. The feasibility of mechanisms in which the reduced ferrous dioxygen intermediate mediates androgen aromatization is explored and determined to be unlikely. However, proton-assisted homolysis of the peroxo hemiacetal intermediate to produce P450 compound I and the C19 gem-diol likely proceeds with a low energetic barrier. Mechanisms for the aromatization and deformylation sequence which are initiated by 1beta-hydrogen atom abstraction by P450 compound I are considered. 1beta-Hydrogen atom abstraction from substrates in the presence of the 2,3-enol encounters strikingly low barriers (5.3-7.8 kcal/mol), whereas barriers for this same process rise to 17.0-27.1 kcal/mol in the keto tautomer. Transition states for 1beta-hydrogen atom abstraction from enolized substrates in the presence of the 19-gem-diol decayed directly to the experimentally observed products. If the C19 aldehyde remains unhydrated, aromatization occurs with concomitant decarbonylation and therefore does not support dehydration of the C19 aldehyde prior to the final catalytic step. On the doublet surface, the transition state connects to a potentially labile 1(10) dehydrogenated product, which may undergo rapid aromatization, as well as formic acid. Ab initio molecular dynamics confirmed that the 1beta-hydrogen atom abstraction and deformylation or decarbonylation occur in a nonsynchronous, coordinated manner. These calculations support a dehydrogenase behavior of aromatase in the final catalytic step, which can be summarized by 1beta-hydrogen atom abstraction followed by gem-diol deprotonation.

  4. Membrane properties induced by anionic phospholipids and phosphatidylethanolamine are critical for the membrane binding and catalytic activity of human cytochrome P450 3A4.

    PubMed

    Kim, Keon-Hee; Ahn, Taeho; Yun, Chul-Ho

    2003-12-30

    Human cytochrome P450 (CYP) 3A4, a membrane anchoring protein, is the major CYP enzyme present in both liver and small intestine. The enzyme plays a major role in the metabolism of many drugs and procarcinogens. The roles of individual phospholipids and membrane properties in the catalytic activity, membrane binding, and insertion into the membrane of CYP3A4 are poorly understood. Here we report that the catalytic activity of testosterone 6beta-hydroxylation, membrane binding, and membrane insertion of CYP3A4 increase as a function of anionic phospholipid concentration in the order phosphatidic acid (PA) > phosphatidylserine (PS) in a binary system of phosphatidylcholine (PC)/anionic phospholipid and as a function of phosphatidylethanolamine (PE) content in ternary systems of PC/PE/PA or PC/PE/PS having a fixed concentration of anionic phospholipids. These results suggest that PA and PE might help the binding of CYP3A4 to the membrane and the interaction with NPR. Cytochrome b(5) (b(5)) and apolipoprotein b(5) further enhanced the testosterone 6beta-hydroxylation activities of CYP3A4 in all tested phospholipids vesicles with various compositions. Phospholipid-dependent changes of the CYP3A4 conformation were also revealed by altered Trp fluorescence and CD spectra. We also found that PE induced the formation of anionic phospholipid-enriched domains in ternary systems using extrinsic fluorescent probes incorporated into lipid bilayers. Taken together, it can be suggested that the chemical and physical properties of membranes induced by anionic phospholipids and PE are critical for the membrane binding and catalytic activity of CYP3A4.

  5. Surface-Enhanced Separation of Water from Hydrocarbons: Potential Dewatering Membranes for the Catalytic Fast Pyrolysis of Pine Biomass

    DOE PAGES

    Engtrakul, Dr. Chaiwat; Hu, Michael Z.; Bischoff, Brian L; ...

    2016-01-01

    The impact of surface-selective coatings on water permeation through a membrane when exposed to catalytic fast pyrolysis (CFP) vapor products was studied by tailoring the surface properties of the membrane coating from superhydrophilic to superhydrophobic. Our approach utilized high-performance architectured surface-selective (HiPAS) membranes that were inserted after a CFP reactor. At this insertion point, the inner wall surface of a tubular membrane was exposed to a mixture of water and upgraded product vapors, including light gases and deoxygenated hydrocarbons. Under proper membrane operating conditions, a high selectivity for water over 1-ring upgraded biomass pyrolysis hydrocarbons was observed due to amore » surface-enhanced capillary condensation process. Owing to this surface-enhanced effect, HiPAS membranes have the potential to enable high flux separations suggesting that water can be selectively removed from the CFP product vapors.« less

  6. Surface-Enhanced Separation of Water from Hydrocarbons: Potential Dewatering Membranes for the Catalytic Fast Pyrolysis of Pine Biomass

    SciTech Connect

    Engtrakul, Dr. Chaiwat; Hu, Michael Z.; Bischoff, Brian L; Jang, Gyoung Gug

    2016-01-01

    The impact of surface-selective coatings on water permeation through a membrane when exposed to catalytic fast pyrolysis (CFP) vapor products was studied by tailoring the surface properties of the membrane coating from superhydrophilic to superhydrophobic. Our approach utilized high-performance architectured surface-selective (HiPAS) membranes that were inserted after a CFP reactor. At this insertion point, the inner wall surface of a tubular membrane was exposed to a mixture of water and upgraded product vapors, including light gases and deoxygenated hydrocarbons. Under proper membrane operating conditions, a high selectivity for water over 1-ring upgraded biomass pyrolysis hydrocarbons was observed due to a surface-enhanced capillary condensation process. Owing to this surface-enhanced effect, HiPAS membranes have the potential to enable high flux separations suggesting that water can be selectively removed from the CFP product vapors.

  7. Surface-Enhanced Separation of Water from Hydrocarbons: Potential Dewatering Membranes for the Catalytic Fast Pyrolysis of Pine Biomass

    SciTech Connect

    Engtrakul, Chaiwat; Hu, Michael Z.; Bischoff, Brian L.; Jang, Gyoung G.

    2016-10-20

    The impact of surface-selective coatings on water permeation through a membrane when exposed to catalytic fast pyrolysis (CFP) vapor products was studied by tailoring the surface properties of the membrane coating from superhydrophilic to superhydrophobic. Our approach used high-performance architectured surface-selective (HiPAS) membranes that were inserted after a CFP reactor. At this insertion point, the inner wall surface of a tubular membrane was exposed to a mixture of water and upgraded product vapors, including light gases and deoxygenated hydrocarbons. Under proper membrane operating conditions, a high selectivity for water over one-ring upgraded biomass pyrolysis hydrocarbons was observed as a result of a surface-enhanced capillary condensation process. Owing to this surface-enhanced effect, HiPAS membranes have the potential to enable high flux separations, suggesting that water can be selectively removed from the CFP product vapors.

  8. Metal nanoparticle/ionic liquid/cellulose: new catalytically active membrane materials for hydrogenation reactions.

    PubMed

    Gelesky, Marcos A; Scheeren, Carla W; Foppa, Lucas; Pavan, Flavio A; Dias, Silvio L P; Dupont, Jairton

    2009-07-13

    Transition metal-containing membrane films of 10, 20, and 40 μm thickness were obtained by the combination of irregularly shaped nanoparticles with monomodal size distributions of 4.8 ± 1.1 nm (Rh(0)) and 3.0 ± 0.4 nm (Pt(0)) dispersed in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI·(NTf)(2)) with a syrup of cellulose acetate (CA) in acetone. The Rh(0) and Pt(0) metal concentration increased proportionally with increases in film thickness up to 20 μm, and then the material became metal saturated. The presence of small and stable Rh(0) or Pt(0) nanoparticles induced an augmentation in the CA/IL film surface areas. The augmentation of the IL content resulted in an increase of elasticity and decrease in tenacity and toughness, whereas the stress at break was not influenced. The introduction of IL probably causes an increase in the separation between the cellulose macromolecules that results in a higher flexibility, lower viscosity, and better formability of the cellulose material. The nanoparticle/IL/CA combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The nanoparticle/IL/cellulose acetate film membranes display higher catalytic activity (up to 7353 h(-1) for the 20 μm film of CA/IL/Pt(0)) and stability than the nanoparticles dispersed only in the IL.

  9. Architecture of a single membrane spanning cytochrome P450 suggests constraints that orient the catalytic domain relative to a bilayer

    PubMed Central

    Monk, Brian C.; Tomasiak, Thomas M.; Keniya, Mikhail V.; Huschmann, Franziska U.; Tyndall, Joel D. A.; O’Connell, Joseph D.; Cannon, Richard D.; McDonald, Jeffrey G.; Rodriguez, Andrew; Finer-Moore, Janet S.; Stroud, Robert M.

    2014-01-01

    Bitopic integral membrane proteins with a single transmembrane helix play diverse roles in catalysis, cell signaling, and morphogenesis. Complete monospanning protein structures are needed to show how interaction between the transmembrane helix and catalytic domain might influence association with the membrane and function. We report crystal structures of full-length Saccharomyces cerevisiae lanosterol 14α-demethylase, a membrane monospanning cytochrome P450 of the CYP51 family that catalyzes the first postcyclization step in ergosterol biosynthesis and is inhibited by triazole drugs. The structures reveal a well-ordered N-terminal amphipathic helix preceding a putative transmembrane helix that would constrain the catalytic domain orientation to lie partly in the lipid bilayer. The structures locate the substrate lanosterol, identify putative substrate and product channels, and reveal constrained interactions with triazole antifungal drugs that are important for drug design and understanding drug resistance. PMID:24613931

  10. Removal of selected nitrogenous heterocyclic compounds in biologically pretreated coal gasification wastewater (BPCGW) using the catalytic ozonation process combined with the two-stage membrane bioreactor (MBR).

    PubMed

    Zhu, Hao; Han, Yuxing; Ma, Wencheng; Han, Hongjun; Ma, Weiwei

    2017-09-06

    Three identical anoxic-aerobic membrane bioreactors (MBRs) were operated in parallel for 300 consecutive days for raw (R1), ozonated (R2) and catalytic ozonated (R3) biologically pretreated coal gasification wastewater (BPCGW) treatment. The results demonstrated that catalytic ozonation process (COP) applied asa pretreatment remarkably improved the performance of the unsatisfactory single MBR. The overall removal efficiencies of COD, NH3-N and TN in R3 were 92.7%, 95.6% and 80.6%, respectively. In addition, typical nitrogenous heterocyclic compounds (NHCs) of quinoline, pyridine and indole were completely removed in the integrated process. Moreover, COP could alter sludge properties and reshape microbial community structure, thus delaying the occurrence of membrane fouling. Finally, the total cost for this integrated process was estimated to be lower than that of single MBR. The results of this study suggest that COP is a good option to enhance pollutants removal and alleviate membrane fouling in the MBR for BPCGW treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Hierarchical structured MnO2@SiO2 nanofibrous membranes with superb flexibility and enhanced catalytic performance.

    PubMed

    Wang, Xueqin; Dou, Lvye; Yang, Liu; Yu, Jianyong; Ding, Bin

    2017-02-15

    Constructing nanostructured catalyst-embedded ceramic fibrous membranes would facilitate the remediation or preliminary treatment of dyeing wastewater, however, most of such membranes are brittle with low deformation resistance, thus, restricting their widely applications. Herein, the flexible and hierarchical nanostructured MnO2-immobilized SiO2 nanofibrous membranes (MnO2@SiO2 NFM) were fabricated by combining the electrospinning technique with hydrothermal method. The morphologies of membranes could be regulated from nanowires and nanoflower to mace-like structure via varying concentration of reactants. The resultant MnO2@SiO2 NFM could cooperate with hydrogen peroxide to form a Fenton-like reagent for the degradation of methylene blue (MB). The resultant membrane exhibited prominent catalytic performance towards MB, including high degradation degree of 95% within 40min, fast degradation rate of 0.0865min(-1), and excellent reusability in 5 cycles. Moreover, the membranes could be used in a wide pH range of 0 to 14 and the degradation degree reached 76% during dynamic filtration process with a flux of 490,000Lm(-2)h(-1). The successful fabricating of such membrane with extraordinary catalytic performance would provide a platform for preparing high-performance catalysts for remediation of dyeing wastewater. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Characterization of the catalytic activity of the membrane-anchored metalloproteinase ADAM15 in cell-based assays.

    PubMed

    Maretzky, Thorsten; Yang, Guangli; Ouerfelli, Ouathek; Overall, Christopher M; Worpenberg, Susanne; Hassiepen, Ulrich; Eder, Joerg; Blobel, Carl P

    2009-04-28

    ADAM15 (a disintegrin and metalloproteinase 15) is a membrane-anchored metalloproteinase, which is overexpressed in several human cancers and has been implicated in pathological neovascularization and prostate cancer metastasis. Yet, little is known about the catalytic properties of ADAM15. Here, we purified soluble recombinant ADAM15 to test for its ability to cleave a library of peptide substrates. However, we found no processing of any of the peptide substrates tested here, and therefore turned to cell-based assays to characterize the catalytic properties of ADAM15. Overexpression of full-length membrane-anchored ADAM15 or the catalytically inactive ADAM15E-->A together with various membrane proteins resulted in increased release of the extracellular domain of the fibroblast growth factor receptor 2iiib (FGFR2iiib) by ADAM15, but not ADAM15E-->A. This provided a robust assay for a characterization of the catalytic properties of ADAM15 in intact cells. We found that increased expression of ADAM15 resulted in increased FGFR2iiib shedding, but that ADAM15 was not stimulated by phorbol esters or calcium ionophores, two commonly used activators of ectodomain shedding. Moreover, ADAM15-dependent processing of FGFR2iiib was inhibited by the hydroxamate-based metalloproteinase inhibitors marimastat, TAPI-2 and GM6001, and by 50 nM TIMP-3 (tissue inhibitor of metalloproteinases 3), but not by 100 nM TIMP-1, and only weakly by 100 nM TIMP-2. These results define key catalytic properties of ADAM15 in cells and its response to stimulators and inhibitors of ectodomain shedding. A cell-based assay for the catalytic activity of ADAM15 could aid in identifying compounds, which could be used to block the function of ADAM15 in pathological neovascularization and cancer.

  13. Research and development to overcome fouling of membranes. Final report

    SciTech Connect

    Narang, S.C.; Sharma, S.K.; Hum, G.; Ventura, S.C.; Roberts, D.L.; Gottschlich, D.; Ahner, N.

    1998-11-01

    To overcome fouling of membranes, SRI International is developing a unique piezoelectric backing for ultrafiltration membranes. This backing is capable of producing local turbulence next to the membrane to minimize concentration polarization and the rate of buildup of solutes and particulate matter on the membrane surface. We have studied piezoelectrically assisted ultrafiltration in more detail, with the objective to apply this process to industrial ultrafiltrations. We conducted several ultrafiltration experiments on flat sheet membranes with model dextran solutions and with electrocoat paint to study flux enhancement as a function of parameters such as feed flow rate, feed pressure, as well as the piezodriver-membrane system.

  14. Development of ceramic membrane reactors for high temperature gas cleanup. Final report

    SciTech Connect

    Roberts, D.L.; Abraham, I.C.; Blum, Y.; Gottschlich, D.E.; Hirschon, A.; Way, J.D.; Collins, J.

    1993-06-01

    The objective of this project was to develop high temperature, high pressure catalytic ceramic membrane reactors and to demonstrate the feasibility of using these membrane reactors to control gaseous contaminants (hydrogen sulfide and ammonia) in integrated gasification combined cycle (IGCC) systems. Our strategy was to first develop catalysts and membranes suitable for the IGCC application and then combine these two components as a complete membrane reactor system. We also developed a computer model of the membrane reactor and used it, along with experimental data, to perform an economic analysis of the IGCC application. Our results have demonstrated the concept of using a membrane reactor to remove trace contaminants from an IGCC process. Experiments showed that NH{sub 3} decomposition efficiencies of 95% can be achieved. Our economic evaluation predicts ammonia decomposition costs of less than 1% of the total cost of electricity; improved membranes would give even higher conversions and lower costs.

  15. Modeling and simulation of ammonia removal from purge gases of ammonia plants using a catalytic Pd-Ag membrane reactor.

    PubMed

    Rahimpour, M R; Asgari, A

    2008-05-01

    In this work, the removal of ammonia from synthesis purge gas of an ammonia plant has been investigated. Since the ammonia decomposition is thermodynamically limited, a membrane reactor is used for complete decomposition. A double pipe catalytic membrane reactor is used to remove ammonia from purge gas. The purge gas is flowing in the reaction side and is converted to hydrogen and nitrogen over nickel-alumina catalyst. The hydrogen is transferred through the Pd-Ag membrane of tube side to the shell side. A mathematical model including conservation of mass in the tube and shell side of reactor is proposed. The proposed model was solved numerically and the effects of different parameters on the rector performance were investigated. The effects of pressure, temperature, flow rate (sweep ratio), membrane thickness and reactor diameter have been investigated in the present study. Increasing ammonia conversion was observed by raising the temperature, sweep ratio and reducing membrane thickness. When the pressure increases, the decomposition is gone toward completion but, at low pressure the ammonia conversion in the outset of reactor is higher than other pressures, but complete destruction of the ammonia cannot be achieved. The proposed model can be used for design of an industrial catalytic membrane reactor for removal of ammonia from ammonia plant and reducing NO(x) emissions.

  16. Ceramic membranes for gas separation at high temperatures. Final report

    SciTech Connect

    Wang, C.J.

    1994-03-01

    Superior heat, wear, erosion, and corrosion resistance of ceramic materials have motivated the studies of processing-structure-performance interrelationships of ceramic membranes for high temperature gas separations. A literature review on pore transport mechanisms, physical structure of membranes, and module configuration of industrial membrane processes has been made to obtain a better understanding of membrane performance in gas separations. The research experience in decomposing polymer resins for ablative composites has stimulated a research interest in developing a dynamic model for membrane processes, incorporating a temperature effects on material and fluid properties. Brief summaries of the reviewed literature, permeability experiments, and process modeling are presented in this report.

  17. Development of catalytically active and highly stable catalyst supports for polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Taekeun; Xie, Tianyuan; Jung, Wonsuk; Gadala-Maria, Francis; Ganesan, Prabhu; Popov, Branko N.

    2015-01-01

    Novel procedures are developed for the synthesis of highly stable carbon composite catalyst supports (CCCS-800 °C and CCCS-1100 °C) and an activated carbon composite catalyst support (A-CCCS). These supports are synthesized through: (i) surface modification with acids and inclusion of oxygen groups, (ii) metal-catalyzed pyrolysis, and (iii) chemical leaching to remove excess metal used to dope the support. The procedure results in increasing carbon graphitization and inclusion of non-metallic active sites on the support surface. Catalytic activity of CCCS indicates an onset potential of 0.86 V for the oxygen reduction reaction (ORR) with well-defined kinetic and mass-transfer regions and ∼2.5% H2O2 production in rotating ring disk electrode (RRDE) studies. Support stability studies at 1.2 V constant potential holding for 400 h indicate high stability for the 30% Pt/A-CCCS catalyst with a cell potential loss of 27 mV at 800 mA cm-2 under H2-air, 32% mass activity loss, and 30% ECSA loss. Performance evaluation in polymer electrolyte membrane (PEM) fuel cell shows power densities (rated) of 0.18 and 0.23 gPt kW-1 for the 30% Pt/A-CCCS and 30% Pt/CCCS-800 °C catalysts, respectively. The stabilities of various supports developed in this study are compared with those of a commercial Pt/C catalyst.

  18. Microwave assisted esterification of acidified oil from waste cooking oil by CERP/PES catalytic membrane for biodiesel production.

    PubMed

    Zhang, Honglei; Ding, Jincheng; Zhao, Zengdian

    2012-11-01

    The traditional heating and microwave assisted method for biodiesel production using cation ion-exchange resin particles (CERP)/PES catalytic membrane were comparatively studied to achieve economic and effective method for utilization of free fatty acids (FFAs) from waste cooking oil (WCO). The optimal esterification conditions of the two methods were investigated and the experimental results showed that microwave irradiation exhibited a remarkable enhanced effect for esterification compared with that of traditional heating method. The FFAs conversion of microwave assisted esterification reached 97.4% under the optimal conditions of reaction temperature 60°C, methanol/acidified oil mass ratio 2.0:1, catalytic membrane (annealed at 120°C) loading 3g, microwave power 360W and reaction time 90min. The study results showed that it is a fast, easy and green way to produce biodiesel applying microwave irradiation. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. Silica membranes for hydrogen separation from coal gas. Final report

    SciTech Connect

    Gavalas, G.R.

    1996-01-01

    This project is a continuation of a previous DOE-UCR project (DE-FG22- 89PC89765) dealing with the preparation of silica membranes highly permselective to hydrogen at elevated temperatures, suitable for hydrogen separation from coal gas. The membranes prepared in the previous project had very high selectivity but relatively low permeance. Therefore, the general objectives of this project were to improve the permeance of these membranes and to obtain fundamental information about membrane structure and properties. The specific objectives were: (1) to explore new silylation reagents and reaction conditions with the purpose of reducing the thickness and increasing the permeance of silica membranes prepared by chemical vapor deposition (CVD), (2) to characterize the membrane structure, (3) to delineate mechanism and kinetics of deposition, (4) to measure the permeability of silica layers at different extents of deposition, and (5) to mathematically model the relationship between structure and deposition kinetics.

  20. Influence of lysophospholipid hydrolysis by the catalytic domain of neuropathy target esterase on the fluidity of bilayer lipid membranes.

    PubMed

    Greiner, Aaron J; Richardson, Rudy J; Worden, R Mark; Ofoli, Robert Y

    2010-08-01

    Neuropathy target esterase (NTE) is an integral membrane protein localized in the endoplasmic reticulum in neurons. Irreversible inhibition of NTE by certain organophosphorus compounds produces a paralysis known as organophosphorus compound-induced delayed neuropathy. In vitro, NTE has phospholipase/lysophospholipase activity that hydrolyses exogenously added single-chain lysophospholipids in preference to dual-chain phospholipids, and NTE mutations have been associated with motor neuron disease. NTE's physiological role is not well understood, although recent studies suggest that it may control the cytotoxic accumulation of lysophospholipids in membranes. We used the NTE catalytic domain (NEST) to hydrolyze palmitoyl-2-hydroxy-sn-glycero-3-phosphocholine (p-lysoPC) to palmitic acid in bilayer membranes comprising 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and the fluorophore 1-oleoyl-2-[12-[(7-nitro-2-1,3-benzoxadiazol-4-yl)amino]dodecanoyl]-sn-glycero-3-phosphocholine (NBD-PC). Translational diffusion coefficients (D(L)) in supported bilayer membranes were measured by fluorescence recovery after pattern photobleaching (FRAPP). The average D(L) for DOPC/p-lysoPC membranes without NEST was 2.44 microm(2)s(-1)+/-0.09; the D(L) for DOPC/p-lysoPC membranes containing NEST and diisopropylphosphorofluoridate, an inhibitor, was nearly identical at 2.45+/-0.08. By contrast, the D(L) for membranes comprising NEST, DOPC, and p-lysoPC was 2.28+/-0.07, significantly different from the system with inhibited NEST, due to NEST hydrolysis. Likewise, a system without NEST containing the amount of palmitic acid that would have been produced by NEST hydrolysis of p-lysoPC was identical at 2.26+/-0.06. These results indicate that NTE's catalytic activity can alter membrane fluidity. Copyright 2010 Elsevier B.V. All rights reserved.

  1. Final Report - Membranes and MEA's for Dry, Hot Operating Conditions

    SciTech Connect

    Hamrock, Steven J

    2011-06-30

    The focus of this program was to develop a new Proton Exchange Membrane (PEM) which can operate under hotter, dryer conditions than the state of the art membranes today and integrate it into a Membrane Electrode Assembly (MEA). These MEA's should meet the performance and durability requirements outlined in the solicitation, operating under low humidification conditions and at temperatures ranging from -20ºC to 120ºC, to meet 2010 DOE technical targets for membranes. This membrane should operate under low humidification conditions and at temperatures ranging from -20ºC to 120ºC in order to meet DOE HFCIT 2010 commercialization targets for automotive fuel cells. Membranes developed in this program may also have improved durability and performance characteristics making them useful in stationary fuel cell applications. The new membranes, and the MEA's comprising them, should be manufacturable at high volumes and at costs which can meet industry and DOE targets. This work included: A) Studies to better understand factors controlling proton transport within the electrolyte membrane, mechanisms of polymer degradation (in situ and ex situ) and membrane durability in an MEA; B) Development of new polymers with increased proton conductivity over the range of temperatures from -20ºC to 120ºC and at lower levels of humidification and with improved chemical and mechanical stability; C) Development of new membrane additives for increased durability and conductivity under these dry conditions; D) Integration of these new materials into membranes and membranes into MEA's, including catalyst and gas diffusion layer selection and integration; E) Verification that these materials can be made using processes which are scalable to commercial volumes using cost effective methods; F) MEA testing in single cells using realistic automotive testing protocols. This project addresses technical barriers A (Durability) and C (Performance) from the Fuel Cells section of the 2005 Hydrogen

  2. The development of manganese oxide coated ceramic membranes for combined catalytic ozonation and ultrafiltration of drinking water

    NASA Astrophysics Data System (ADS)

    Corneal, Lindsay Marie

    A novel method for the preparation of hydrated MnO2 by the ozonation of MnCl2 in water is described. The hydrated MnO 2 was used to coat titania water filtration membranes using a layer-by-layer technique. The coated membranes were then sintered in air at 500°C for 45 minutes. Upon sintering, the MnO2 is converted to alpha-Mn 2O3 (as characterized by x-ray and electron diffraction). Atomic force microscopy (AFM) imaging showed no significant change in the roughness or height of the surface features of coated membranes, while scanning electron microscopy (SEM) imaging showed an increase in grain size with increasing number of coating layers. Energy dispersive x-ray spectroscopy (EDS) mapping and line scans revealed manganese present throughout the membrane, indicating that manganese dispersed into the porous membrane during the coating process and diffused into the titania grains during sintering. Selected area diffraction (SAD) of the coated and sintered membrane was used to index the surface layer as alpha-Mn2O3. The surface layer was uneven, although there was a trend of increasing thickness with increasing coating layers. The coating acts as a catalyst for the oxidation of organic matter when coated membranes are used in a hybrid ozonation-membrane filtration system. A trend of decreasing total organic carbon (TOC) in the permeate water was observed with increasing number of coating layers. The catalytic activity also manifests itself as improved recovery of the water flux due to oxidation of foulants on the membrane surface. Ceramic nanoparticle coatings on ceramic water filtration membranes must undergo high temperature sintering. However, this means that the underlying membrane, which has been engineered for a given molecular weight cut-off (MWCO), also undergoes a high temperature heat treatment that serves to increase pore size that have resulted in increases in permeability of titania membranes. Coating the titania membrane with manganese oxide followed

  3. Driven chemical kinetics: Optimalization of catalytic action of membrane proteins by rectangular alternating electric field

    NASA Astrophysics Data System (ADS)

    Fuliński, Andrzej

    1992-03-01

    The chemical kinetics driven by external force in the form of a train of alternating rectangular impulses is discussed. The model of the conformational transition of a membrane protein exposed to an ac electric field, proposed by R. D. Astumian and B. Robertson [J. Chem. Phys. 91, 4891 (1989)], is reconsidered. On the example of this model we show that the use of the driving field in the form of rectangular impulses has two distinct advantages over the usual sinusoidal driving. The first one is that the use of a rectangular driving field makes it possible to obtain the exact solution of the basic kinetic equation of the system. This in turn enables one to write down the simple and very good approximate solution for any form of the driving field, better than the harmonic expansion used by Astumian and Robertson. A more important advantage is the greater flexibility of the rectangular driving, which makes possible the better optimalization of the process of interest. Astumian and Robertson demonstrated that the movement of charge within the catalytic cycle provides a mechanism for the enzyme to absorb energy from an ac electric field and to use that energy to enhance the catalyzed process. In this paper we show that the use of the driving ac field in the form of alternating rectangular impulses of variable duration and amplitude (instead of the usual sinusoidal modulation) leads to further optimalization of the process. The efficiency of the energy transduction, for example, can be increased from about 25% for sinusoidal driving to about 37% for suitably chosen alternating rectangular pulses.

  4. Thermal and chemical degradation of inorganic membrane materials. Final report, August 1992--May 1995

    SciTech Connect

    Damle, A.S.; Krishnan, G.N.; Sanjurjo, A.; Wood, B.J.; Lau, K.H.

    1995-05-01

    SRI International conducted a theoretical and experimental program to evaluate the long-term thermal and chemical degradation of inorganic membranes that are being developed to separate the gaseous products of coal gasification. A variety of developmental efforts are underway, including a number of projects sponsored by the US Department of Energy (DOE), to improve the selectivity and permeability of porous inorganic membranes. DOE is also sponsoring efforts to extend the use of metallic membranes to new applications. Most developmental efforts have focused on hydrogen separation by inorganic membranes, which may be used to maximize hydrogen production from coal gas or to remove H{sub 2}S and NH{sub 3} contaminants via thermal or catalytic decomposition in integrated-gasification combined-cycle (IGCC) systems. Inorganic membranes that have a high separation efficiency and exhibit both thermal and chemical stability would improve the economics of power generation from coal. Membrane materials that have been investigated include glass (silica), alumina, carbon, and metals (Pd and Pt). This report describes inorganic membrane materials, long term membrane exposure tests, membrane permeation tests, coal gasifier exposure tests, conclusions, and recommendations.

  5. Catalytic membrane program. Quarterly report for the period August 1999--October 1999

    SciTech Connect

    Liu, Paul K.T.

    1999-11-12

    For both power generation and pipeline-quality gas applications, the projected performance of the membrane currently under development is economically attractive. Aspects of membrane development include hollow fiber substrate production, reproducibility of membrane synthesis, chemical vapor deposition as a post treatment technique, and testing of membrane thermal and hydrothermal stability.

  6. Advanced membrane separation technology for biosolvents. Final CRADA report.

    SciTech Connect

    Snyder, S. W.; Energy Systems

    2010-02-08

    Argonne and Vertec Biosolvents investigated the stability and perfonnance for a number of membrane systems to drive the 'direct process' for pervaporation-assisted esterification to produce lactate esters. As outlined in Figure 1, the target is to produce ammonium lactate by fennentation. After purification and concentration, ammonium lactate is reacted with ethanol to produce the ester. Esterification is a reversible reaction so to drive the reaction forward, the produced ammonia and water must be rapidly separated from the product. The project focused on selecting pervaporation membranes with (1) acid functionality to facilitate ammonia separation and (2) temperature stability to be able to perform that reaction at as high a temperature as possible (Figure 2). Several classes of commercial membrane materials and functionalized membrane materials were surveyed. The most promising materials were evaluated for scale-up to a pre-commercial application. Over 4 million metric tons per year of solvents are consumed in the U.S. for a wide variety of applications. Worldwide the usage exceeds 10 million metric tons per year. Many of these, such as the chlorinated solvents, are environmentally unfriendly; others, such as the ethylene glycol ethers and N Methyl Pyrrolidone (NMP), are toxic or teratogenic, and many other petroleum-derived solvents are coming under increasing regulatory restrictions. High performance, environmentally friendly solvents derived from renewable biological resources have the potential to replace many of the chlorinated and petrochemical derived solvents. Some of these solvents, such as ethyl lactate; d-limonene, soy methyl esters, and blends ofthese, can give excellent price/perfonnance in addition to the environmental and regulatory compliance benefits. Advancement of membrane technologies, particularly those based on pervaporation and electrodialysis, will lead to very efficient, non-waste producing, and economical manufacturing technologies for

  7. Solid support membrane-aerated catalytic biofilm reactor for the continuous synthesis of (S)-styrene oxide at gram scale.

    PubMed

    Halan, Babu; Letzel, Thomas; Schmid, Andreas; Buehler, Katja

    2014-10-01

    Catalytic biofilms minimize reactant toxicity and maximize biocatalyst stability in selective transformations of chemicals to value-added products in continuous processes. The scaling up of such catalytic biofilm processes is challenging, due to fluidic and biological parameters affording a special reactor design affecting process performance. A solid support membrane-aerated biofilm reactor was optimized and scaled-up to yield gram amounts of (S)-styrene oxide, a toxic and instable high value chemical synthon. A sintered stainless steel membrane unit was identified as an optimal choice as biofilm substratum and for high oxygen mass transfer. A stable expanded polytetrafluoroethylene (ePTFE) membrane was best suited for in situ substrate delivery and product extraction. For the verification of scalability, catalytic biofilms of Pseudomonas sp. strain VLB120ΔC produced (S)-styrene oxide to an average concentration of 390 mM in the organic phase per day (equivalent to 24.4 g Laq (-1) day(-1) ). This productivity was gained by efficiently using the catalyst with an excellent product yield on biomass of 13.6 gproduct gbiomass (-1) . This product yield on biomass is in the order of magnitude reported for other continuous systems based on artificially immobilized biocatalysts and is fulfilling the minimum requirements for industrial biocatalytic processes. Overall, 46 g of (S)-styrene oxide were produced and isolated (purity: 99%; enantiomeric excess [ee]: >99.8%. yield: 30%). The productivity is in a similar range as in comparable small-scale biofilm reactors highlighting the large potential of this methodology for continuous bioprocessing of bulk chemicals and biofuels. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Kinetics of esterification of acidified oil with different alcohols by a cation ion-exchange resin/polyethersulfone hybrid catalytic membrane.

    PubMed

    Zhang, Honglei; Ding, Jincheng; Qiu, Yanli; Zhao, Zengdian

    2012-05-01

    Hybrid catalytic membranes consisting of cation ion-exchange resin particles (CERP) and polyethersulfone (PES) were prepared by immersion phase inversion and used as heterogeneous catalysts for the esterification of acidified oil with methanol, ethanol, propanol and butanol. The membranes were characterized by ion exchange capacity and swelling degree tests. The membranes were annealed at different temperatures to improve catalytic activity and membranes annealed at 393 K had the highest catalytic activity. Butanol allowed the highest free fatty acids (FFAs) conversion of 95.28% since it has better miscibility than the other alcohols which strengthened mass and heat transfer. Furthermore, pseudo-homogeneous kinetic models of the esterification of acidified oil with the four alcohols were established according to the experimental data. The kinetic models can well predict the FFA conversion. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Catalytic partial oxidation and membrane separation to optimize the conversion of natural gas to syngas and hydrogen.

    PubMed

    Capoferri, Daniela; Cucchiella, Barbara; Iaquaniello, Gaetano; Mangiapane, Alessia; Abate, Salvatore; Centi, Gabriele

    2011-12-16

    The multistep integration of hydrogen-selective membranes into catalytic partial oxidation (CPO) technology to convert natural gas into syngas and hydrogen is reported. An open architecture for the membrane reactor is presented, in which coupling of the reaction and hydrogen separation is achieved independently and the required feed conversion is reached through a set of three CPO reactors working at 750, 750 and 920 °C, compared to 1030 °C for conventional CPO technology. Obtaining the same feed conversion at milder operating conditions translates into less natural gas consumption (and CO(2) emissions) and a reduction of variable operative costs of around 10 %. It is also discussed how this energy-efficient process architecture, which is suited particularly to small-to-medium applications, may improve the sustainability of other endothermic, reversible reactions to form hydrogen. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Development of chlorine resistant membrane, asymmetric polyimide membrane and porous substrates. Final report

    SciTech Connect

    Sudak, R.G.; Chirrick, J.M.; Fox, R.L.; McKee, M.E.; Bott, J.B.; Tomaschke, J.E.

    1980-09-01

    The development of chlorine resistant membrane, asymmetric polymide membrane, and porous substrates was studied. The development of supports with different polymeric materials was undertaken to increase: (1) the number of possible solvents for use in membrane barrier layer formation, and (2) the allowable temperature for such formation. The materials were developed with pore size variations for use in ultrafiltration/ microfiltration applications as well as hyperfiltration. It was found that cellulose acetate is stable to low residual chlorine concentrations in feedwaters, but polymide in sheet composite membrane or asymmetric hollow fine fibers was not. The mechanism of residual chlorine degradation of various polymers which caused synthesis of several polymers and their subsquent reaction to form polyimide membrane layers was also investigated.

  11. 2011 Alkaline Membrane Fuel Cell Workshop Final Report

    SciTech Connect

    Pivovar, B.

    2012-02-01

    A workshop addressing the current state-of-the-art in alkaline membrane fuel cells (AMFCs) was held May 8-9, 2011, at the Crystal Gateway Marriott in Arlington, Virginia. This workshop was the second of its kind, with the first being held December 11-13, 2006, in Phoenix, Arizona. The 2011 workshop and associated workshop report were created to assess the current state of AMFC technology (taking into account recent advances), investigate the performance potential of AMFC systems across all possible power ranges and applications, and identify the key research needs for commercial competitiveness in a variety of areas.

  12. Synthetic and Thermodynamic Investigations of Ancillary Ligand Influence on Catalytic Organometallic Systems. Final Report

    SciTech Connect

    Nolan, Steven

    2003-03-20

    During the grant period we have been involved in synthesizing and experimentally determining solution enthalpy values associated with partially fluorinated ligands. This has lead to the publication of manuscripts dealing with synthetic, calorimetric and catalytic behavior of partially fluorinated ligands. The collaboration with Los Alamos researchers has lead to the publication of catalytic results in sc CO{sub 2} which have proven very interesting. Furthermore, we have also examined ligands that behave as phosphine mimics. The N-heterocyclic carbenes have been explored as alternatives for tertiary phosphines and have resulted in the design and construction of efficient palladium and nickel system capable of performing C-C and C-N cross coupling reactions. The initial studies in this areas were made possible by exploratory work conducted under the DOE/EPSCoR grant.

  13. Catalytic mechanism of hydrogenase from Azotobacter vinelandii. Final technical report, August 1, 1994--July 31, 1997

    SciTech Connect

    Arp, D.J.

    1997-10-01

    This project is focused on investigations of the catalytic mechanism of the hydrogenase found in the aerobic, N{sub 2}-fixing microorganism Azotobacter vinelandii. This report summarizes the progress during the first two years of the current project and include the anticipated course of the research for the remaining year of the current project. Because the current proposal represents a change in direction, the authors also include a brief progress report of prior DOE-sponsored research dealing with hydrogenases.

  14. Combined air stripper/membrane vapor separation systems. Final report

    SciTech Connect

    Wijmans, J.G.; Baker, R.W.; Kamaruddin, H.D.; Kaschemekat, J.; Olsen, R.P.; Rose, M.E.; Segelke, S.V.

    1992-11-01

    Air stripping is an economical and efficient method of removing dissolved volatile organic compounds (VOCs) from contaminated groundwater. Air strippers, however, produce a vent air stream, which must meet the local air quality limits. If the VOC content exceeds the limits, direct discharge is not possible; therefore, a carbon adsorption VOC capture system is used to treat the vent air. This treatment step adds a cost of at least $50/lb of VOC captured. In this program, a combined air stripper/membrane vapor separation system was constructed and demonstrated in the laboratory. The membrane system captures VOCs from the stripper vent stream at a projected cost of $15/lb VOC for a water VOC content of 5 ppmw, and $75/lb VOC for a water VOC content of 1 ppmw. The VOCs are recovered as a small, concentrated liquid fraction for disposal or solvent recycling. The concept has been demonstrated in experiments with a system capable of handling up to 150,000 gpd of water. The existing demonstration system is available for field tests at a DOE facility or remediation site. Replacement of the current short air stripping tower (effective height 3 m) with a taller tower is recommended to improve VOC removal.

  15. Catalytic water dissociation using hyperbranched aliphatic polyester (Boltorn series) as the interface of a bipolar membrane.

    PubMed

    Xue, Yanhong; Xu, Tongwen; Fu, Rongqiang; Cheng, Yiyun; Yang, Weihua

    2007-12-15

    The effect of hyperbranched aliphatic polyester (Boltorn series) on the water dissociation in bipolar membranes was firstly investigated in this paper. The bipolar membranes were prepared by immersing the anion exchange layer in a hyperbranched aliphatic polyester solution and then coating on the layer a polyphenylene oxide (SPPO) solution. The SEM observations proved the existence of hyperbranched aliphatic polyester at the membrane intermediate layer. The adsorption amount was evaluated by the oxygen content via XPS. The junction thickness of the prepared bipolar membrane was determined by electrochemical impedance spectroscopy (EIS), and the membrane performances were evaluated by current-voltage curves. The results showed that the amount and generation of Boltorn series, and temperature all affected I-V behaviors of the fabricated bipolar membranes, and the former two played the critical role. These effects were explained on the basis of the water dissociation theory and the characteristics of hyperbranched aliphatic polyester.

  16. Quantitative Immobilization of Phthalocyanine onto Bacterial Cellulose for Construction of a High-Performance Catalytic Membrane Reactor.

    PubMed

    Chen, Shiliang; Teng, Qiaoling

    2017-07-24

    We report the fabrication of a tetra-amino cobalt (II) phthalocyanine (CoPc)-immobilized bacterial cellulose (BC) functional nanocomposite, CoPc@BC, by quantitative immobilization of CoPc onto a BC membrane. Lab-cultured BC was oxidized by NaIO₄ to generate aldehyde groups on BC for the subsequent CoPc immobilization, the processing conditions were optimized by monitoring both the generated aldehyde content and the resulting CoPc loading. X-ray photoelectron spectroscopy (XPS) was employed to characterize the change of the element bonding environment during the functionalization processes. The CoPc@BC functional nanocomposite was utilized for the treatment of reactive red X-3B dye wastewater. The CoPc molecules in the CoPc@BC nanocomposite can function as an "antenna" to adsorb the target anionic dye molecules, the adsorption takes place both on the surface and in the interior of CoPc@BC. A catalytic membrane reactor (CMR) was assembled with the CoPc@BC nanocomposite, the performance of CMR was evaluated based on the catalytic oxidation behavior of reactive red X-3B, with H₂O₂ as an oxidant. Highly-reactive hydroxyl radical (OH) was involved in the catalytic oxidation process, as detected by electron paramagnetic resonance (EPR). Under optimal operating conditions of a flow rate of 6 mL/min, a reaction temperature of 50 °C, and an H₂O₂ concentration of 10 mmol/L, the decoloration rate of CMR was as high as 50 μmol⋅min(-1)⋅g(-1).

  17. Selective catalytic reduction of sulfur dioxide to elemental sulfur. Final report

    SciTech Connect

    Liu, W.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

    1995-06-01

    This project has investigated new metal oxide catalysts for the single stage selective reduction of SO{sub 2} to elemental sulfur by a reductant, such as CO. Significant progress in catalyst development has been made during the course of the project. We have found that fluorite oxides, CeO{sub 2} and ZrO{sub 2}, and rare earth zirconates such as Gd{sub 2}Zr{sub 2}O{sub 7} are active and stable catalysts for reduction Of SO{sub 2} by CO. More than 95% sulfur yield was achieved at reaction temperatures about 450{degrees}C or higher with the feed gas of stoichiometric composition. Reaction of SO{sub 2} and CO over these catalysts demonstrated a strong correlation of catalytic activity with the catalyst oxygen mobility. Furthermore, the catalytic activity and resistance to H{sub 2}O and CO{sub 2} poisoning of these catalysts were significantly enhanced by adding small amounts of transition metals, such as Co, Ni, Co, etc. The resulting transition metal-fluorite oxide composite catalyst has superior activity and stability, and shows promise in long use for the development of a greatly simplified single-step sulfur recovery process to treat variable and dilute SO{sub 2} concentration gas streams. Among various active composite catalyst systems the Cu-CeO{sub 2} system has been extensively studied. XRD, XPS, and STEM analyses of the used Cu-CeO{sub 2} catalyst found that the fluorite crystal structure of ceria was stable at the present reaction conditions, small amounts of copper was dispersed and stabilized on the ceria matrix, and excess copper oxide particles formed copper sulfide crystals of little contribution to catalytic activity. A working catalyst consisted of partially sulfated cerium oxide surface and partially sulfided copper clusters. The overall reaction kinetics were approximately represented by a first order equation.

  18. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification.

    PubMed

    Castro-Dominguez, Bernardo; Mardilovich, Ivan P; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G; Kazantzis, Nikolaos K; Ma, Yi Hua

    2016-09-19

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H₂ to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H₂, CO and CO₂. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H₂O, CO₂ and H₂. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H₂ and induce higher methane and CO conversions while yielding ultrapure H₂ and compressed CO₂ ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H₂ permeance and purity, high CH₄ conversion levels and reduced CO yields.

  19. Catalytic Hydrothermal Gasification of Lignin-Rich Biorefinery Residues and Algae Final Report

    SciTech Connect

    Elliott, Douglas C.; Neuenschwander, Gary G.; Hart, Todd R.; Rotness, Leslie J.; Zacher, Alan H.; Santosa, Daniel M.; Valkenburt, Corinne; Jones, Susanne B.; Tjokro Rahardjo, Sandra A.

    2009-11-03

    This report describes the results of the work performed by PNNL using feedstock materials provided by the National Renewable Energy Laboratory, KL Energy and Lignol lignocellulosic ethanol pilot plants. Test results with algae feedstocks provided by Genifuel, which provided in-kind cost share to the project, are also included. The work conducted during this project involved developing and demonstrating on the bench-scale process technology at PNNL for catalytic hydrothermal gasification of lignin-rich biorefinery residues and algae. A technoeconomic assessment evaluated the use of the technology for energy recovery in a lignocellulosic ethanol plant.

  20. Control of industrial VOC (volatile organic compound) emissions by catalytic incineration. volume 5. catalytic incinerator performance at industrial site c-3. Final report, May 1982-August 1983

    SciTech Connect

    Blacksmith, J.R.; Randall, J.L.

    1984-07-01

    The report is part of a two-phase EPA effort to assess the performance, suitability, and costs of various technologies to control emissions of volatile organic compounds (VOCs). In Phase 1, information was assembled from the literature on the use and cost of using catalytic incineration for VOC control. Results included: (1) a review of current and developing catalytic incineration technology, (2) an assessment of the overall performance of catalytic incinerators, (3) a review of applications where catalytic incinerators are used, (4) a comparative analysis of catalytic incineration with other competing VOC controls, (5) an examination of available methods for emission testing catalytic incinerators, and (6) an assessment of the need for additional performance test data. Phase 2 was a test program designed to increase the catalytic incinerator performance data base. It resulted in reports documenting the performance of eight catalytic incinerators at six industrial sites. The incinerators were used to control VOC emissions from solvent evaporation processes at can coating, coil coating, magnet wire, and graphic arts printing plants. Performance was measured at several process conditions at each site. Incinerator performance was characterized in terms of destruction efficiency, outlet solvent concentration, and energy usage. Design and operating data were collected. This report preseents test resultls and data evaluation for the testing conducted at the third test site, which involved the testing of two catalytic incinerators at Plant C-3, a graphic arts printing establishment.

  1. The selective catalytic cracking of Fischer-Tropsch liquids to high value transportation fuels. Final report

    SciTech Connect

    Schwartz, M.M.; Reagon, W.J.; Nicholas, J.J.; Hughes, R.D.

    1994-11-01

    Amoco Oil Company, investigated a selective catalytic cracking process (FCC) to convert the Fischer-Tropsch (F-T) gasoline and wax fractions to high value transportation fuels. The primary tasks of this contract were to (1) optimize the catalyst and process conditions of the FCC process for maximum conversion of F-T wax into reactive olefins for later production of C{sub 4}{minus}C{sub 8} ethers, and (2) use the olefin-containing light naphtha obtained from FCC processing of the F-T wax as feedstock for the synthesis of ethers. The catalytic cracking of F-T wax feedstocks gave high conversions with low activity catalysts and low process severities. HZSM-5 and beta zeolite catalysts gave higher yields of propylene, isobutylene, and isoamylenes but a lower gasoline yield than Y zeolite catalysts. Catalyst selection and process optimization will depend on product valuation. For a given catalyst and process condition, Sasol and LaPorte waxes gave similar conversions and product selectivities. The contaminant iron F-T catalyst fines in the LaPorte wax caused higher coke and hydrogen yields.

  2. Identification of a region that assists membrane insertion and translocation of the catalytic domain of Bordetella pertussis CyaA toxin.

    PubMed

    Karst, Johanna C; Barker, Robert; Devi, Usha; Swann, Marcus J; Davi, Marilyne; Roser, Stephen J; Ladant, Daniel; Chenal, Alexandre

    2012-03-16

    The adenylate cyclase (CyaA) toxin, one of the virulence factors secreted by Bordetella pertussis, the pathogenic bacteria responsible for whooping cough, plays a critical role in the early stages of respiratory tract colonization by this bacterium. The CyaA toxin is able to invade eukaryotic cells by translocating its N-terminal catalytic domain directly across the plasma membrane of the target cells, where, activated by endogenous calmodulin, it produces supraphysiological levels of cAMP. How the catalytic domain is transferred from the hydrophilic extracellular medium into the hydrophobic environment of the membrane and then to the cell cytoplasm remains an unsolved question. In this report, we have characterized the membrane-interacting properties of the CyaA catalytic domain. We showed that a protein covering the catalytic domain (AC384, encompassing residues 1-384 of CyaA) displayed no membrane association propensity. However, a longer polypeptide (AC489), encompassing residues 1-489 of CyaA, exhibited the intrinsic property to bind to membranes and to induce lipid bilayer destabilization. We further showed that deletion of residues 375-485 within CyaA totally abrogated the toxin's ability to increase intracellular cAMP in target cells. These results indicate that, whereas the calmodulin dependent enzymatic domain is restricted to the amino-terminal residues 1-384 of CyaA, the membrane-interacting, translocation-competent domain extends up to residue 489. This thus suggests an important role of the region adjacent to the catalytic domain of CyaA in promoting its interaction with and its translocation across the plasma membrane of target cells.

  3. Identification of a Region That Assists Membrane Insertion and Translocation of the Catalytic Domain of Bordetella pertussis CyaA Toxin*

    PubMed Central

    Karst, Johanna C.; Barker, Robert; Devi, Usha; Swann, Marcus J.; Davi, Marilyne; Roser, Stephen J.; Ladant, Daniel; Chenal, Alexandre

    2012-01-01

    The adenylate cyclase (CyaA) toxin, one of the virulence factors secreted by Bordetella pertussis, the pathogenic bacteria responsible for whooping cough, plays a critical role in the early stages of respiratory tract colonization by this bacterium. The CyaA toxin is able to invade eukaryotic cells by translocating its N-terminal catalytic domain directly across the plasma membrane of the target cells, where, activated by endogenous calmodulin, it produces supraphysiological levels of cAMP. How the catalytic domain is transferred from the hydrophilic extracellular medium into the hydrophobic environment of the membrane and then to the cell cytoplasm remains an unsolved question. In this report, we have characterized the membrane-interacting properties of the CyaA catalytic domain. We showed that a protein covering the catalytic domain (AC384, encompassing residues 1–384 of CyaA) displayed no membrane association propensity. However, a longer polypeptide (AC489), encompassing residues 1–489 of CyaA, exhibited the intrinsic property to bind to membranes and to induce lipid bilayer destabilization. We further showed that deletion of residues 375–485 within CyaA totally abrogated the toxin's ability to increase intracellular cAMP in target cells. These results indicate that, whereas the calmodulin dependent enzymatic domain is restricted to the amino-terminal residues 1–384 of CyaA, the membrane-interacting, translocation-competent domain extends up to residue 489. This thus suggests an important role of the region adjacent to the catalytic domain of CyaA in promoting its interaction with and its translocation across the plasma membrane of target cells. PMID:22241477

  4. Characterization of the catalytic properties of the membrane-anchored metalloproteinase ADAM9 in cell-based assays.

    PubMed

    Maretzky, Thorsten; Swendeman, Steven; Mogollon, Elin; Weskamp, Gisela; Sahin, Umut; Reiss, Karina; Blobel, Carl P

    2017-04-13

    ADAM9 (A Disintegrin And Metalloprotease 9) is a membrane-anchored metalloproteinase that has been implicated in pathological retinal neovascularization and in tumor progression. ADAM9 has constitutive catalytic activity in both biochemical and cell-based assays and can cleave several membrane proteins, including epidermal growth factor and Ephrin receptor B4; yet little is currently known about the catalytic properties of ADAM9 and its post-translational regulation and inhibitor profile in cell-based assays. To address this question, we monitored processing of the membrane-anchored Ephrin receptor B4 (EphB4) by co-expressing ADAM9, with the catalytically inactive ADAM9 E > A mutant serving as a negative control. We found that ADAM9-dependent shedding of EphB4 was not stimulated by three commonly employed activators of ADAM-dependent ectodomain shedding: phorbol esters, pervanadate or calcium ionophores. With respect to the inhibitor profile, we found that ADAM9 was inhibited by the hydroxamate-based metalloprotease inhibitors marimastat, TAPI-2, BB94, GM6001 and GW280264X, and by 10 nM of the tissue inhibitor of metalloproteinases (TIMP)-3, but not by up to 20 nM of TIMP-1 or -2. Additionally, we screened a non-hydroxamate small-molecule library for novel ADAM9 inhibitors and identified four compounds that selectively inhibited ADAM9-dependent proteolysis over ADAM10- or ADAM17-dependent processing. Taken together, the present study provides new information about the molecular fingerprint of ADAM9 in cell-based assays by showing that it is not stimulated by strong activators of ectodomain shedding and by defining a characteristic inhibitor profile. The identification of novel non-hydroxamate inhibitors of ADAM9 could provide the basis for designing more selective compounds that block the contribution of ADAM9 to pathological neovascularization and cancer. © 2017 The Author(s); published by Portland Press Limited on behalf of the Biochemical Society.

  5. X-ray structure of a CDP-alcohol phosphatidyltransferase membrane enzyme and insights into its catalytic mechanism.

    PubMed

    Nogly, Przemyslaw; Gushchin, Ivan; Remeeva, Alina; Esteves, Ana M; Borges, Nuno; Ma, Pikyee; Ishchenko, Andrii; Grudinin, Sergei; Round, Ekaterina; Moraes, Isabel; Borshchevskiy, Valentin; Santos, Helena; Gordeliy, Valentin; Archer, Margarida

    2014-06-19

    Phospholipids have major roles in the structure and function of all cell membranes. Most integral membrane proteins from the large CDP-alcohol phosphatidyltransferase family are involved in phospholipid biosynthesis across the three domains of life. They share a conserved sequence pattern and catalyse the displacement of CMP from a CDP-alcohol by a second alcohol. Here we report the crystal structure of a bifunctional enzyme comprising a cytoplasmic nucleotidyltransferase domain (IPCT) fused with a membrane CDP-alcohol phosphotransferase domain (DIPPS) at 2.65 Å resolution. The bifunctional protein dimerizes through the DIPPS domains, each comprising six transmembrane α-helices. The active site cavity is hydrophilic and widely open to the cytoplasm with a magnesium ion surrounded by four highly conserved aspartate residues from helices TM2 and TM3. We show that magnesium is essential for the enzymatic activity and is involved in catalysis. Substrates docking is validated by mutagenesis studies, and a structure-based catalytic mechanism is proposed.

  6. Catalytic fabric filtration for simultaneous NO{sub x} and particulate control. Final report

    SciTech Connect

    Weber, G.F.; Dunham, G.E.; Laudal, D.L.; Ness, S.R.; Schelkoph, G.L.

    1994-08-01

    The overall objective of the project proposed was to evaluate the catalyst-coated fabric filter concept for effective control of NO{sub 2} and particulate emissions simultaneously. General goals included demonstrating high removal efficiency of NO{sub x} and particulate matter, acceptable bag and catalyst life, and that process economics show a significant cost savings in comparison to a commercial SCR process and conventional particulate control. Specific goals included the following: reduce NO{sub x} emissions to 60 ppM or less; demonstrate particulate removal efficiency of >99.5%; demonstrate a bag/catalyst life of >1 year; Control ammonia slip to <25 ppM; show that catalytic fabric filtration can achieve a 50% cost savings over conventional fabric filtration and SCR control technology; determine compatibility with S0{sub 2} removal systems; and show that the concept results in a nonhazardous waste product.

  7. Selectable sets of novel proteins: catalytic and other properties. Final report, 1 July-30 September 1988

    SciTech Connect

    Kauffman, S.A.

    1989-05-08

    This proposal aimed at the development of mathematical, computer, recombinant DNA, selection and screening procedures to attain adaptive evolution of entirely novel peptides or fusion proteins with useful catalytic, ligand binding, structural, or other features. Potential uses range from industrial catalysis to production of new drugs and vaccines. A broad purpose of the experimental effort is to obtain novel peptides that can mimic the biological effects of almost arbitrary signal molecules such as hormones, growth factors, even pathogenic antigens. Mathematical models were developed to explore rugged 'adaptive landscapes' associated with protein evolution. The fundamental importance of this work includes analysis of the distribution of function in peptide space and opening the way towards a technology of applied molecular evolution.

  8. Infrared and catalytic burner technology assessment. Final report, 21 February 1980-20 February 1981

    SciTech Connect

    Kesselring, J.P.; Krill, W.V.; Schreiber, R.J.

    1981-02-01

    The results of a review of the state of the art in infrared and catalytic burner development are presented. Four basic types of IR burners are currently is use. Eight commercial and/or residential appliances were characterized to assess the applicability of these burners. The refractory monolith tile and the fiber matrix burners appear most applicable for appliance use. Conceptual designs for the eight appliances with IR burners were prepared to evaluate the technical feasibility. These appliances are shown to have significant fuel efficiency increase and NOx and CO emission reduction benefits. Four appliances -- the commercial rangetop, deep fat fryer, commercial water heater, and warm air furnace -- also appear economically competitive, and recommended approaches for further development are presented. Lists of IR burner literature and patents are also included.

  9. Replacement of chemical intensive water treatment processes with energy saving membrane. Final report

    SciTech Connect

    Mickley, M.C.; Goering, S.W.

    1983-11-01

    The project investigated the use of charged ultrafiltration membranes to treat hard water. More specifically, the work was undertaken to (1) make charged ultrafiltration membranes to demonstrate the technical feasibility of the chemical grafting approach; (2) evaluate the market potential for charged ultrafiltration membranes; and (3) evaluate the cost and energy savings for using charged ultrafiltration as compared to lime-based clarification and other treatment methods. The results suggest that chemical grafting is a relatively simple, reproducible and low-cost way to modify existing substrate materials to give them enhanced transport performance. Process studies lead to the identification of good market potential for membrane processes using charged ultrafiltration membranes. Capital and operating costs relative to lime-based clarification are favorable for low- and medium-sized treatment plants. Finally, substantial energy savings are apparent as compared to lime-based precipitation systems which incur substantial energy consumption in the lime production and transportation steps.

  10. Advanced treatment of biologically pretreated coal gasification wastewater by a novel integration of catalytic ultrasound oxidation and membrane bioreactor.

    PubMed

    Jia, Shengyong; Han, Hongjun; Zhuang, Haifeng; Xu, Peng; Hou, Baolin

    2015-01-01

    Laboratorial scale experiments were conducted to investigate a novel system integrating catalytic ultrasound oxidation (CUO) with membrane bioreactor (CUO-MBR) on advanced treatment of biologically pretreated coal gasification wastewater. Results indicated that CUO with catalyst of FeOx/SBAC (sewage sludge based activated carbon (SBAC) which loaded Fe oxides) represented high efficiencies in eliminating TOC as well as improving the biodegradability. The integrated CUO-MBR system with low energy intensity and high frequency was more effective in eliminating COD, BOD5, TOC and reducing transmembrane pressure than either conventional MBR or ultrasound oxidation integrated MBR. The enhanced hydroxyl radical oxidation, facilitation of substrate diffusion and improvement of cell enzyme secretion were the mechanisms for CUO-MBR performance. Therefore, the integrated CUO-MBR was the promising technology for advanced treatment in engineering applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Enhanced catalytic stability of lipase immobilized on oxidized and disulfide-rich eggshell membrane for esters hydrolysis and transesterification.

    PubMed

    Jiang, Chenyu; Cheng, Chuanchuan; Hao, Mei; Wang, Hongbin; Wang, Ziying; Shen, Cai; Cheong, Ling-Zhi

    2017-07-30

    Eggshell membrane (ESM) is an industrial waste that is available in abundance from food industry. Present study investigated the physicochemical properties of oxidized ESM and compared the efficiency of ESM and oxidized ESM as carrier for Burkholderia cepacia lipase (BCL) used in esters hydrolysis and transesterification. Following oxidation treatment, FTIR analysis and Ellman's assay showed amino acid cysteine in ESM was oxidized to form disulfide bond-containing cystine. In addition, AFM analysis showed ESM which exhibited a highly porous filamentous structure appeared to be coalesce following oxidation treatment. Oxidized ESM also showed reduced porosity (38.67%) in comparison to native ESM (51.65%). BCL were successfully immobilized on oxidized ESM through carrier activation method (enzyme loading of 5.01mg protein/g oxidized ESM). These immobilized lipase demonstrated significantly (P<0.05) enhanced catalytic stability with close to 100% of initial hydrolysis (12.03±0.29mmol/min/g) activity; and more than 85% of its initial transesterification (7.83±0.05) activity for at least 10 consecutive runs. Enhanced catalytic stability of BCL immobilized on oxidized ESM might be due to stabilization of the protein structure in oxidized ESM by disulfide bonds which helped formation of a stable bonding with BCL. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Expression, purification and crystallization of a membrane-associated, catalytically active type I signal peptidase from Staphylococcus aureus.

    PubMed

    Ting, Yi Tian; Batot, Gaëlle; Baker, Edward N; Young, Paul G

    2015-01-01

    Staphylococcus aureus infections are becoming increasingly difficult to treat as they rapidly develop resistance to existing antibiotics. Bacterial type I signal peptidases are membrane-associated, cell-surface serine proteases with a unique catalytic mechanism that differs from that of eukaryotic endoplasmic reticulum signal peptidases. They are thus potential antimicrobial targets. S. aureus has a catalytically active type I signal peptidase, SpsB, that is essential for cell viability. To elucidate its structure, the spsB gene from S. aureus Newman strain was cloned and overexpressed in Escherichia coli. After exploring many different protein-modification constructs, SpsB was expressed as a fusion protein with maltose-binding protein and crystallized by hanging-drop vapour diffusion. The crystals belonged to the monoclinic space group P2(1) and diffracted to 2.05 Å resolution. The crystal structure of SpsB is anticipated to provide structural insight into Gram-positive signal peptidases and to aid in the development of antibacterial agents that target type I signal peptidases.

  13. Final technical report for the Center for Catalytic Hydrocarbon Functionalization (an EFRC)

    SciTech Connect

    Gunnoe, Thomas Brent

    2016-11-11

    Greater than 95% of all materials produced by the chemical industry are derived from a small slate of simple hydrocarbons that are derived primarily from natural gas and petroleum, predominantly through oxygenation, C–C bond formation, halogenation or amination. Yet, current technologies for hydrocarbon conversion are typically high temperature, multi-step processes that are energy and capital intensive and result in excessive emissions (including carbon dioxide). The Center for Catalytic Hydrocarbon Functionalization (CCHF) brought together research teams with the broad coalition of skills and knowledge needed to make the fundamental advances in catalysis required for next-generation technologies to convert hydrocarbons (particularly light alkanes and methane) at high efficiency and low cost. Our new catalyst technologies offer many opportunities including enhanced utilization of natural gas in the transportation sector (via conversion to liquid fuels), more efficient generation of electricity from natural gas using direct methane fuel cells, reduced energy consumption and waste production for large petrochemical processes, and the preparation of high value molecules for use in biological/medical applications or the agricultural sector. The five year collaborative project accelerated fundamental understanding of catalyst design for the conversion of C–H bonds to functionalized products, essential to achieve the goals listed above, as evidenced by the publication of 134 manuscripts. Many of these fundamental advancements provide a foundation for potential commercialization, as evidenced by the submission of 11 patents from research support by the CCHF.

  14. Spatially resolved characterization of catalyst-coated membranes by distance-controlled scanning mass spectrometry utilizing catalytic methanol oxidation as gas-solid probe reaction.

    PubMed

    Li, Nan; Assmann, Jens; Schuhmann, Wolfgang; Muhler, Martin

    2007-08-01

    The spatially resolved catalytic activity of a catalyst-coated membrane (CCM), which is the essential part of PEM fuel cells, was visualized rapidly without any damage by a distance-controlled scanning mass spectrometer with an improved resolution of 250 microm. Methanol oxidation was identified as a suitable gas-solid probe reaction for the characterization of local catalytic activity. In addition, defects were manually generated in the CCM to simulate inhomogeneous coating and pinholes. The measurements successfully demonstrated that catalytically active and less active regions can be clearly distinguished. Simultaneously, the local topography was recorded, providing additional information on the location of the scratches and pinholes. The catalytic results were highly reproducible due to the constant-distance feedback loop rendering scanning mass spectrometry a promising tool for the quantitative quality control of CCMs.

  15. Removal of diatrizoate with catalytically active membranes incorporating microbially produced palladium nanoparticles.

    PubMed

    Hennebel, Tom; De Corte, Simon; Vanhaecke, Lynn; Vanherck, Katrien; Forrez, Ilse; De Gusseme, Bart; Verhagen, Pieter; Verbeken, Kim; Van der Bruggen, Bart; Vankelecom, Ivo; Boon, Nico; Verstraete, Willy

    2010-03-01

    There is an increasing concern about the fate of iodinated contrast media (ICM) in the environment. Limited removal efficiencies of currently applied techniques such as advanced oxidation processes require more performant strategies. The aim of this study was to establish an innovative degradation process for diatrizoate, a highly recalcitrant ICM, by using biogenic Pd nanoparticles as free suspension or immobilized in polyvinylidene fluoride (PVDF) and polysulfone (PSf) membranes. As measured by HPLC-UV, the removal of 20mg L(-1) diatrizoate by a 10mg L(-1) Pd suspension was completed after 4h at a pH of 10. LC-MS analysis provided evidence for the sequential hydrodeiodination of diatrizoate. Pd did not lose its activity after incorporation in the PVDF and PSf matrix and the highest activity (k(cat)=30.0+/-0.4h(-1) L g(-1) Pd) was obtained with a casting solution of 10% PSf and 500mg L(-1) Pd. Subsequently, water containing 20mg L(-1) diatrizoate was treated in a membrane contactor, in which the water was supplied at one side of the membrane while hydrogen was provided at the other side. In a fed batch configuration, a removal efficiency of 77% after a time period of 48h was obtained. This work showed that membrane contactors with encapsulated biogenic nanoparticles can be instrumental for treatment of water contaminated with diatrizoate.

  16. Catalytic conversion of light alkanes-proof-of-concept stage -- Phase 6. Final report, February 1--October 31, 1994

    SciTech Connect

    1994-12-31

    During the course of the first three years of the Cooperative Agreement, the authors uncovered a family of metal perhaloporphyrin complexes which had unprecedented activity for the selective air-oxidation of light alkanes to alcohols. The reactivity of light hydrocarbon substrates with air or oxygen was in the order: isobutane > propane > ethane > methane, in accord with their homolytic bond dissociation energies. Isobutane was so reactive that the proof-of-concept stage of a process for producing tert-butyl alcohol from isobutane was begun (Phase 5). It was proposed that as more active catalytic systems were developed (Phases 4, 6), propane, then ethane and finally methane oxidations will move into this stage (Phases 7 through 9). As of this writing, however, the program has been terminated during the later stages of Phase 5 and 6 so that further work is not anticipated. 72 refs.

  17. Continuous esterification to produce biodiesel by SPES/PES/NWF composite catalytic membrane in flow-through membrane reactor: experimental and kinetic studies.

    PubMed

    Shi, Wenying; He, Benqiao; Cao, Yuping; Li, Jianxin; Yan, Feng; Cui, Zhenyu; Zou, Zhiqun; Guo, Shiwei; Qian, Xiaomin

    2013-02-01

    A novel composite catalytic membrane (CCM) was prepared from sulfonated polyethersulfone (SPES) and polyethersulfone (PES) blend supported by non-woven fabrics, as a heterogeneous catalyst to produce biodiesel from continuous esterification of oleic acid with methanol in a flow-through mode. A kinetic model of esterification was established based on a plug-flow assumption. The effects of the CCM structure (thickness, area, porosity, etc.), reaction temperature and the external and internal mass transfer resistances on esterification were investigated. The results showed that the CCM structure had a significant effect on the acid conversion. The external mass transfer resistance could be neglected when the flow rate was over 1.2 ml min(-1). The internal mass transfer resistance impacted on the conversion when membrane thickness was over 1.779 mm. An oleic acid conversion kept over 98.0% for 500 h of continuous running. The conversions obtained from the model are in good agreement with the experimental data. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Final Report: Investigation of Catalytic Pathways for Lignin Breakdown into Monomers and Fuels

    SciTech Connect

    Gluckstein, Jeffrey A; Hu, Michael Z.; Kidder, Michelle; McFarlane, Joanna; Narula, Chaitanya Kumar; Sturgeon, Matthew R

    2010-12-01

    Lignin is a biopolymer that comprises up to 35% of woody biomass by dry weight. It is currently underutilized compared to cellulose and hemicellulose, the other two primary components of woody biomass. Lignin has an irregular structure of methoxylated aromatic groups linked by a suite of ether and alkyl bonds which makes it difficult to degrade selectively. However, the aromatic components of lignin also make it promising as a base material for the production of aromatic fuel additives and cyclic chemical feed stocks such as styrene, benzene, and cyclohexanol. Our laboratory research focused on three methods to selectively cleave and deoxygenate purified lignin under mild conditions: acidolysis, hydrogenation and electrocatalysis. (1) Acidolysis was undertaken in CH2Cl2 at room temperature. (2) Hydrogenation was carried out by dissolving lignin and a rhodium catalyst in 1:1 water:methoxyethanol under a 1 atm H2 environment. (3) Electrocatalysis of lignin involved reacting electrically generated hydrogen atoms at a catalytic palladium cathode with lignin dissolved in a solution of aqueous methanol. In all of the experiments, the lignin degradation products were identified and quantified by gas chromatography mass spectroscopy and flame ionization detection. Yields were low, but this may have reflected the difficulty in recovering the various fractions after conversion. The homogeneous hydrogenation of lignin showed fragmentation into monomers, while the electrocatalytic hydrogenation showed production of polyaromatic hydrocarbons and substituted benzenes. In addition to the experiments, promising pathways for the conversion of lignin were assessed. Three conversion methods were compared based on their material and energy inputs and proposed improvements using better catalyst and process technology. A variety of areas were noted as needing further experimental and theoretical effort to increase the feasibility of lignin conversion to fuels.

  19. Preconversion catalytic deoxygenation of phenolic functional groups. Final technical report, September 1, 1989--August 31, 1992

    SciTech Connect

    Kubiak, C.P.

    1992-12-31

    Several new catalysts for phenol deoxygenation by CO were developed in our laboratories during the grant period. The deoxygenation of phenols by CO represents a.novel approach to the upgrading of coal liquids. The deoxygenation of phenols by CO is thermodynamically more favorable and potentially less expensive than current phenol hydrodeoxygenation (HDO) methods. The reaction was not known to be kinetically feasible until our recent discovery of appropriate catalysts. The catalyst precursor [Ir(triphos)({eta}{sup 4{minus}}C{sub 8}H{sub 12})][C1] was found to catalytically deoxygenate phenol and p-cresol. Reactions were conducted with varying amounts of AR-OH (Ar = C{sub 6}H{sub 5}, p-Me-C{sub 6}H{sub 4}), NaO-Ar, and catalyst precursor. In some reactions, triethyl amine was substituted for NaO-Ar to deprotonate the ArOH. All reactions took place at 55{degrees}C so that AR-OH was the solvent One atmosphere of CO was introduced into each reactor. Periodically, gasses were sampled by gas chromatography (GC) to monitor the disappearance of CO and the appearance of CO{sub 2}. After the amount of CO{sub 2} had reached a plateau, organic products were distilled from the reaction mixture and analyzed by high pressure liquid chromatography (HPLC). Significant quantities of arene (benzene or toluene) were obtained. These results are general. Initial use of phenol results in only benzene. Initial use of p-cresol results in only toluene. Control reactions eliminate the catalyst precursor as the source Of CO{sub 2} or arene. No evidence is obtained for diarylcarbonate formation. HPLC and GC data from consistently demonstrated that toluene and CO{sub 2} were the only products obtained from the deoxygenation of p-cresol by CO. These results were extended to a series of variously substituted phenolic and naptholic substrates related to those found in coal liquids.

  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. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor.

    PubMed

    Morejudo, S H; Zanón, R; Escolástico, S; Yuste-Tirados, I; Malerød-Fjeld, H; Vestre, P K; Coors, W G; Martínez, A; Norby, T; Serra, J M; Kjølseth, C

    2016-08-05

    Nonoxidative methane dehydroaromatization (MDA: 6CH4 ↔ C6H6 + 9H2) using shape-selective Mo/zeolite catalysts is a key technology for exploitation of stranded natural gas reserves by direct conversion into transportable liquids. However, this reaction faces two major issues: The one-pass conversion is limited by thermodynamics, and the catalyst deactivates quickly through kinetically favored formation of coke. We show that integration of an electrochemical BaZrO3-based membrane exhibiting both proton and oxide ion conductivity into an MDA reactor gives rise to high aromatic yields and improved catalyst stability. These effects originate from the simultaneous extraction of hydrogen and distributed injection of oxide ions along the reactor length. Further, we demonstrate that the electrochemical co-ionic membrane reactor enables high carbon efficiencies (up to 80%) that improve the technoeconomic process viability. Copyright © 2016, American Association for the Advancement of Science.

  2. Energy Efficient Catalytic Activation of Hydrogen peroxide for Green Chemical Processes: Final Report

    SciTech Connect

    Collins, Terrence J.; Horwitz, Colin

    2004-11-12

    A new, highly energy efficient approach for using catalytic oxidation chemistry in multiple fields of technology has been pursued. The new catalysts, called TAML® activators, catalyze the reactions of hydrogen peroxide and other oxidants for the exceptionally rapid decontamination of noninfectious simulants (B. atrophaeus) of anthrax spores, for the energy efficient decontamination of thiophosphate pesticides, for the facile, low temperature removal of color and organochlorines from pulp and paper mill effluent, for the bleaching of dyes from textile mill effluents, and for the removal of recalcitrant dibenzothiophene compounds from diesel and gasoline fuels. Highlights include the following: 1) A 7-log kill of Bacillus atrophaeus spores has been achieved unambiguously in water under ambient conditions within 15 minutes. 2) The rapid total degradation under ambient conditions of four thiophosphate pesticides and phosphonate degradation intermediates has been achieved on treatment with TAML/peroxide, opening up potential applications of the decontamination system for phosphonate structured chemical warfare agents, for inexpensive, easy to perform degradation of stored and aged pesticide stocks (especially in Africa and Asia), for remediation of polluted sites and water bodies, and for the destruction of chemical warfare agent stockpiles. 3) A mill trial conducted in a Pennsylvanian bleached kraft pulp mill has established that TAML catalyst injected into an alkaline peroxide bleach tower can significantly lower color from the effluent stream promising a new, more cost effective, energy-saving approach for color remediation adding further evidence of the value and diverse engineering capacity of the approach to other field trials conducted on effluent streams as they exit the bleach plant. 4) Dibenzothiophenes (DBTs), including 4,6-dimethyldibenzothiophene, the most recalcitrant sulfur compounds in diesel and gasoline, can be completely removed from model gasoline

  3. Process engineering and economic evaluations of diaphragm and membrane chlorine cell technologies. Final report

    SciTech Connect

    Not Available

    1980-12-01

    The chlor-alkali manufacturing technologies of (1), diaphragm cells (2), current technology membrane cells (3), catalytic cathode membrane cells (4), oxygen-cathode membrane cells and to a lesser extent several other related emerging processes are studied. Comparisons have been made on the two bases of (1) conventional industrial economics, and (2) energy consumption. The current diaphragm cell may have a small economic advantage over the other technologies at the plant size of 544 metric T/D (600 T/D). The three membrane cells all consume less energy, with the oxygen-cathode cell being the lowest. The oxygen-cathode cell appears promising as a low energy chlor-alkali cell where there is no chemical market for hydrogen. Federal funding of the oxygen-cathode cell has been beneficial to the development of the technology, to electrochemical cell research, and may help maintain the US's position in the international chlor-alkali technology marketplace. Tax law changes inducing the installation of additional cells in existing plants would produce the quickest reduction in power consumption by the chlor-alkali industry. Alternative technologies such as the solid polymer electrolyte cell, the coupling of diaphragm cells with fuel cells and the dynamic gel diaphragm have a strong potential for reducing chloralkali industry power consumption. Adding up all the recent and expected improvements that have become cost-effective, the electrical energy required to produce a unit of chlorine by 1990 should be only 50% to 60% of that used in 1970. In the United States the majority of the market does not demand salt-free caustic. About 75% of the electrolytic caustic is produced in diaphragm cells and only a small part of that is purified. This study indicates that unless membrane cell costs are greatly reduced or a stronger demand develops for salt-free caustic, the diaphragm cells will remain competitive. (WHK)

  4. Porous Au-Ag Alloy Particles Inlaid AgCl Membranes As Versatile Plasmonic Catalytic Interfaces with Simultaneous, in Situ SERS Monitoring.

    PubMed

    Cao, Qi; Yuan, Kaiping; Liu, Qinghe; Liang, Chongyun; Wang, Xiang; Cheng, Yi-Feng; Li, Qingqing; Wang, Min; Che, Renchao

    2015-08-26

    We present a novel porous Au-Ag alloy particles inlaid AgCl membrane as plasmonic catalytic interfaces with real-time, in situ surface-enhanced Raman spectroscopy (SERS) monitoring. The Au-Ag alloy particles inlaid AgCl membranes were obtained via a facile two-step, air-exposed, and room-temperature immersion reaction with appropriate annealing process. Owing to the designed integration of semiconductor component AgCl and noble metal Au-Ag particles, both the catalytic reduction and visible-light-driven photocatalytic activities toward organic contaminants were attained. Specifically, the efficiencies of about 94% of 4-nitrophenol (4-NP, 5 × 10(-5) M) reduction after 8 min of reaction, and degradation of rhodamine 6G (R6G, 10(-5) M) after 12 min of visible light irradiation were demonstrated. Moreover, efficiencies of above 85% of conversion of 4-NP to 4-aminophenol (4-AP) and 90% of R6G degradation were achieved as well after 6 cycles of reactions, by which robust recyclability was confirmed. Further, with distinct SERS signals generated simultaneously from the surfaces of Au-Ag particles under laser excitation, in situ SERS monitoring of the process of catalytic reactions with superior sensitivity and linearity has been realized. Overall, the capability of the Au-Ag particles inlaid AgCl membranes to provide SERS monitored catalytic and visible-light-driven photocatalytic conversion of organic pollutants, along with their mild and cost-effective fabrication method, would make sense for in-depth understanding of the mechanisms of (photo)catalytic reactions, and also future development of potable, multifunctional and integrated catalytic and sensing devices.

  5. Separation of Olefin/Paraffin Mixtures with Carrier Facilitated Membrane Final Report

    SciTech Connect

    Merkel, T.C.; Blanc, R.; Zeid, J.; Suwarlim, A.; Firat, B.; Wijmans, H.; Asaro, M.; Greene, M.

    2007-03-12

    to improve membrane coating solution stability resulted in the finding that membrane performance loss could be reversed for all poisoning cases except hydrogen sulfide exposure. This discovery offers the potential to extend membrane lifetime through cyclic regeneration. We also found that certain mixed carriers exhibited greater stability in reducing environments than exhibited by silver salt alone. These results offer promise that solutions to deal with carrier poisoning are possible. The main achievement of this program was the progress made in gaining a more complete understanding of the membrane stability challenges faced in the use of facilitated olefin transport membranes. Our systematic study of facilitated olefin transport uncovered the full extent of the stability challenge, including the first known identification of olefin conditioning and its impact on membrane development. We believe that significant additional fundamental research is required before facilitated olefin transport membranes are ready for industrial implementation. The best-case scenario for further development of this technology would be identification of a novel carrier that is intrinsically more stable than silver ions. If the stability problems could be largely circumvented by development of a new carrier, it would provide a clear breakthrough toward finally recognizing the potential of facilitated olefin transport. However, even if such a carrier is identified, additional development will be required to insure that the membrane matrix is a benign host for the olefin-carrier complexation reaction and shows good long-term stability.

  6. Development of a Novel Catalytic Membrane Reactor for Heterogeneous Catalysis in Supercritical CO2

    PubMed Central

    Islam, Nazrul M.; Chatterjee, Maya; Ikushima, Yutaka; Yokoyama, Toshiro; Kawanami, Hajime

    2010-01-01

    A novel type of high-pressure membrane reactor has been developed for hydrogenation in supercritical carbon dioxide (scCO2). The main objectives of the design of the reactor are the separate feeding of hydrogen and substrate in scCO2 for safe reactions in a continuous flow process, and to reduce the reaction time. By using this new reactor, hydrogenation of cinnamaldehyde into hydrocinnamaldehyde has been successfully carried out with 100% selectivity at 50 °C in 10 MPa (H2: 1 MPa, CO2: 9 MPa) with a flow rate of substrate ranging from 0.05 to 1.0 mL/min. PMID:20162008

  7. Development of a novel catalytic membrane reactor for heterogeneous catalysis in supercritical CO₂.

    PubMed

    Islam, Nazrul M; Chatterjee, Maya; Ikushima, Yutaka; Yokoyama, Toshiro; Kawanami, Hajime

    2010-01-13

    A novel type of high-pressure membrane reactor has been developed for hydrogenation in supercritical carbon dioxide (scCO(2)). The main objectives of the design of the reactor are the separate feeding of hydrogen and substrate in scCO(2) for safe reactions in a continuous flow process, and to reduce the reaction time. By using this new reactor, hydrogenation of cinnamaldehyde into hydrocinnamaldehyde has been successfully carried out with 100% selectivity at 50 degrees C in 10 MPa (H(2): 1 MPa, CO(2): 9 MPa) with a flow rate of substrate ranging from 0.05 to 1.0 mL/min.

  8. Integration of Methane Steam Reforming and Water Gas Shift Reaction in a Pd/Au/Pd-Based Catalytic Membrane Reactor for Process Intensification

    PubMed Central

    Castro-Dominguez, Bernardo; Mardilovich, Ivan P.; Ma, Liang-Chih; Ma, Rui; Dixon, Anthony G.; Kazantzis, Nikolaos K.; Ma, Yi Hua

    2016-01-01

    Palladium-based catalytic membrane reactors (CMRs) effectively remove H2 to induce higher conversions in methane steam reforming (MSR) and water-gas-shift reactions (WGS). Within such a context, this work evaluates the technical performance of a novel CMR, which utilizes two catalysts in series, rather than one. In the process system under consideration, the first catalyst, confined within the shell side of the reactor, reforms methane with water yielding H2, CO and CO2. After reforming is completed, a second catalyst, positioned in series, reacts with CO and water through the WGS reaction yielding pure H2O, CO2 and H2. A tubular composite asymmetric Pd/Au/Pd membrane is situated throughout the reactor to continuously remove the produced H2 and induce higher methane and CO conversions while yielding ultrapure H2 and compressed CO2 ready for dehydration. Experimental results involving (i) a conventional packed bed reactor packed (PBR) for MSR, (ii) a PBR with five layers of two catalysts in series and (iii) a CMR with two layers of two catalysts in series are comparatively assessed and thoroughly characterized. Furthermore, a comprehensive 2D computational fluid dynamics (CFD) model was developed to explore further the features of the proposed configuration. The reaction was studied at different process intensification-relevant conditions, such as space velocities, temperatures, pressures and initial feed gas composition. Finally, it is demonstrated that the above CMR module, which was operated for 600 h, displays quite high H2 permeance and purity, high CH4 conversion levels and reduced CO yields. PMID:27657143

  9. Degradative inactivation of cyclic AMP-dependent protein kinase by a membranal proteinase is restricted to the free catalytic subunit in its native conformation.

    PubMed Central

    Alhanaty, E; Patinkin, J; Tauber-Finkelstein, M; Shaltiel, S

    1981-01-01

    A membranal proteinase from brush-border epithelial cells of the rat small intestine was shown to bring about a restricted and limited degradation of the free catalytic subunit (C) of cyclic AMP-dependent protein kinase (ATP:protein phosphotransferase, EC 2.7.1.37) with concomitant inactivation of the kinase. This membranal proteinase exhibits a remarkable specificity. (i) It degrades C in its native conformation, but not after it has been heat-denatured. (ii) The degradation of C (Mr 40,000) does not proceed further, once a distinct clipped product (Mr 34,000) is formed. (iii) The undissociated ("stored") form of the enzyme (R2C2) is not attacked by the membranal proteinase, preserving both its potential catalytic activity and its molecular integrity. Only upon addition of cyclic AMP to release free C does the proteinase attack it. (iv) The membranal proteinase does not degrade the regulatory subunit (R), released by cyclic AMP from R2C2, although R is quite susceptible to degradation by other proteolytic enzymes. None of these features of the membranal proteinase could be reproduced with trypsin, chymotrypsin, clostripain, or papain. The specific, restricted, and limited action of this membranal enzyme raises the possibility that it may have a distinct physiological assignment associated with the bioregulation of cyclic AMP-dependent protein kinase. Images PMID:6267595

  10. Degradative inactivation of cyclic AMP-dependent protein kinase by a membranal proteinase is restricted to the free catalytic subunit in its native conformation.

    PubMed

    Alhanaty, E; Patinkin, J; Tauber-Finkelstein, M; Shaltiel, S

    1981-06-01

    A membranal proteinase from brush-border epithelial cells of the rat small intestine was shown to bring about a restricted and limited degradation of the free catalytic subunit (C) of cyclic AMP-dependent protein kinase (ATP:protein phosphotransferase, EC 2.7.1.37) with concomitant inactivation of the kinase. This membranal proteinase exhibits a remarkable specificity. (i) It degrades C in its native conformation, but not after it has been heat-denatured. (ii) The degradation of C (Mr 40,000) does not proceed further, once a distinct clipped product (Mr 34,000) is formed. (iii) The undissociated ("stored") form of the enzyme (R2C2) is not attacked by the membranal proteinase, preserving both its potential catalytic activity and its molecular integrity. Only upon addition of cyclic AMP to release free C does the proteinase attack it. (iv) The membranal proteinase does not degrade the regulatory subunit (R), released by cyclic AMP from R2C2, although R is quite susceptible to degradation by other proteolytic enzymes. None of these features of the membranal proteinase could be reproduced with trypsin, chymotrypsin, clostripain, or papain. The specific, restricted, and limited action of this membranal enzyme raises the possibility that it may have a distinct physiological assignment associated with the bioregulation of cyclic AMP-dependent protein kinase.

  11. Facile in situ synthesis of silver nanoparticles on procyanidin-grafted eggshell membrane and their catalytic properties.

    PubMed

    Liang, Miao; Su, Rongxin; Huang, Renliang; Qi, Wei; Yu, Yanjun; Wang, Libing; He, Zhimin

    2014-04-09

    Facile, efficient, and robust immobilization of metal nanostructures on porous bioscaffolds is an interesting topic in materials chemistry and heterogeneous catalysis. This study reports a facile in situ method for the synthesis and immobilization of small silver nanoparticles (AgNPs) at room temperature on natural eggshell membrane (ESM), which presents interwoven fibrous structure and can be used as a unique protein-based biotemplate. Procyanidin (Pro), a typical plant polyphenol extracted from grape seeds and skins, was first grafted onto ESM fibers to serve as both reductant and stabilizer during the synthesis process. As a result, the AgNPs were facilely synthesized and robustly immobilized on the ESM fibers without additional chemical reductant or physical treatments. The morphology and microstructure of the as-prepared AgNPs@Pro-ESM composites were characterized by combined microscopy and spectroscopy technologies. The results indicate that small AgNPs with mean diameter of 2.46 nm were successfully prepared on the Pro-ESM biotemplate. The composites exhibited good catalytic activity toward the reduction of 4-nitrophenol (4-NP). More importantly, these composite catalysts can be easily recovered and reused for more than eight cycles because of their high stability.

  12. Final Report: Computer Simulation of Osmosis and Reverse Osmosis in Structured Membranes

    SciTech Connect

    Sohail Murad

    2012-01-03

    Molecular simulation methods were developed as part of this project to increase our fundamental understanding of membrane based separation systems. Our simulations clarified for example that steric (size) effects had a significant impact on the desalination membranes. Previously it was thought the separation was entirely driven by coulombic force (attractive/repulsive forces at the membrane surfaces). Steric effects played an important role, because salt ions in brackish water are never present alone, but are strongly hydrated which effectively increases their size, and makes it impossible to enter a membrane, while the smaller water molecules can enter more readily. Membrane surface effects did play a role in increasing the flux of water, but not in the separation itself. In addition we also developed simulation methods to study ion exchange, gas separations, and pervaporation. The methods developed were used to once again increase our fundamental understanding of these separation processes. For example our studies showed that when the separation factor of gases in membranes can be significantly affected by the presence of another gas, it is generally because the separation mechanism has changed. For example in the case of nitrogen and carbon dioxide, in their pure state the separation factor is determined by diffusion, while in mixtures it is influenced more by adsorption in the membrane (zeolite in our case) Finally we developed a new technique using the NMR chemical shift to determine intermolecular interactions for mixtures. For polar-nonpolar systems such as Xe dissolved in water we were able to significantly improve the accuracy of gas solubilities, which are very sensitive to the cross interaction between water and Xe.

  13. Shape-dependent plasma-catalytic activity of ZnO nanomaterials coated on porous ceramic membrane for oxidation of butane.

    PubMed

    Sanjeeva Gandhi, M; Mok, Young Sun

    2014-12-01

    In order to explore the effects of the shape of ZnO nanomaterials on the plasma-catalytic decomposition of butane and the distribution of byproducts, three types of ZnO nanomaterials (nanoparticles (NPs), nanorods (NRs) and nanowires (NWs)) were prepared and coated on multi-channel porous alumina ceramic membrane. The structures and morphologies of the nanomaterials were confirmed by X-ray diffraction method and scanning electron microscopy. The observed catalytic activity of ZnO in the oxidative decomposition of butane was strongly shape-dependent. It was found that the ZnO NWs exhibited higher catalytic activity than the other nanomaterials and could completely oxidize butane into carbon oxides (COx). When using the bare or ZnO NPs-coated ceramic membrane, several unwanted partial oxidation and decomposition products like acetaldehyde, acetylene, methane and propane were identified during the decomposition of butane. When the ZnO NWs- or ZnO NRs-coated membrane was used, however, the formation of such unwanted byproducts except methane was completely avoided, and full conversion into COx was achieved. Better carbon balance and COx selectivity were obtained with the ZnO NWs and NRs than with the NPs. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Norbin Stimulates the Catalytic Activity and Plasma Membrane Localization of the Guanine-Nucleotide Exchange Factor P-Rex1*

    PubMed Central

    Pan, Dingxin; Barber, Mark A.; Hornigold, Kirsti; Baker, Martin J.; Toth, Judit M.; Oxley, David; Welch, Heidi C. E.

    2016-01-01

    P-Rex1 is a guanine-nucleotide exchange factor (GEF) that activates the small G protein (GTPase) Rac1 to control Rac1-dependent cytoskeletal dynamics, and thus cell morphology. Three mechanisms of P-Rex1 regulation are currently known: (i) binding of the phosphoinositide second messenger PIP3, (ii) binding of the Gβγ subunits of heterotrimeric G proteins, and (iii) phosphorylation of various serine residues. Using recombinant P-Rex1 protein to search for new binding partners, we isolated the G-protein-coupled receptor (GPCR)-adaptor protein Norbin (Neurochondrin, NCDN) from mouse brain fractions. Coimmunoprecipitation confirmed the interaction between overexpressed P-Rex1 and Norbin in COS-7 cells, as well as between endogenous P-Rex1 and Norbin in HEK-293 cells. Binding assays with purified recombinant proteins showed that their interaction is direct, and mutational analysis revealed that the pleckstrin homology domain of P-Rex1 is required. Rac-GEF activity assays with purified recombinant proteins showed that direct interaction with Norbin increases the basal, PIP3- and Gβγ-stimulated Rac-GEF activity of P-Rex1. Pak-CRIB pulldown assays demonstrated that Norbin promotes the P-Rex1-mediated activation of endogenous Rac1 upon stimulation of HEK-293 cells with lysophosphatidic acid. Finally, immunofluorescence microscopy and subcellular fractionation showed that coexpression of P-Rex1 and Norbin induces a robust translocation of both proteins from the cytosol to the plasma membrane, as well as promoting cell spreading, lamellipodia formation, and membrane ruffling, cell morphologies generated by active Rac1. In summary, we have identified a novel mechanism of P-Rex1 regulation through the GPCR-adaptor protein Norbin, a direct P-Rex1 interacting protein that promotes the Rac-GEF activity and membrane localization of P-Rex1. PMID:26792863

  15. Effect of the catalytic ink preparation method on the performance of high temperature polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Lobato, J.; Rodrigo, M. A.; Linares, J. J.; Scott, K.

    Two methods of preparation of the membrane-electrode-assemblies based on polybenzimidazole membranes have been studied for high temperatures PEMFCs. One is called the "colloidal method" (using acetone as solvent), and the other is the "solution method" (using dimethylacetamide as solvent). Physical property studies (SEM micrographs and pore size distribution) and electrochemical analyses in half-cell (Electrochemical Impedance Spectroscopy, Polarization Curves for Oxygen Reduction and Cyclic Voltammetry) were carried out to characterise the structural and electrochemical behaviour of both methods. Finally, a cell performance investigation, using electrodes prepared by both methods was carried out at three different temperatures (125, 150, and 175 °C), in a single PEMFC setup. A better behaviour was obtained for the "solution method" at the two highest temperatures at intermediate current densities, whereas at 125 °C the best results were obtained with the "colloidal method" in all the current densities ranges. A discussion of the behaviours observed with the different characterisation techniques is made.

  16. High temperature ceramic membrane reactors for coal liquid upgrading. Final report, September 21, 1989--November 20, 1992

    SciTech Connect

    Tsotsis, T.T.; Liu, P.K.T.; Webster, I.A.

    1992-12-31

    Membrane reactors are today finding extensive applications for gas and vapor phase catalytic reactions (see discussion in the introduction and recent reviews by Armor [92], Hsieh [93] and Tsotsis et al. [941]). There have not been any published reports, however, of their use in high pressure and temperature liquid-phase applications. The idea to apply membrane reactor technology to coal liquid upgrading has resulted from a series of experimental investigations by our group of petroleum and coal asphaltene transport through model membranes. Coal liquids contain polycyclic aromatic compounds, which not only present potential difficulties in upgrading, storage and coprocessing, but are also bioactive. Direct coal liquefaction is perceived today as a two-stage process, which involves a first stage of thermal (or catalytic) dissolution of coal, followed by a second stage, in which the resulting products of the first stage are catalytically upgraded. Even in the presence of hydrogen, the oil products of the second stage are thought to equilibrate with the heavier (asphaltenic and preasphaltenic) components found in the feedstream. The possibility exists for this smaller molecular fraction to recondense with the unreacted heavy components and form even heavier undesirable components like char and coke. One way to diminish these regressive reactions is to selectively remove these smaller molecular weight fractions once they are formed and prior to recondensation. This can, at least in principle, be accomplished through the use of high temperature membrane reactors, using ceramic membranes which are permselective for the desired products of the coal liquid upgrading process. An additional incentive to do so is in order to eliminate the further hydrogenation and hydrocracking of liquid products to undesirable light gases.

  17. Hybrid membrane with TiO2 based bio-catalytic nanoparticle suspension system for the degradation of bisphenol-A.

    PubMed

    Hou, Jingwei; Dong, Guangxi; Luu, Belinda; Sengpiel, Robert G; Ye, Yun; Wessling, Matthias; Chen, Vicki

    2014-10-01

    The removal of micropollutant in wastewater treatment has become a key environmental challenge for many industrialized countries. One approach is to use enzymes such as laccase for the degradation of micropollutants such as bisphenol-A. In this work, laccase was covalently immobilized on APTES modified TiO2 nanoparticles, and the effects of particle modification on the bio-catalytic performance were examined and optimized. These bio-catalytic particles were then suspended in a hybrid membrane reactor for BPA removal with good BPA degradation efficiency observed. Substantial improvement in laccase stability was achieved in the hybrid system compared with free laccase under simulated harsh industrial wastewater treatment conditions (such as a wide range of pH and presence of inhibitors). Kinetic study provided insight of the effect of immobilization on the bio-degradation reaction. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Purge gas recovery of ammonia synthesis plant by integrated configuration of catalytic hydrogen-permselective membrane reactor and solid oxide fuel cell as a novel technology

    NASA Astrophysics Data System (ADS)

    Siavashi, Fakhteh; Saidi, Majid; Rahimpour, Mohammad Reza

    2014-12-01

    The purge gas emission of ammonia synthesis plant which contains hazardous components is one of the major sources of environmental pollution. Using integrated configuration of catalytic hydrogen-permselective membrane reactor and solid oxide fuel cell (SOFC) system is a new approach which has a great impact to reduce the pollutant emission. By application of this method, not only emission of ammonia and methane in the atmosphere is prevented, hydrogen is produced through the methane steam reforming and ammonia decomposition reactions that take place simultaneously in a catalytic membrane reactor. The pure generated hydrogen by recovery of the purge gas in the Pd-Ag membrane reactor is used as a feed of SOFC. Since water is the only byproduct of the electrochemical reaction in the SOFC, it is recycled to the reactor for providing the required water of the reforming reaction. Performance investigation of the reactor represents that the rate of hydrogen permeation increases with enhancing the reactor temperature and pressure. Also modeling results indicate that the SOFC performance improves with increasing the temperature and fuel utilization ratio. The generated power by recovery of the purging gas stream of ammonia synthesis plant in the Razi petrochemical complex is about 8 MW.

  19. High temperature size selective membranes. Final report, September 1992--March 1995

    SciTech Connect

    1996-02-01

    Availability of a high temperature size selective membrane capable of separating hydrogen from carbon dioxide and other gases is seen as highly desirable from an economic perspective. Preparation of such a membrane is technically very difficult due to the limitations that the high temperature places on materials selection. We have prepared high temperature membranes as thin film composites of a porous Blackglas{trademark} support and a carbon molecular sieve selective film. Porous Blackglail{trademark} supports have been prepared by pyrolysis of a formed mixture of Blackglas{trademark} B-staged precursor and short Carbon fibers. Such supports have the necessary smoothness for use as a membrane support, good mechanical properties, and an appropriate pore size distribution. These supports can be made either in flat sheet form or in a tubular configuration. A carbon molecular sieve layer can be added to the support by repeated coating/pyrolysis with a dilute solution of precursor polymer. The preferred precursors are polyimide or polyamic acid. Crack formation is observed after the first pyrolyses, but these cracks are repaired during later pyrolyses. The final membrane thickness is only 2.5 {mu}m. The permeation flux of the membrane for hydrogen ranges from 8.1 x 10{sup -5} at room temperature to 3.0 x 10{sup -3} cm{sup 3} (STP) cm{sup -2} sec{sup -1} cmHg{sup -1} at 717{degrees}C, and the selectivity for hydrogen over nitrogen from 2.8 to 3.8, and a selectivity for hydrogen over carbon dioxide of 2.4. This selectivity is close to the Knudsen diffusion limit. In a companion study, unsupported carbon molecular sieve films were also prepared under pyrolysis conditions similar to those used for the supported film. Hydrogen adsorption porosimetry at 19.7{degrees}K was used to show that, under appropriate activation or pyrolysis conditions, such films can be prepared which adsorb hydrogen to a much greater extent than carbon dioxide.

  20. FINAL REPORT:Observation and Simulations of Transport of Molecules and Ions Across Model Membranes

    SciTech Connect

    MURAD, SOHAIL; JAMESON, CYNTHIA J

    2013-10-22

    During the this new grant we developed a robust methodology for investigating a wide range of properties of phospho-lipid bilayers. The approach developed is unique because despite using periodic boundary conditions, we can simulate an entire experiment or process in detail. For example, we can follow the entire permeation process in a lipid-membrane. This includes transport from the bulk aqueous phase to the lipid surface; permeation into the lipid; transport inside the lipid; and transport out of the lipid to the bulk aqueous phase again. We studied the transport of small gases in both the lipid itself and in model protein channels. In addition, we have examined the transport of nanocrystals through the lipid membrane, with the main goal of understanding the mechanical behavior of lipids under stress including water and ion leakage and lipid flip flop. Finally we have also examined in detail the deformation of lipids when under the influence of external fields, both mechanical and electrostatic (currently in progress). The important observations and conclusions from our studies are described in the main text of the report

  1. Cryogenic methane separation/catalytic hydrogasification process analysis. Final technical report, 23 July 1980-23 September 1981

    SciTech Connect

    Klosek, J.; Gramse, C.J.; Tsao, T.R.

    1981-10-20

    In a continuing effort to further optimize the CS/R (Rockwell) Coal Hydrogasification process and the Exxon Catalytic Coal Gasification (CCG) process, DOE extended the contract study, Cryogenic Methane Separation/Catalytic Hydrogasification Process Analysis (ET-78-C-01-3044). Air Products and Chemicals, Inc. was authorized to perform additional trade-off studies which were of interest to DOE, Rockwell, and Exxon as potential capital and operating cost savings for the two, third generation coal gasification processes. The scope of this contract extension was comprised of two (2) subtasks for the CS/R (Rockwell) process and nine (9) subtasks for the Exxon CCG process. A Task I type screening study was performed for all subtasks. The results of the evaluations are summarized below.

  2. Fundamental and exploratory studies of catalytic steam gasification of carbonaceous materials. Final report, fiscal years 1985--1994

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.

    1994-03-01

    The major purpose of this project was to find catalysts which will permit steam gasification of carbonaceous material at reasonable rates and at lower temperatures than currently practiced. Rapid catalyst deactivation must be avoided. An understanding of the catalytic mechanism is necessary to provide leads towards this aim. This report describes the gasification of graphite studies and the gasification of coals, chars, and petroleum cokes.

  3. The acidic domain of the endothelial membrane protein GPIHBP1 stabilizes lipoprotein lipase activity by preventing unfolding of its catalytic domain.

    PubMed

    Mysling, Simon; Kristensen, Kristian Kølby; Larsson, Mikael; Beigneux, Anne P; Gårdsvoll, Henrik; Fong, Loren G; Bensadouen, André; Jørgensen, Thomas Jd; Young, Stephen G; Ploug, Michael

    2016-01-03

    GPIHBP1 is a glycolipid-anchored membrane protein of capillary endothelial cells that binds lipoprotein lipase (LPL) within the interstitial space and shuttles it to the capillary lumen. The LPL•GPIHBP1 complex is responsible for margination of triglyceride-rich lipoproteins along capillaries and their lipolytic processing. The current work conceptualizes a model for the GPIHBP1•LPL interaction based on biophysical measurements with hydrogen-deuterium exchange/mass spectrometry, surface plasmon resonance, and zero-length cross-linking. According to this model, GPIHBP1 comprises two functionally distinct domains: (1) an intrinsically disordered acidic N-terminal domain; and (2) a folded C-terminal domain that tethers GPIHBP1 to the cell membrane by glycosylphosphatidylinositol. We demonstrate that these domains serve different roles in regulating the kinetics of LPL binding. Importantly, the acidic domain stabilizes LPL catalytic activity by mitigating the global unfolding of LPL's catalytic domain. This study provides a conceptual framework for understanding intravascular lipolysis and GPIHBP1 and LPL mutations causing familial chylomicronemia.

  4. Biodiesel production from waste chicken fat with low free fatty acids by an integrated catalytic process of composite membrane and sodium methoxide.

    PubMed

    Shi, Wenying; Li, Jianxin; He, Benqiao; Yan, Feng; Cui, Zhenyu; Wu, Kaiwei; Lin, Ligang; Qian, Xiaomin; Cheng, Yu

    2013-07-01

    An integrated process of catalytic composite membranes (CCMs) and sodium methoxide was developed to produce biodiesel from waste chicken fat. The free fatty acids (FFAs) in the chicken oil were converted to methyl esters by esterification with methanol using a novel sulfonated polyethersulfone (SPES)/PES/non-woven fabric (NWF) CCMs in a flow-through catalytic membrane reactor. The CCM is that the NWF fibers were fully embedded in SPES/PES with a homogeneous and microporous structure. The oil obtained after esterification was carried out by transesterification of sodium methoxide. The results showed that the FFAs conversion obtained by CCMs with the acid capacity of 25.28 mmol (H(+)) was 92.8% at the residence time 258s. The CCMs present a good stability during the continuous running of 500 h. The conversion of transesterification was 98.1% under the optimum conditions. The quality of the biodiesel met the international standards. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Expression of rat heme oxygenase in Escherichia coli as a catalytically active, full-length form that binds to bacterial membranes.

    PubMed

    Ishikawa, K; Sato, M; Yoshida, T

    1991-11-15

    A plasmid, pKK-RHO, was constructed by incorporating the coding sequence of a cDNA for rat heme oxygenase into the expression vector pKK233-2. Escherichia coli strain XL1-blue transformed with pKK-RHO produced a catalytically active, full-length heme oxygenase. The 32-kDa native enzyme expressed, was localized in the bacterial membranes, possibly due to the spontaneous membrane-binding properties of a hydrophobic segment in its C-terminal region. During cultivation, a few degraded forms of heme oxygenase that had lost their membrane-associative properties appeared. Probably, some bacterial proteases cut the native heme oxygenase at sites near its C-terminus and so release hydrophilic peptides of heme oxygenase from the membranes. A 30-kDa polypeptide, one of the degraded forms of heme oxygenase, retained ability to accept electrons from NADPH--cytochrome P450 reductase and also activity for catalyzing breakdown of heme to biliverdin. The cultured cells were pale green. From them we extracted green pigment(s), of which the absorption spectrum closely resembled that of biliverdin, suggesting that a large amount of the endogenous heme of E. coli was actually degraded to biliverdin by the expressed heme oxygenase.

  6. Catalytic unit-independent phosphorylation and dephosphorylation of type II regulatory subunit of cyclic AMP-dependent protein kinase in rat liver plasma membranes.

    PubMed Central

    Kiss, Z; Luo, Y; Vereb, G

    1986-01-01

    Rat liver plasma membranes contain a 55 kDa protein which proved to be identical with type II regulatory subunit (RII) of the cyclic AMP-dependent protein kinase (kinase A) by several criteria (gel electrophoretic behaviour, peptide map, position of the autophosphorylated site). Analysis of phosphopeptide maps revealed that the membrane-bound RII was phosphorylated by a kinase which is unrelated to the catalytic unit (C) of kinase A. Dephosphorylation of the membrane-bound RII by an endogenous phosphatase was stimulated by both cyclic AMP and fluoride. Addition of C did not stimulate dephosphorylation even in the presence of ADP; moreover, protein inhibitor of C did not modify the effects of cyclic AMP or fluoride. The effects of both cyclic AMP and fluoride were, however, inhibited by C. Results indicate that rat liver plasma membranes contain a phosphorylation-dephosphorylation system for which RII is a relatively specific substrate. Images Fig. 1. Fig. 2. Fig. 3. Fig. 4. Fig. 5. Fig. 6. PMID:3010951

  7. The catalytic activity of the endoplasmic reticulum-resident protein microsomal epoxide hydrolase towards carcinogens is retained on inversion of its membrane topology.

    PubMed Central

    Friedberg, T; Holler, R; Löllmann, B; Arand, M; Oesch, F

    1996-01-01

    Diol epoxides formed by the sequential action of cytochrome P-450 and the microsomal epoxide hydrolase (mEH) in the endoplasmic reticulum (ER) represent an important class of ultimate carcinogenic metabolites of polycyclic aromatic hydrocarbons. The role of the membrane orientation of cytochrome P-450 and mEH relative to each other in this catalytic cascade is not known. Cytochrome P-450 is known to have a type I topology. According to the algorithm of Hartman, Rapoport and Lodish [(1989) Proc. Natl. Acad. Sci. U.S.A. 86, 5786-5790], which allows the prediction of the membrane topology of proteins, mEH should adopt a type II membrane topology. Experimentally, mEH membrane topology has been disputed. Here we demonstrate that, in contrast with the theoretical prediction, the rat mEH has exclusively a type I membrane topology. Moreover we show that this topology can be inverted without affecting the catalytic activity of mEH. Our conclusions are supported by the observation that two mEH constructs (mEHg1 and mEHg2), containing engineered potential glycosylation sites at two separate locations after the C-terminal site of the membrane anchor, were not glycosylated in fibroblasts. However, changing the net charge at the N-terminus of these engineered mEH proteins by +3 resulted in proteins (++mEHg1 and ++mEHg2) that became glycosylated and consequently had a type II topology. The sensitivity of these glycosylated proteins to endoglycosidase H indicated that, like the native mEH, they are still retained in the ER. The engineered mEH proteins were integrated into membranes as they were resistant to alkaline extraction. Interestingly, an insect mEH with a charge distribution in its N-terminus similar to ++mEHg1 has recently been isolated. This enzyme might well display a type II topology instead of the type I topology of the rat mEH. Importantly, mEHg1, having the natural cytosolic orientation, as well as ++mEHg1, having an artificial huminal orientation, displayed rather

  8. Novel selective surface flow (SSF{sup TM}) membranes for the recovery of hydrogren from waste gas streams. Final report

    SciTech Connect

    Anand, M.

    1995-08-01

    The waste streams are off-gas streams from various chemical/refinery operations. In Phase I, the architecture of the membrane and the separation device were defined and demonstrated. The system consists of a shell-and-tube separator in which the gas to be separated is fed to the tube side, the product is collected as high pressure effluent and the permeate constitutes the waste/fuel stream. Each tube, which has the membrane coated on the interior, does the separation. A multi- tube separator device containing 1 ft{sup 2} membrane area was built and tested. The engineering data were used for designing a process for hydrogen recovery from a fluid catalytic cracker off-gas stream. First-pass economics showed that overall cost for hydrogen production is reduced by 35% vs on-purpose production of hydrogen by steam- methane reforming. The hydrogen recovery process using the SSF membrane results in at least 15% energy reduction and significant decrease in CO{sub 2} and NO{sub x} emissions.

  9. Role of PSD95 in membrane association and catalytic activity of nNOSalpha in nitrergic varicosities in mice gut.

    PubMed

    Chaudhury, Arun; He, Xue-Dao; Goyal, Raj K

    2009-10-01

    We have recently shown that membrane association of neuronal nitric oxide synthase-alpha (nNOSalpha) is critical in the regulation of synthesis of NO during nitrergic neurotransmission. The purpose of this study was to examine the role of the synapse-associated proteins (SAPs) in membrane association of nNOSalpha. Varicosities (swellings on terminal axons) were isolated from mice gastrointestinal tract and examined for nNOSalpha, postsynaptic density protein 95 (PSD95), and membrane interactions by coimmunoprecipitation and SDS-PAGE. Our results show that PSD95 protein was present in the membrane fraction of the nerve varicosity, whereas both PSD95 and SAP97 were present in the cytosol. nNOSalpha was associated with PSD95 but not SAP97. nNOSalpha-PSD95 complex was bound to the membrane via palmitoylation of PSD95. Depalmitoylation of PSD95 with 2-bromopalmitate dislocates nNOSalpha and PSD95 from the varicosity membrane and abolishes NO production. These studies show that palmitoylation of PSD95 anchors nNOSalpha to the varicosity membrane and that it is obligatory for NO production by the enzyme. Palmitoylation of PSD95 may provide a novel target for regulation of nitrergic neurotransmission.

  10. New nanosized catalytic membrane reactors for hydrogenation with stored hydrogen: Prerequisites and the experimental basis for their creation

    NASA Astrophysics Data System (ADS)

    Soldatov, A. P.; Tsodikov, M. V.; Parenago, O. P.; Teplyakov, V. V.

    2010-12-01

    The prerequisites and prospects for creating a new generation of nanosized membrane reactors are considered. For the first time, hydrogenation reactions take place in ceramic membrane pores with hydrogen adsorbed beforehand in mono- and multilayered oriented carbon nanotubes with graphene walls (OCNTGs) formed on the internal pore surface. It is shown for Trumem microfiltration membranes with D avg ˜130 nm that oxidation reactions of CO on a Cu0.03Ti0.97O2 ± δ catalyst and the oxidative conversion of methane into synthesis gas and light hydrocarbons on La + Ce/MgO are considerably enhanced when they occur in membranes. Regularities of hydrogen adsorption, storage, and desorption in nanosized membrane reactors are investigated through OCNTG formation in Trumem ultrafiltration membrane pores with D avg = 50 and 90 nm and their saturation with hydrogen at a pressure of 10-13 MPa. It is shown that the amount of adsorbed hydrogen reaches 14.0% of OCNTG mass. Using thermogravimetric analysis in combination with mass-spectrometric analysis, hydrogen adsorption in OCNTG is first determined and its desorption is found to proceed at atmospheric pressure at a temperature of ˜175°C. It is shown that adsorbed hydrogen affects the transport properties of the membranes, reducing their efficiency with respect to liquids by 4-26 times. This is indirect confirmation of its high activity, due apparently the dissociative mechanism of adsorption.

  11. Catalytic Two-Stage Liquefaction (CTSL) process bench studies with bituminous coal. Final report, [October 1, 1988--December 31, 1992

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Karolkiewicz, W.F.; Lee, L.K.; Stalzer, R.H.; Smith, T.O.

    1993-03-01

    Reported herein are the details and results of Laboratory and Bench-Scale experiments using bituminous coal concluded at Hydrocarbon Research, Inc., under DOE contract during the period October 1, 1988 to December 31, 1992. The work described is primarily concerned with the application of coal cleaning methods and solids separation methods to the Catalytic Two-Stage Liquefaction (CTSL) Process. Additionally a predispersed catalyst was evaluated in a thermal/catalytic configuration, and an alternative nickel molybdenum catalyst was evaluated for the CTSL process. Three coals were evaluated in this program: Bituminous Illinois No. 6 Burning Star and Sub-bituminous Wyoming Black Thunder and New Mexico McKinley Mine seams. The results from a total of 16 bench-scale runs are reported and analyzed in detail. The tests involving the Illinois coal are reported herein, and the tests involving the Wyoming and New Mexico coals are described in Topical Report No. 1. On the laboratory scale, microautoclave tests evaluating coal, start-up oils, catalysts, thermal treatment, CO{sub 2} addition and sulfur compound effects are reported in Topical Report No. 3. Other microautoclave tests, such as tests on rejuvenated catalyst, coker liquids, and cleaned coals, are described in the Bench Run sections to which they refer. The microautoclave tests conducted for modelling the CTSL process are described in the CTSL Modelling section of Topical Report No. 3 under this contract.

  12. A Broad Spectrum Catalytic System for Removal of Toxic Organics from Water by Deep Oxidation - Final Report

    SciTech Connect

    Sen, Ayusman

    2000-12-01

    A most pressing need for the DOE environmental management program is the removal of toxic organic compounds present in groundwater and soil at specific DOE sites. While several remediation procedures have been proposed, they suffer from one or more drawbacks. The objective of the present research was to develop new catalytic procedures for the removal of toxic organic compounds from the environment through their deep oxidation to harmless products. In water, metallic palladium was found to catalyze the deep oxidation of a wide variety of toxic organic compounds by dioxygen at 80-90 C in the presence of carbon monoxide or dihydrogen. Several classes of organic compounds were examined: benzene, phenol and substituted phenols, nitro and halo organics, organophosphorus, and organosulfur compounds. In every case, deep oxidation to carbon monoxide, carbon dioxide, and water occurred in high yields, resulting in up to several hundred turnovers over a 24 hour period. For substrates susceptible to hydrogenation, the conversions were generally high with dihydrogen than with carbon monoxide. It is clear from the results obtained that we have discovered an exceptionally versatile catalytic system for the deep oxidation of toxic organic compounds in water. This system possesses several attractive features not found simultaneously in other reported systems. These are (a) the ability to directly utilize dioxygen as the oxidant, (b) the ability to carry out the deep oxidation of a particularly wide range of functional organics, and (c) the ease of recovery of the catalyst by simple filtration.

  13. The Translocation Domain of Botulinum Neurotoxin A Moderates the Propensity of the Catalytic Domain to Interact with Membranes at Acidic pH

    PubMed Central

    Araye, Anne; Goudet, Amélie; Barbier, Julien; Pichard, Sylvain; Baron, Bruno; England, Patrick; Pérez, Javier; Zinn-Justin, Sophie; Chenal, Alexandre; Gillet, Daniel

    2016-01-01

    Botulinum neurotoxin A (BoNT/A) is composed of three domains: a catalytic domain (LC), a translocation domain (HN) and a receptor-binding domain (HC). Like most bacterial toxins BoNT/A is an amphitropic protein, produced in a soluble form that is able to interact, penetrate and/or cross a membrane to achieve its toxic function. During intoxication BoNT/A is internalized by the cell by receptor-mediated endocytosis. Then, LC crosses the membrane of the endocytic compartment and reaches the cytosol. This translocation is initiated by the low pH found in this compartment. It has been suggested that LC passes in an unfolded state through a transmembrane passage formed by HN. We report here that acidification induces no major conformational change in either secondary or tertiary structures of LC and HN of BoNT/A in solution. GdnHCl-induced denaturation experiments showed that the stability of LC and HN increases as pH drops, and that HN further stabilizes LC. Unexpectedly we found that LC has a high propensity to interact with and permeabilize anionic lipid bilayers upon acidification without the help of HN. This property is downplayed when LC is linked to HN. HN thus acts as a chaperone for LC by enhancing its stability but also as a moderator of the membrane interaction of LC. PMID:27070312

  14. The Translocation Domain of Botulinum Neurotoxin A Moderates the Propensity of the Catalytic Domain to Interact with Membranes at Acidic pH.

    PubMed

    Araye, Anne; Goudet, Amélie; Barbier, Julien; Pichard, Sylvain; Baron, Bruno; England, Patrick; Pérez, Javier; Zinn-Justin, Sophie; Chenal, Alexandre; Gillet, Daniel

    2016-01-01

    Botulinum neurotoxin A (BoNT/A) is composed of three domains: a catalytic domain (LC), a translocation domain (HN) and a receptor-binding domain (HC). Like most bacterial toxins BoNT/A is an amphitropic protein, produced in a soluble form that is able to interact, penetrate and/or cross a membrane to achieve its toxic function. During intoxication BoNT/A is internalized by the cell by receptor-mediated endocytosis. Then, LC crosses the membrane of the endocytic compartment and reaches the cytosol. This translocation is initiated by the low pH found in this compartment. It has been suggested that LC passes in an unfolded state through a transmembrane passage formed by HN. We report here that acidification induces no major conformational change in either secondary or tertiary structures of LC and HN of BoNT/A in solution. GdnHCl-induced denaturation experiments showed that the stability of LC and HN increases as pH drops, and that HN further stabilizes LC. Unexpectedly we found that LC has a high propensity to interact with and permeabilize anionic lipid bilayers upon acidification without the help of HN. This property is downplayed when LC is linked to HN. HN thus acts as a chaperone for LC by enhancing its stability but also as a moderator of the membrane interaction of LC.

  15. Membrane/distillation hybrid process research and development. Final report, phase II

    SciTech Connect

    Mazanec, T.J.

    1997-07-01

    This report covers work conducted under the grant awarded to BP by DOE in late 1991 entitled {open_quotes}Membrane/Distillation Hybrid Process Research and Development.{close_quotes} The program was directed towards development and commercialization of the BP process for separation of vapor phase olefins from non-olefins via facilitated transport using an aqueous facilitator. The program has come to a very successful conclusion, with formation of a partnership between BP and Stone and Webster Engineering Corporation (SWEC) to market and commercialize the technology. The focus of this report is the final portion of the program, during which engineering re-design, facilitator optimization, economic analysis, and marketing have been the primary activities. At the end of Phase II BP was looking to partner with an engineering firm to advance the selective olefin recovery (SOR) technology from the lab/demo stage to full commercialization. In August 1995 BP and SWEC reached an agreement to advance the technology by completing additional Phase III work with DOE and beginning marketing activities.

  16. Advanced treatment of biologically pretreated coal gasification wastewater by a novel integration of three-dimensional catalytic electro-Fenton and membrane bioreactor.

    PubMed

    Jia, Shengyong; Han, Hongjun; Hou, Baolin; Zhuang, Haifeng

    2015-12-01

    Laboratorial scale experiments were conducted to investigate a novel system three-dimensional catalytic electro-Fenton (3DCEF, catalyst of sewage sludge based activated carbon which loaded Fe3O4) integrating with membrane bioreactor (3DCEF-MBR) on advanced treatment of biologically pretreated coal gasification wastewater. The results indicated that 3DCEF-MBR represented high efficiencies in eliminating COD and total organic carbon, giving the maximum removal efficiencies of 80% and 75%, respectively. The integrated 3DCEF-MBR system significantly reduced the transmembrane pressure, giving 35% lower than conventional MBR after 30 days operation. The enhanced hydroxyl radical oxidation and bacteria self repair function were the mechanisms for 3DCEF-MBR performance. Therefore, the integrated 3DCEF-MBR was expected to be the promising technology for advanced treatment in engineering applications.

  17. P-glycoprotein senses its substrates and the lateral membrane packing density: consequences for the catalytic cycle.

    PubMed

    Aänismaa, Päivi; Gatlik-Landwojtowicz, Ewa; Seelig, Anna

    2008-09-23

    P-glycoprotein (ABCB1) prevents absorption (e.g., blood-brain barrier) or enhances excretion (e.g., kidney) by moving substrates from the cytosolic to the extracellular membrane leaflet at the expense of ATP hydrolysis. It translocates various drugs and functions in membranes exhibiting different lateral packing densities. To gain more functional insight, we measured the temperature dependence of the P-glycoprotein ATPase activity in NIH-MDR1-G185 cell membranes in the absence and presence of three drugs (promazine, verapamil, and PSC833), exhibiting significantly different transporter affinities. Activation enthalpies (Delta H(++)) and entropies ( TDelta S(++)) were derived from Eyring plots. In the absence of drugs, the activation enthalpy and the free energy of activation for P-glycoprotein ATPase activity was determined as Delta H(++) = 92.6 +/- 4.2 kJ/mol and Delta G(++) = 73.1 +/- 7.2 kJ/mol, respectively. Increasing the drug concentration reduced the activation enthalpy, whereby the drug with the highest transporter affinity had the strongest effect (DeltaDelta H(++) = -21%). The free energy of activation decreased for activating (DeltaDelta G(++) = approximately -3.8%) and increased for inhibitory compounds (DeltaDelta G(++) = approximately +0.7%). The drug-specific changes of the free energy of activation are thus barely above thermal energy. A comparison with literature data revealed that a decrease of the lateral membrane packing density reduces the enthalpic and the entropic contribution to the free energy of activation. Although the P-glycoprotein ATPase activity increases only slightly with decreasing lateral membrane packing density, the mode of action changes from strongly entropy-driven at high, to essentially enthalpy-driven at low packing densities. This suggests that the transporter and the membrane form a functional entity.

  18. Homology modeling of the three membrane proteins of the dhurrin metabolon: catalytic sites, membrane surface association and protein-protein interactions.

    PubMed

    Jensen, Kenneth; Osmani, Sarah Anne; Hamann, Thomas; Naur, Peter; Møller, Birger Lindberg

    2011-12-01

    Formation of metabolons (macromolecular enzyme complexes) facilitates the channelling of substrates in biosynthetic pathways. Metabolon formation is a dynamic process in which transient structures mediated by weak protein-protein interactions are formed. In Sorghum, the cyanogenic glucoside dhurrin is derived from l-tyrosine in a pathway involving the two cytochromes P450 (CYPs) CYP79A1 and CYP71E1, a glucosyltransferase (UGT85B1), and the redox partner NADPH-dependent cytochrome P450 reductase (CPR). Experimental evidence suggests that the enzymes of this pathway form a metabolon. Homology modeling of the three membrane bound proteins was carried out using the Sybyl software and available relevant crystal structures. Residues involved in tight positioning of the substrates and intermediates in the active sites of CYP79A1 and CYP71E1 were identified. In both CYPs, hydrophobic surface domains close to the N-terminal trans-membrane anchor and between the F' and G helices were identified as involved in membrane anchoring. The proximal surface of both CYPs showed positively charged patches complementary to a negatively charged bulge on CPR carrying the FMN domain. A patch of surface exposed, positively charged amino acid residues positioned on the opposite face of the membrane anchor was identified in CYP71E1 and might be involved in binding UGT85B1 via a hypervariable negatively charged loop in this protein. Copyright © 2011 Elsevier Ltd. All rights reserved.

  19. Preparation of pervaporation membranes. Final report on Phase 1. Report for 1 January-31 October 1989

    SciTech Connect

    Baker, R.W.; Athayede, A.L.; Castro, R.

    1989-10-15

    The goal of the Phase 1 program was to prepare improved pervaporation membranes for the separation of polar solvents from water. Membranes were prepared from modified polysiloxanes and other rubbery materials. These membranes were tested with ethanol/water and ethyl acetate/water mixtures to determine their performance in a pervaporation test loop. Polydimethylsiloxane with polyamide blocks was the most selective material for ethanol/water separation. Polybutadiene membranes were preferred for ethyl acetate/water separation. The performance of the polydimethysiloxane-polyamide block copolymer demonstrates that the inclusion of hydrophilic groups into polydimethylsiloxane increases the ethanol/water selectivity, but the improvement is not significant. Testing of polyvinylmethylsiloxane membranes indicated that the degree of cross-linking in a polysiloxane membrane has a significant effect on ethanol/water selectivity. A highly cross-linked siloxane has a much lower ethanol/water selectivity than a less cross-linked material.

  20. FY05 LDRD Final Report Molecular Engineering of Electrodialysis Membranes 03-ERD-060

    SciTech Connect

    Bourcier, W; O'Brien, K; Sawvel, A; Johnson, M; Bettencourt, K; Letant, S; Felter, T; Langry, K; Wilson, B; Haslam, J; Schaldach, C; Sopchak, D

    2006-02-22

    Using a combination of modeling and experimental work we have developed a new method for purifying water that uses less energy than conventional methods and that can be made selective for removing targeted contaminants. The method uses nanoporous membranes that are permselective for anion or cation transfer. Ion selectivity results from double layer overlap inside the pores such that they dominantly contain ions opposite in charge to the surface charge of the membrane. Membrane charge can be adjusted through functionalization. Experiments confirm membrane permselectivity and overall energy use less than that for conventional electrodialysis. The nanoporous membranes are used in a conventional electrodialysis configuration and can be incorporated in existing electrodialysis systems without modification. The technology merits further development and testing in real systems, and could result in a significant reduction in water treatment costs.

  1. High temperature direct methanal-fuel proton exchange membrane fuel cells. Final report

    SciTech Connect

    Lvov, S. N.; Allcock, H. R.; Zhou, X. Y.; Hofmann, M. A.; Chalkova, E.; Fedkin, M. V.; Weston, J. A.; Ambler, C. M.

    2001-10-01

    The lack of proton conductive polymeric membranes stable at high temperatures is one of the main issues impeding the development of DMFCs. The currently employed Nafion membranes are not suitable at temperatures abouve 100 degrees C due to a substantial methanol crossover and poor thermal stability. Therefore, the development of a polymeric membrane stable at high temperatures for DMFCs was the main task of the project. Our approach is based on an interdisciplinary effort that brings together a research group with expertise in the design and synthesis of polyphosphazenes polymer membranes (Allcock Research Laboratory) and a team that has experience in the fields of high temperature electrochemistry and electrochemical energy conversion systems (Lvov Research Laboratory). We have synthesized a new class of ion-exchange membranes for DMFCs.

  2. Direct catalytic conversion of methane and light hydrocarbon gases. Final report, October 1, 1986--July 31, 1989

    SciTech Connect

    Wilson, R.B. Jr.; Posin, B.M.; Chan, Yee-Wai

    1995-06-01

    This project explored conversion of methane to useful products by two techniques that do not involve oxidative coupling. The first approach was direct catalytic dehydrocoupling of methane to give hydrocarbons and hydrogen. The second approach was oxidation of methane to methanol by using heterogenized versions of catalysts that were developed as homogeneous models of cytochrome-P450, an enzyme that actively hydroxylates hydrocarbons by using molecular oxygen. Two possibilities exist for dehydrocoupling of methane to higher hydrocarbons: The first, oxidative coupling to ethane/ethylene and water, is the subject of intense current interest. Nonoxidative coupling to higher hydrocarbons and hydrogen is endothermic, but in the absence of coke formation the theoretical thermodynamic equilibrium yield of hydrocarbons varies from 25% at 827{degrees}C to 65% at 1100{degrees}C (at atmospheric pressure). In this project we synthesized novel, highly dispersed metal catalysts by attaching metal clusters to inorganic supports. The second approach mimics microbial metabolism of methane to produce methanol. The methane mono-oxygenase enzyme responsible for the oxidation of methane to methanol in biological systems has exceptional selectivity and very good rates. Enzyme mimics are systems that function as the enzymes do but overcome the problems of slow rates and poor stability. Most of that effort has focused on mimics of cytochrome P-450, which is a very active selective oxidation enzyme and has a metalloporphyrin at the active site. The interest in nonporphyrin mimics coincides with the interest in methane mono-oxygenase, whose active site has been identified as a {mu}-oxo dinuclear iron complex.We employed mimics of cytochrome P-450, heterogenized to provide additional stability. The oxidation of methane with molecular oxygen was investigated in a fixed-bed, down-flow reactor with various anchored metal phthalocyanines (PC) and porphyrins (TPP) as the catalysts.

  3. A novel approach to highly dispersing catalytic materials in coal for gasification. Final technical report, September 1989--November 1992

    SciTech Connect

    Abotsi, G.M.K.; Bota, K.B.

    1992-12-01

    The objectives of this project were to investigate the effects of coal surface charge on the uptake of aqueous soluble metal catalysts from solution and to determine the influence of the interfacial interaction on char reactivity. Another goal is to assess the potential of using potassium carbonate, potassium acetate or their mixtures as catalysts for char gasification. The lower cost and the high catalytic activity of the latter compound will produce economic benefits by reducing the amount of potassium carbonate required for efficient char reactivities on a commercial scale. To minimize the interference of the coals` inherent inorganic materials with the added calcium or potassium, the gasification studies were restricted to the demineralized coals. In a manner similar to the effect of pH on the surface electrochemistry of the coals, the reactivities of the calcium- or potassium-loaded chars in bon dioxide at 800{degree}C were dependent upon the pH at which the catalysts were ion-exchanged onto the coals. For the calcium-containing chars, the reactivities increased in the order: pH 6 > pH 10 > pH 1. In contrast, the variation of the gasification rates with potassium loading pH was: pH 6 {approximately} pH 10 {much_gt} pH 1. However, simultaneous adsorption of the metals at {approximately} pH 1 enhanced char reactivity relative to metals loading at pH 6 or 10. These findings are attributed to the differences in the extent of electrostatic interaction between the calcium or potassium ions and the charged coal surface during catalyst loading from solution.

  4. Superior catalysts for selective catalytic reduction of nitric oxide. Final technical report, October 1, 1993--September 30, 1995

    SciTech Connect

    Yang, R.T.; Li, W.B.; Chen, J.P.; Hausladen, M.C.; Cheng, L.S.; Kikkinides, E.S.

    1995-12-31

    The most advanced and proven technology for NO{sub x} control for stationary sources is Selective Catalytic Reduction (SCR). In SCR, NO{sub x} is reduced by NH{sub 3} to N{sub 2} and H{sub 2}O. The commercial catalysts are based on V{sub 2}O{sub 5}/TiO{sub 2}, and the vanadium-based catalysts are patented by the Japanese (Mitsubishi). However, there are three main advantages for the vanadium-based SCR catalyst: (a) a tendency to be poisoned in the flue gas; (b) oxidation of SO{sub 2} to SO{sub 3} by V{sub 2}O{sub 5}, this is a particularly severe problem due to the higher sulfur content of American coals compared with coals used in Japan (from Australia) and in Europe; (c) environmental problems involved in the disposal of the spent catalyst (due to the toxicity of vanadium). In order to overcome these problems, in addition to the undesirable dominance by the Japanese patent position, the authors have studied in this project a new type of catalyst for the SCR reaction; namely, pillared clays, which have adjustable, unique structures and acidity. Three types of catalysts were developed and tested for this reaction, i.e. Fe{sub 2}O{sub 3}-pillared clays, delaminated Fe{sub 2}O{sub 3}-pillared clays, and ion-exchanged pillared clays. The project was divided into sixteen tasks, and will be reported as such.

  5. Technical and economic feasibility of membrane technology. Final report, September 17, 1979-November 16, 1981

    SciTech Connect

    Not Available

    1981-01-01

    The first phase of the project involved the development of a literature survey relative to the state-of-the-art for reverse osmosis (RO), electrodialysis (ED), and ultra filtration (UF). A comprehensive examination of both domestic and foreign literature provided a basis for selection of membrane candidates evaluated in Phase II and III of the project. In addition, an investigation was conducted identifying the development of other commercial membrane materials for use other than in the sugar industry (cheese industry). During Phase II, selected membranes were evaluated using a prototype mounting configuration, different temperatures, pressures, feed streams as well as some preliminary testing on ED and UF. The feed streams evaluated included diffusion juice, thin juice, hot Steffan waste, and ion exchanged purified effluents. Replicated runs were performed on several different batches of membranes and feeds to establish significant differences. The activity conducted during Phase III consisted of evaluating selected membranes over a long-term performance basis, i.e., pilot plant evaluation. Membrane material were mounted in pilot hardware for testing purposes. Determinations of membrane life cycles were made as well as establishing the preliminary economics of the operation as related to replacement module service life and on-line operating characteristics.

  6. Final Report - Energy Reduction and Advanced Water Removal via Membrane Solvent Extraction Technology

    SciTech Connect

    Reed, John; Fanselow, Dan; Abbas, Charles; Sammons, Rhea; Kinchin, Christopher

    2014-08-06

    3M and Archer Daniels Midland (ADM) collaborated with the U.S. Department of Energy (DOE) to develop and demonstrate a novel membrane solvent extraction (MSE) process that can substantially reduce energy and water consumption in ethanol production, and accelerate the fermentation process. A cross-flow membrane module was developed, using porous membrane manufactured by 3M. A pilot process was developed that integrates fermentation, MSE and vacuum distillation. Extended experiments of 48-72 hours each were conducted to develop the process, verify its performance and begin establishing commercial viability.

  7. Structural relationship in chloroplast membranes. Final report, August 1, 1977-August 31, 1980

    SciTech Connect

    1980-09-01

    Methodology has been developed for the isolation and characterization of pigment-proteins from chloroplast membranes. Characterization of these pigment-proteins has increased our understanding of mechanisms regulating the efficiency of photosynthetic light harvesting during photosynthesis. Incorporation of isolated pigment-protein complexes into model membranes has allowed simulation of grana stacks; these structural features of chloroplasts play a key role in maintaining appropriate interactions among light-harvesting assembles to regulate photosynthetic solar energy conversion.

  8. Molecular cloning and catalytic activity of a membrane-bound prenyl diphosphate phosphatase from Croton stellatopilosus Ohba.

    PubMed

    Nualkaew, Natsajee; Guennewich, Nils; Springob, Karin; Klamrak, Anuwatchakit; De-Eknamkul, Wanchai; Kutchan, Toni M

    2013-07-01

    Geranylgeraniol (GGOH), a bioactive acyclic diterpene with apoptotic induction activity, is the immediate precursor of the commercial anti-peptic, plaunotol (18-hydroxy geranylgeraniol), which is found in Croton stellatopilosus (Ohba). From this plant, a cDNA encoding a prenyl diphosphate phosphatase (CsPDP), which catalyses the dephosphorylation of geranylgeranyl diphosphate (GGPP) to GGOH, was isolated using a PCR approach. The full-length cDNA contained 888bp and encoded a 33.6 kDa protein (295 amino acids) that was phylogenetically grouped into the phosphatidic acid phosphatase (PAP) enzyme family. The deduced amino acid sequence showed 6 hydrophobic transmembrane regions with 57-85% homology to the sequences of other plant PAPs. The recombinant CsPDP and its 4 truncated constructs exhibited decreasing dephosphorylation activities relative to the lengths of the N-terminal deletions. While the full-length CsPDP successfully performed the two sequential monodephosphorylation steps on GGPP to form GGOH, the larger N-terminal deletion in the truncated enzymes appeared to specifically decrease the catalytic efficiency of the second monodephosphorylation step. The information presented here on the CsPDP cDNA and factors affecting the dephosphorylation activity of its recombinant protein may eventually lead to the discovery of the specific GGPP phosphatase gene and enzyme that are involved in the formation of GGOH in the biosynthetic pathway of plaunotol in C. stellatopilosus.

  9. 2nd Pan American Workshop on Plant Membrane Biology: Final Report for DOE

    SciTech Connect

    Hirschi, Kendal D.

    2006-05-15

    The entire DOE funds were used to provide funds for students, postdoctoral fellows and faculty to attend the Plant Membrane Plant Biology meeting from May 17-21, 2006 in South Padre Texas. The meeting had an attendance of approximately 130 people from approximately 10 different countries. The location was selected for its proximity to the US-Mexico border. This was the second Pan American Plant Membrane Biology meeting (2003 for the first one) and it was a great success as we forged research relationships between South America and the United States. We provided an opportunity for researchers from the Western Hemisphere to exchange the most recent information and ideas relating to the biology of plant membranes in a workshop environment. The conference addressed such topics as Hormone Responses, Environmental Signal Perception, Nutrient Acquisition, Membranes and Development, Source/Sink Transport, Water Relations,Genomics, Evolution of Transporters, Structure/Function Relationships and Practical Applications of Membrane Research. Oral and poster presentations were thematically grouped and sessions included a representative mixture of experimental and intellectual approaches to important topics in plant membrane biology. Sections were led by prominent researchers in the specific focus area with talks presented by postdocs, graduate students, and undergraduate researchers. In keeping with the workshop format, provisions were made for extended discussion following talks. PIs and faculty advisors of speakers attended and contributed to the discussion of presentations. The lineup included forty speakers. This document also includes a list of participants funded by DOE and the amount of money spent.

  10. Facilitated transport ceramic membranes for high-temperature gas cleanup. Final report, February 1990--April 1994

    SciTech Connect

    Quinn, R.; Minford, E.; Damle, A.S.; Gangwal, S.K.; Hart, B.A.

    1994-04-01

    The objective of this program was to demonstrate the feasibility of developing high temperature, high pressure, facilitated transport ceramic membranes to control gaseous contaminants in Integrated Gasification Combined Cycle (IGCC) power generation systems. Meeting this objective requires that the contaminant gas H{sub 2}S be removed from an IGCC gas mixture without a substantial loss of the other gaseous components, specifically H{sub 2} and CH{sub 4}. As described above this requires consideration of other, nonconventional types of membranes. The solution evaluated in this program involved the use of facilitated transport membranes consisting of molten mixtures of alkali and alkaline earth carbonate salts immobilized in a microporous ceramic support. To accomplish this objective, Air Products and Chemicals, Inc., Golden Technologies Company Inc., and Research Triangle Institute worked together to develop and test high temperature facilitated membranes for the removal of H{sub 2}S from IGCC gas mixtures. Three basic experimental activities were pursued: (1) evaluation of the H{sub 2}S chemistry of a variety of alkali and alkaline earth carbonate salt mixtures; (2) development of microporous ceramic materials which were chemically and physically compatible with molten carbonate salt mixtures under IGCC conditions and which could function as a host to support a molten carbonate mixture and; (3) fabrication of molten carbonate/ceramic immobilized liquid membranes and evaluation of these membranes under conditions approximating those found in the intended application. Results of these activities are presented.

  11. Catalytic Conversion of Lipophilic Substrates by Phase constrained Enzymes in the Aqueous or in the Membrane Phase

    PubMed Central

    Cebula, Marcus; Turan, Ilke Simsek; Sjödin, Birgitta; Thulasingam, Madhuranayaki; Brock, Joseph; Chmyrov, Volodymyr; Widengren, Jerker; Abe, Hiroshi; Mannervik, Bengt; Haeggström, Jesper Z.; Rinaldo-Matthis, Agnes; Akkaya, Engin U.; Morgenstern, Ralf

    2016-01-01

    Both soluble and membrane-bound enzymes can catalyze the conversion of lipophilic substrates. The precise substrate access path, with regard to phase, has however, until now relied on conjecture from enzyme structural data only (certainly giving credible and valuable hypotheses). Alternative methods have been missing. To obtain the first experimental evidence directly determining the access paths (of lipophilic substrates) to phase constrained enzymes we here describe the application of a BODIPY-derived substrate (PS1). Using this tool, which is not accessible to cytosolic enzymes in the presence of detergent and, by contrast, not accessible to membrane embedded enzymes in the absence of detergent, we demonstrate that cytosolic and microsomal glutathione transferases (GSTs), both catalyzing the activation of PS1, do so only within their respective phases. This approach can serve as a guideline to experimentally validate substrate access paths, a fundamental property of phase restricted enzymes. Examples of other enzyme classes with members in both phases are xenobiotic-metabolizing sulphotransferases/UDP-glucuronosyl transferases or epoxide hydrolases. Since specific GSTs have been suggested to contribute to tumor drug resistance, PS1 can also be utilized as a tool to discriminate between phase constrained members of these enzymes by analyzing samples in the absence and presence of Triton X-100. PMID:27917951

  12. Catalytic hydrogen/oxygen reaction assisted the proton exchange membrane fuel cell (PEMFC) startup at subzero temperature

    NASA Astrophysics Data System (ADS)

    Sun, Shucheng; Yu, Hongmei; Hou, Junbo; Shao, Zhigang; Yi, Baolian; Ming, Pingwen; Hou, Zhongjun

    Fuel cells for automobile application need to operate in a wide temperature range including freezing temperature. However, the rapid startup of a proton exchange membrane fuel cell (PEMFC) at subfreezing temperature, e.g., -20 °C, is very difficult. A cold-start procedure was developed, which made hydrogen and oxygen react to heat the fuel cell considering that the FC flow channel was the characteristic of microchannel reactor. The effect of hydrogen and oxygen reaction on fuel cell performance at ambient temperature was also investigated. The electrochemical characterizations such as I- V plot and cyclic voltammetry (CV) were performed. The heat generated rate for either the single cell or the stack was calculated. The results showed that the heat generated rate was proportional to the gas flow rate when H 2 concentration and the active area were constant. The fuel cell temperature rose rapidly and steadily by controlling gas flow rate.

  13. Crystallization and preliminary X-ray crystallographic analysis of the catalytic domain of membrane type 1 matrix metalloproteinase

    PubMed Central

    Ogata, Hideaki; Decaneto, Elena; Grossman, Moran; Havenith, Martina; Sagi, Irit; Lubitz, Wolfgang; Knipp, Markus

    2014-01-01

    Membrane type 1 matrix metalloproteinase (MT1-MMP) belongs to the large family of zinc-dependent endopeptidases termed MMPs that are located in the extracellular matrix. MT1-MMP was crystallized at 277 K using the vapour-diffusion method with PEG as a precipitating agent. Data sets for MT1-MMP were collected to 2.24 Å resolution at 100 K. The crystals belonged to space group P43212, with unit-cell parameters a = 62.99, c = 122.60 Å. The crystal contained one molecule per asymmetric unit, with a Matthews coefficient (V M) of 2.90 Å3 Da−1; the solvent content is estimated to be 57.6%. PMID:24637763

  14. Final Step of Phosphatidic Acid Synthesis in Pea Chloroplasts Occurs in the Inner Envelope Membrane 1

    PubMed Central

    Andrews, Jaen; Ohlrogge, John B.; Keegstra, Kenneth

    1985-01-01

    The second enzyme of phosphatidic acid synthesis from glycerol-3-phosphate, 1-acylglycerophospate acyltransferase, was localized to the inner envelope membrane of pea chloroplasts. The activity of this enzyme was measured by both a coupled enzyme assay and a direct enzyme assay. Using the coupled enzyme assay, phosphatidic acid phosphatase was also localized to the inner envelope membrane, although this enzyme has very low activity in pea chloroplasts. The addition of UDP-galactose to unfractionated pea chloroplast envelope preparations did not result in significant conversion of newly synthesized diacylglycerol to monogalactosyldiacylglycerol. Thus, the envelope synthesized phosphatidic acid may not be involved in galactolipid synthesis in pea chloroplasts. PMID:16664266

  15. SEPARATION OF HAZARDOUS ORGANICS BY LOW PRESSURE REVERSE OSMOSIS MEMBRANES - PHASE II FINAL REPORT

    EPA Science Inventory

    Extensive experimental studies showed that thin-film, composite membranes can be used effectively for the separation of selected hazardous organic compounds. This waste treatment technique offers definite advantages in terms of high solute separations at low pressures (<2MPa) and...

  16. High flux ceramic membrane for hydrogen separation. Final technical progress report

    SciTech Connect

    K. Durai-Swamy

    1999-05-04

    Fuel cells that convert hydrogen to electricity will play an increasingly important role in the generation of future electric power for stationary and transportation sector applications. However, more economic methods to produce hydrogen from fossil fuels are needed. This project addresses the need to develop low cost ceramic membranes for hydrogen separation from reformed fuels.

  17. Photoproduction of hydrogen using plant and microbial membrane systems. Final subcontract report

    SciTech Connect

    Olson, J.M.

    1983-12-01

    A solar hydrogen generator has been assembled from unit-membrane vesicles from green photosynthetic bacteria. The vesicles contain light-harvesting bacteriochlorophyll A, photochemical reaction centers and various electron carriers that deliver electrons from ascorbic acid to exogenous ferredoxin and hydrogenase. Hydrogen is formed with an overall quantum requirement of about 10 photons per electron transferred. Of 21 polypeptides found in the vesicle membranes five (25.0, 25.5, 38.5, 69, and 93 kD) have the possibility of a specific association with the reaction center. Another type of photosynthetic membrane from a thermophilic cyanobacterium contains both photosystem I and photosystem II reaction centers. Photosystem II particles prepared with the detergent lauryl dimethylamine oxide evolve oxygen from water and deliver electrons to a weak reductant, dimethylbenzoquinone, with an overall quantum requirement of about 5 photons per electron. If vesicles from green bacteria can be coupled to membranes or photosystem II particles from cyanobacteria, the combined system in sunlight should generate hydrogen from water with a maximum energy conversion efficiency of about 10%. 39 references, 9 figures, 4 tables.

  18. SEPARATION OF HAZARDOUS ORGANICS BY LOW PRESSURE REVERSE OSMOSIS MEMBRANES - PHASE II FINAL REPORT

    EPA Science Inventory

    Extensive experimental studies showed that thin-film, composite membranes can be used effectively for the separation of selected hazardous organic compounds. This waste treatment technique offers definite advantages in terms of high solute separations at low pressures (<2MPa) and...

  19. Energy-efficient membrane separations in the sweetener industry. Final report

    SciTech Connect

    Ray, R.J.

    1986-02-14

    Objective was to investigate the use of membrane processes as energy-efficient alternatives to certain conventional separation processes now in use in the corn-sweetener industry. Three applications of membranes were studied during the program: the concentration of corn steep water by reverse osmosis; the concentration of dilute wastes, called ''sweetwater,'' by a combination of reverse osmosis and countercurrent reverse osmosis; and the enrichment of corn syrup in fructose by a process involving selective complexation of fructose by membrane filtration. Laboratory experiments were conducted for all three applications, and the results were used to conduct technical and economic analyses of the process. Calculations indicate that the use of reverse osmosis in combination with conventional mechanical-vapor-recompression evaporation to concentrate steep water, offers savings of a factor of 2.5 in capital costs and a factor of 4.5 in operating costs over currently used evaporation alone. In the concentration of sweetwater by reverse osmosis and countercurrent reverse osmosis, capital costs would be about the same as those for evaporation, but operating costs would only be about one-half those of evaporation. For the fructose-enrichment scheme, preliminary results indicate that the savings in energy alone for the membrane process would be about $0.01/lb of sweetener produced by the process, or about $20 million annually, for the corn-sweetener industry.

  20. Molecular-scale studies of single-channel membrane pores : final report.

    SciTech Connect

    Fleming, James Grant; Evans, Kervin O.; Burns, Alan Richard; Swartzentruber, Brian Shoemaker

    2003-10-01

    We present our research results on membrane pores. The study was divided into two primary sections. The first involved the formation of protein pores in free-standing lipid bilayer membranes. The second involved the fabrication via surface micromachining techniques and subsequent testing of solid-state nanopores using the same characterization apparatus and procedures as that used for the protein pores. We were successful in our ability to form leak-free lipid bilayers, to detect the formation of single protein pores, and to monitor the translocation dynamics of individual homogeneous 100 base strands of DNA. Differences in translocation dynamics were observed when the base was switched from adenine to cytosine. The solid state pores (2-5 nm estimated) were fabricated in thin silicon nitride membranes. Testing of the solid sate pores indicated comparable currents for the same size protein pore with excellent noise and sensitivity. However, there were no conditions under which DNA translocation was observed. After considerable effort, we reached the unproven conclusion that multiple (<1 nm) pores were formed in the nitride membrane, thus explaining both the current sensitivity and the lack of DNA translocation blockages.

  1. Novel macrocyclic carriers for proton-coupled liquid membrane transport. Final report

    SciTech Connect

    Lamb, J.D.; Izatt, R.M.; Bradshaw, J.S.; Shirts, R.B.

    1996-08-24

    The objective of this research program is to elucidate the chemical principles which are responsible for the cation selectivity and permeability of liquid membranes containing macrocyclic carriers. Several new macrocyclic carriers were synthesized during the last three year period. In addition, new, more convenient synthetic routes were achieved for several nitrogen-containing bicyclic and tricyclic macrocycles. The cation binding properties of these macrocycles were investigated by potentiometric titration, calorimetric titration, solvent extraction and NMR techniques. In addition, hydrophobic macrocycles were incorporated into dual hollow fiber and other membrane systems to investigate their membrane performance, especially in the proton-coupled transport mode. A study of the effect of methoxyalkyl macrocycle substituents on metal ion transport was completed. A new calorimeter was constructed which made it possible to study the thermodynamics of macrocycle-cation binding to very high temperatures. Measurements of thermodynamic data for the interaction of crown ethers with alkali and alkaline earth cations were achieved to 473 K. Molecular modeling work was begun for the first time on this project and fundamental principles were identified and developed for the establishment of working models in the future.

  2. Membrane vapor recovery systems; Phase 1, Final report, 29 September 1990--29 April 1991

    SciTech Connect

    1991-01-01

    This report describes the work performed at Membrane Technology and Research, Inc. (MTR). The period covered is from September 29, 1990 to April 29, 1991, representing Phase 1 of the project. The overall objective of the project is the design, construct and demonstrate in the field a 50 scfm condensation/membrane separation system able to recover volatile organic compounds from effluent air streams. In the first phase of the program, a number of the high-pressure membranes modules to be installed in the system were constructed and evaluated. The results were satisfactory and no further module development work is required. The Field Demonstration Unit has also been designed. All of the major components have been selected and costed. The system can be constructed within the proposed budget. As a result of a visit to the host demonstration site (Great Lakes Chemical (GLC), El Dorado, Arkansas Plant), the Phase 2 program has been modified to include construction of small, high-pressure Field Module Evaluation Unit to be installed at GLC during the Phase 2 program. The host site engineers are prepared to install and monitor this unit. This additional work can be accomplished within the current budget and will provide valuable data prior to installation of the large Field Demonstration Unit. 18 figs., 8 tabs.

  3. Demonstration of membrane aeration panels: City of Geneva Wastewater Treatment Plant. Final report

    SciTech Connect

    1995-01-01

    This report describes the design, construction, and testing of membrane aeration panels at the Marsh Creek wastewater treatment plant (WWTP) in Geneva, NY. The operators at the Geneva plant have undertaken a long-term program to upgrade wastewater treatment processes and lower operating costs. The aging mechanical surface aerators at the Marsh Creek treatment plant were replaced by a state-of-the-art membrane panel system. This fine-bubble diffused air system offers higher oxygen transfer efficiency than surface aerators or other types of fine-bubble diffused-air systems. The project had four objectives: to decrease the amount of electricity used at the plant for aeration; to enable the plant`s existing aeration basins to accommodate higher organic loads and/or nitrify the wastewater should the need arise; to provide an even distribution of dissolved oxygen within the aeration basins to enhance biological wastewater treatment activity; and to provide technical data to assess the performance of the membrane panel system versus other forms of wastewater aeration.

  4. Membrane vesicles: A simplified system for studying auxin transport. Final technical report

    SciTech Connect

    Goldsmith, M.H.M.

    1989-12-31

    Indoleacetic acid (IAA), the auxin responsible for regulation of growth, is transported polarly in plants. Several different models have been suggested to account for IAA transport by cells and its accumulation by membrane vesicles. One model sees diffusion of IAA driven by a pH gradient. The anion of a lipophilic weak acid like IAA or butyrate accumulates in an alkaline compartment in accord with the size of the pH gradient The accumulation of IAA may be diminished by the permeability of its lipophilic anion. This anion leak may be blocked by NPA. With anion efflux blocked, a gradient of two pH units would support an IAA accumulation of less than 50-fold at equilibrium (2) Another model sees diffusion of IAA in parallel with a saturable symport (IAA{sup {minus}} + nH{sup +}), driven by both the pH gradient and membrane voltage. Such a symport should be highly accumulative, however, with a lipophilic weak acid such as IAA, net diffusive efflux of IAAH whenever IAAHI{sub i} > IAAH{sub o} would constitute a leak. (3) A third model sees a pH change driven IAA uptake and saturable symport enhanced by internal binding sites. Following pH gradient-driven accumulation of IAA, the anion may bind to an intravesicular site, permitting further uptake of IAA. NPA, by blocking anion efflux, enhances this binding. We have reported that membrane vesicles isolated from actively growing plant tissues are a good system for studying the mechanisms involved in the transport and accumulation of auxin.

  5. Catalytic Reforming

    SciTech Connect

    Little, D.M.

    1985-01-01

    Don Little's Catalytic Reforming deals exclusively with reforming. With the increasing need for unleaded gasoline, the importance of this volume has escalated since it combines various related aspects of reforming technology into a single publication. For those with no practical knowledge of catalytic reforming, the chemical reactions, flow schemes and how the cat reformer fits into the overall refinery process will be of interest. Contents include: Catalytic reforming in refinery processing: How catalytic reformers work - chemical reactions; Process design; The catalyst, process variables and unit operation; Commercial processes; BTX operation; Feed preparation; naphtha hydrotreating and catalytic reforming; Index.

  6. Energy-efficient membrane separations in the sweetener industry. Final report for Phase I

    SciTech Connect

    Babcock, W.C.

    1984-02-14

    The objective of the program is to investigate the use of membrane processes as energy-efficient alternatives to conventional separation processes in current use in the corn sweetener industry. Two applications of membranes were studied during the program: (1) the concentration of corn steep water by reverse osmosis; and (2) the concentration of dilute wastes called sweetwater with a combination of reverse osmosis and a process known as countercurrent reverse osmosis. Laboratory experiments were conducted for both applications, and the results were used to conduct technical and economic analyses of the process. It was determined that the concentration of steep water by reverse osmosis plus triple-effect evaporation offers savings of a factor of 2.5 in capital costs and a factor of 4.5 in operating costs over currently used triple-effect evaporation. In the concentration of sweetwater by reverse osmosis and countercurrent reverse osmosis, capital costs would be about the same as those for triple-effect evaporation, but operating costs would be only about one-half those of triple-effect evaporation.

  7. Photochemical energy conversion by membrane-bound photoredox systems. Final report

    SciTech Connect

    Tollin, G.

    1994-06-16

    This project has received DOE support since July 1, 1978. During this period, 40 papers have been published dealing predominantly with chlorophyll-photosensitized electron transfer reactions in a variety of media (solutions, polymer films, lipid bilayer membranes). The overall theme of this work has been to develop mechanistic strategies f or photochemical energy storage via chlorophyll, using the green plant photosynthetic system as a paradigm for designing in vitro systems. Microheterogeneous lipid vesicle suspensions allow ready application of time-resolved optical spectroscopy to follow the course of light-induced electron transfer processes. Both the yields and the lifetimes of electron transfer products were markedly improved in the vesicle systems. In subsequent studies, this compartmentalization was favorably manipulated by controlling the electrical charge on the membrane surface, by controlling the solubility properties of the acceptors, by varying the lipid composition, by using mediators to create a concentration gradient to carry electrons from within the bilayer to the aqueous medium, and by incorporating secondary electron acceptors into the aqueous phase.

  8. Development of alternative oxygen production source using a zirconia solid electrolyte membrane. Final report

    SciTech Connect

    Suitor, J.W.; Clark, D.J.; Losey, R.W.

    1990-08-01

    The objective of this multiyear effort was the development, fabrication and testing of a zirconia oxygen production module capable of delivering approximately 100 liters/minute (LPM) of oxygen. The work discussed in this report consists of development and improvement of the zirconia cell along with manufacture of cell components, preliminary design of the final plant, additional economic analysis and industrial participation. (VC)

  9. Detail design of a 10.4-m stretched-membrane dish. Phase 2, Final report

    SciTech Connect

    Not Available

    1994-01-01

    This report describes efforts conducted under Tasks 3 and 4 of the second phase of the project to develop a single-element stretched-membrane dish concept to reduce the cost of a high-performance concentrating solar collector. We completed the detailed design for such a collector suitable to drive a 25-kWe Stirling motor generator. The design includes the collectors, optical element, the drive, and support systems. The aperture of the optical element was sized to provide the required energy to the engine based on test data and analytical models of the concentrator receiver, and engine. The design of the optical element was improved based on experience gained from the design, fabrication, and testing of several prototypes.

  10. Close-coupled Catalytic Two-Stage Liquefaction (CTSL{trademark}) process bench studies. Final report, [October 1, 1988--July 31, 1993

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Karolkiewicz, W.F.; Lee, L.K.; Popper, G.A.; Stalzer, R.H.; Smith, T.O.

    1993-06-01

    This is the final report of a four year and ten month contract starting on October 1, 1988 to July 31, 1993 with the US Department of Energy to study and improve Close-Coupled Catalytic Two-Stage Direct Liquefaction of coal by producing high yields of distillate with improved quality at lower capital and production costs in comparison to existing technologies. Laboratory, Bench and PDU scale studies on sub-bituminous and bituminous coals are summarized and referenced in this volume. Details are presented in the three topical reports of this contract; CTSL Process Bench Studies and PDU Scale-Up with Sub-Bituminous Coal-DE-88818-TOP-1, CTSL Process Bench Studies with Bituminous Coal-DE-88818-TOP-2, and CTSL Process Laboratory Scale Studies, Modelling and Technical Assessment-DE-88818-TOP-3. Results are summarized on experiments and studies covering several process configurations, cleaned coals, solid separation methods, additives and catalysts both dispersed and supported. Laboratory microautoclave scale experiments, economic analysis and modelling studies are also included along with the PDU-Scale-Up of the CTSL processing of sub-bituminous Black Thunder Mine Wyoming coal. During this DOE/HRI effort, high distillate yields were maintained at higher throughput rates while quality was markedly improved using on-line hydrotreating and cleaned coals. Solid separations options of filtration and delayed coking were evaluated on a Bench-Scale with filtration successfully scaled to a PDU demonstration. Directions for future direct coal liquefaction related work are outlined herein based on the results from this and previous programs.

  11. Porous media for catalytic renewable energy conversion

    NASA Astrophysics Data System (ADS)

    Hotz, Nico

    2012-05-01

    A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

  12. Hot gas cleanup using ceramic cross flow membrane filters. Final report

    SciTech Connect

    Ciliberti, D.F.; Smeltzer, E.E.; Alvin, M.A.; Keairns, D.L.; Bachovchin, D.M.

    1983-12-01

    The single unresolved technical issue in the commercialization of pressurized fluid-bed combustion (PPBC) for electric power production is the hot gas cleaning problem. In this technology, high-temperature and -pressure (HTHP), dust-laden flue gases from the combustor must be cleaned enough to reduce expansion turbine blade erosion to an economically acceptable level. Additionally, the level of particulate emission must be compatible with the New Source Performance Standards (NSPS) for environmental acceptability. The Department of Energy (DOE) has sponsored a wide range of research and development programs directed at the solution of this problem. These programs were divided into two classifications, one dealing with more advanced concepts where testing was to be done at relatively large scale and a second group of less advanced, novel concepts where the testing was to be carried out at a bench scale. The cross-flow ceramic membrane filter program described in this report is a member of the small-scale, novel concept group.

  13. Purification and properties of a shortened form of cytochrome P-450 2E1: deletion of the NH2-terminal membrane-insertion signal peptide does not alter the catalytic activities.

    PubMed Central

    Larson, J R; Coon, M J; Porter, T D

    1991-01-01

    As reported previously, alcohol-inducible cytochrome P-450 2E1 lacking the hydrophobic NH2-terminal segment is located primarily in the inner cell membrane when expressed in Escherichia coli and is active with a typical substrate. To study the catalytic properties in detail, we have purified the truncated P-450 lacking residues 3-29 to electrophoretic homogeneity from the solubilized bacterial membrane fraction in the presence of 4-methylpyrazole as a stabilizing agent. The resulting heme protein with a specific content of 15.8 nmol of P-450 per mg of protein has a reduced CO difference spectrum identical to that of the full-length enzyme, with a Soret maximum at 452 nm. The rates of catalysis of four reactions in the reconstituted enzyme system, including the oxygenation of ethanol to give acetaldehyde, the oxidative dealkylation of N-nitrosodiethylamine to give ethylene and acetaldehyde, and the ring hydroxylation of aniline and p-nitrophenol, are the same with the shortened and full-length enzymes. The apparent Km of p-nitrophenol is also the same, as is that for NADPH-cytochrome P-450 reductase and for cytochrome b5, which stimulates p-nitrocatechol formation about 3-fold. Moreover, the requirement for phosphatidylcholine for full catalytic activity is unchanged despite the absence of the NH2-terminal segment. Although this highly hydrophobic segment is believed to play a role in the intact cell as a membrane-insertion signal sequence, we conclude that it has no function in the catalytic activity of the cytochrome as an oxygenase, including interactions with the other components of the enzyme system. Images PMID:1656462

  14. Novel membranes for proton exchange membrane fuel cell operation above 120°C. Final report for period October 1, 1998 to December 31, 1999

    SciTech Connect

    Srinivasan, Supramaniam; Lee, Seung-Jae; Costamagna, Paola; Yang, Christopher; Adjemian, Kevork; Bocarsly, Andrew; Ogden, Joan M.; Benziger, Jay

    2000-05-01

    In this project we investigated the experimental performance of three new classes of membranes, composites of perfluorosulfonic acid polymers with heteropolyacides, hydrated oxides and fast proton conducting glasses, which are promising candidates as electrolytes for proton exchange membrane fuel cells (PEMFCs), capable of operation at temperatures above 120°C. The motivations for PEMFC's operation at this temperature are to: 1) minimize the CO poisoning problem (adsorption of CO onto the platinum catalyst is greatly reduced at these temperatures), 2) find better solutions for the water and thermal management problems in proton exchange membrane fuel cells, 3) find potentially lower cost materials for proton exchange membranes. We prepared and characterized a variety of novel membrane materials. The most promising of these have been evaluated for performance in a single, small area (5cm2) fuel cell run on hydrogen and oxygen. Our results establish the technical feasibility of PEMFC operation above 120°C.

  15. Final Report: Fiscal Year 1997 NO{sub x} selective catalytic reduction demonstration of Russian DeNO{sub x} catalysts at MSE/WETO Facility

    SciTech Connect

    Zundelevich, Y.; Adamson, M.

    1998-04-01

    The primary purpose of this work was for LLNL to coordinate, analyze and provide general technical support for testing of environmentally- benign catalysts for the selective reduction of NO{sub x} with ammonia. The catalysts were developed at the Boreskov Institute of Catalysis (BIC) in Russia and the testing was performed in WETO facilities at Butte, Montana. In these tests, the performance of the Russian catalysts has been directly compared for effectiveness with a commercial Western selective catalytic reduction (SCR) catalyst.

  16. Effects of dispersion and support on adsorption, catalytic and electronic properties of cobalt/alumina Co hydrogenation catalysts. Final progress report, August 1, 1987--July 31, 1990

    SciTech Connect

    Bartholomew, C.H.

    1990-09-29

    An investigation of the effects of surface structure, dispersion, and support on the adsorption, catalytic, and electronic properties of cobalt/alumina is described, the objectives of which were to determine (1) the effects of surface structure and metal dispersion on the adsorption and catalytic properties of cobalt and (2) the effects of direct electronic interactions between metal clusters and support, on the adsorption, catalytic and electronic properties of cobalt supported on alumina. Effects of surface structure and dispersion on the adsorption, activity/selectivity, and electronic properties of Co/W single crystal surfaces and alumina-supported cobalt were investigated in a surface investigation, lab reactor studies, TPD/TPSR studies, and a Moessbauer spectroscopy study. The structure, stability, surface electronic properties, and chemisorptive properties of vapor-deposited cobalt overlayers (0-4 ML) on W(110) and W(100) were studied by Auger electron spectroscopy, low energy electron diffraction, work function changes, and temperature programmed desorption (TPD) of cobalt, hydrogen, and carbon monoxide. The CO chemisorptive properties of the two cobalt overlayers are quite different, CO adsorption being dissociative on the W(100) surface and nondissociative on the W(110) surface; comparison of the results with those for Ni/W(100) indicate that Co/W(100) dissociates CO as a result of electronic interaction with the tungsten substrate.

  17. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction. Final technical report, Volume 2 - hydrogenative and hydrothermal pretreatments and spectroscopic characterization using pyrolysis-GC-MS, CPMAS {sup 13}C NMR and FT-IR

    SciTech Connect

    Chunshan Song; Hatcher, P.G.; Saini, A.K.; Wenzel, K.A.

    1998-01-01

    It has been indicated by DOE COLIRN panel that low-temperature catalytic pretreatment is a promising approach to the development of an improved liquefaction process. This work is a fundamental study on effects of pretreatments on coal structure and reactivity in liquefaction. The main objectives of this project are to study the coal structural changes induced by low-temperature catalytic and thermal pretreatments by using spectroscopic techniques; and to clarify the pretreatment-induced changes in reactivity or convertibility of coals. As the second volume of the final report, here we summarize our work on spectroscopic characterization of four raw coals including two subbituminous coals and two bituminous coals, tetrahydrofuran (THF)-extracted but unreacted coals, the coals (THF-insoluble parts) that have been thermally pretreated. in the absence of any solvents and in the presence of either a hydrogen-donor solvent or a non-donor solvent, and the coals (THF-insoluble parts) that have been catalytically pretreated in the presence of a dispersed Mo sulfide catalyst in the absence of any solvents and in the presence of either a hydrogen-donor solvent or a non-donor solvent.

  18. Blood coagulation reactions on nanoscale membrane surfaces

    NASA Astrophysics Data System (ADS)

    Pureza, Vincent S.

    Blood coagulation requires the assembly of several membrane-bound protein complexes composed of regulatory and catalytic subunits. The biomembranes involved in these reactions not only provide a platform for these procoagulant proteins, but can also affect their function. Increased exposure of acidic phospholipids on the outer leaflet of the plasma membrane can dramatically modulate the catalytic efficiencies of such membrane-bound enzymes. Under physiologic conditions, however, these phospholipids spontaneously cluster into a patchwork of membrane microdomains upon which membrane binding proteins may preferentially assemble. As a result, the membrane composition surrounding these proteins is largely unknown. Through the development and use of a nanometer-scale bilayer system that provides rigorous control of the phospholipid membrane environment, I investigated the role of phosphatidylserine, an acidic phospholipid, in the direct vicinity (within nanometers) of two critical membrane-bound procoagulant protein complexes and their respective natural substrates. Here, I present how the assembly and function of the tissue factor˙factor VIIa and factor Va˙factor Xa complexes, the first and final cofactor˙enzyme complexes of the blood clotting cascade, respectively, are mediated by changes in their immediate phospholipid environments.

  19. Transient catalytic combustor model

    NASA Technical Reports Server (NTRS)

    Tien, J. S.

    1981-01-01

    A quasi-steady gas phase and thermally thin substrate model is used to analyze the transient behavior of catalytic monolith combustors in fuel lean operation. The combustor response delay is due to the substrate thermal inertia. Fast response is favored by thin substrate, short catalytic bed length, high combustor inlet and final temperatures, and small gas channel diameters. The calculated gas and substrate temperature time history at different axial positions provides an understanding of how the catalytic combustor responds to an upstream condition change. The computed results also suggest that the gas residence times in the catalytic bed in the after bed space are correlatable with the nondimensional combustor response time. The model also performs steady state combustion calculations; and the computed steady state emission characteristics show agreement with available experimental data in the range of parameters covered. A catalytic combustor design for automotive gas turbine engine which has reasonably fast response ( 1 second) and can satisfy the emission goals in an acceptable total combustor length is possible.

  20. Transient catalytic combustor model

    NASA Astrophysics Data System (ADS)

    Tien, J. S.

    1981-05-01

    A quasi-steady gas phase and thermally thin substrate model is used to analyze the transient behavior of catalytic monolith combustors in fuel lean operation. The combustor response delay is due to the substrate thermal inertia. Fast response is favored by thin substrate, short catalytic bed length, high combustor inlet and final temperatures, and small gas channel diameters. The calculated gas and substrate temperature time history at different axial positions provides an understanding of how the catalytic combustor responds to an upstream condition change. The computed results also suggest that the gas residence times in the catalytic bed in the after bed space are correlatable with the nondimensional combustor response time. The model also performs steady state combustion calculations; and the computed steady state emission characteristics show agreement with available experimental data in the range of parameters covered. A catalytic combustor design for automotive gas turbine engine which has reasonably fast response ( 1 second) and can satisfy the emission goals in an acceptable total combustor length is possible.

  1. R&D on an Ultra-Thin Composite Membrane for High-Temperature Operation in PEMFC. Final Report

    SciTech Connect

    Yuh, C.-Y.

    2003-10-06

    FuelCell Energy developed a novel high-temperature proton exchange membrane for PEM fuel cells for building applications. The laboratory PEM fuel cell successfully operated at 100-400{supdegree}C and low relative humidity to improve CO tolerance, mitigate water and thermal management challenges, and reduce membrane cost. The developed high-temperature membrane has successfully completed 500h 120C endurance testing.

  2. Assessment of the potential for refinery applications of inorganic membrane technology: An identification and screening analysis. Final report

    SciTech Connect

    Johnson, H.E.; Schulman, B.L.

    1993-05-01

    Commercial application of membrane technology in the separation of gas, liquid, and solid streams has grown to a business with worldwide revenues exceeding $1 billion annually. Use of organic membranes for industrial gas separation, particularly in the refining industry, is one of the major growth areas. However, organic membranes based on polymeric separation barriers, are susceptible to damage by liquids, and careful precautions must be taken to retain the system integrity. Researchers are currently developing small pore sized inorganic membranes which may substantially increase the efficiency and economics in selected refinery separation applications. Expected advantages of these advanced inorganic membranes include high permeability, high selectivity, and low manufacturing cost. SFA Pacific conducted a screening analysis to identify applications for inorganic membrane technology in the petroleum refining industry and their potential cost advantages over competing separation systems. Two meetings were held in connection with this project. Copies of Viewgraphs presented by SFA Pacific at these meetings are attached in Appendices A and C. Potential high priority applications and market impacts of advanced inorganic membrane technology in the refining industry are addressed in this report, and include the following areas: Competitive separation technologies; application of those technologies; incentives for inorganic membranes; market benefits and impacts of inorganic membranes.

  3. Variability in natural gas fuel composition and its effects on the performance of catalytic combustion systems. Final report for period September 18, 1998 - September 17, 2000

    SciTech Connect

    Ginter, David; Simchick, Chuck; Schlatter, Jim

    2002-03-01

    Natural gas is composed primarily of methane with small amounts of higher hydrocarbons and diluents, which vary by region and over time. Compositions of natural gas from domestic and worldwide sources were surveyed with respect to content of higher hydrocarbons and diluents. The survey showed slight compositional variability between most of the gases, with a small fraction of them containing significantly larger contents of higher hydrocarbons than the mean. As gas-fired turbines will be used for power generation all over the world, they will need to tolerate operation with fuels with a wide variety of compositions, particularly with respect to the concentration of higher hydrocarbons and diluents. Subscale catalytic combustion modules typical of those used in gas turbine power generation with ultra low emissions of pollutants were tested in a subscale test system with natural gas alone and with added known levels of hydrocarbon compounds and diluents. The range of compositions tested contained the range observed in the survey. Test results were used to calculate the effect of composition on catalyst performance. The compositional variability is of little consequence to the catalyst for most of the gases in the survey, including nearly all of the gases delivered in the U.S. To accommodate the remaining gases, the catalyst inlet temperature must be lowered to maintain combustor durability. These results support commercial acceptance of catalytic combustion systems for use in natural gas fired turbines in distributed power generation with ultra low NO{sub x} emissions.

  4. Process for Coating Substrates with Catalytic Materials

    NASA Technical Reports Server (NTRS)

    Klelin, Ric J. (Inventor); Upchurch, Billy T. (Inventor); Schryer, David R. (Inventor)

    2004-01-01

    A process for forming catalysts by coating substrates with two or more catalytic components, which comprises the following sequence of steps. First, the substrate is infused with an adequate amount of solution having a starting material comprising a catalytic component precursor, wherein the thermal decomposition product of the catalytic component precursor is a catalytic component. Second, the excess of the solution is removed from the substrate. thereby leaving a coating of the catalytic component precursor on the surface of the substrate. Third, the coating of the catalytic component precursor is converted to the catalytic component by thermal decomposition. Finally, the coated substance is etched to increase the surface area. The list three steps are then repeated for at least a second catalytic component. This process is ideally suited for application in producing efficient low temperature oxidation catalysts.

  5. Energy efficient membrane processes for the separation of organic liquids: Part 2: Final report, September 28, 1982--December 31, 1986

    SciTech Connect

    Cabasso, I.; Acharya, H.R.; Korngold, E.; Liu, Z.; Stern, S.A.; Li, W.; Makenzie, T.; Poda, E.

    1987-10-01

    The present report demonstrates the use of membrane technology for dehydration processes concentrating on two examples: azeotropic separation of isopropanol-water, and separation of ethanol-water mixtures (starting at 84.5 wt. % ethanol where separation by distillation begins to be progressively more energy intensive). The principles of the membrane separation processes employed in such separations were discussed in Part I of the report. The advantage of the membrane processes is that they do not require the addition of a third component and separation is a continuous process. Pervaporation, perstraction, and air-sweep pervaporation were thoroughly studied for these separations. An urgent need for the identification of the appropriate membrane was realized. This study has revealed that ion-exchange membranes are suited for these separations. Results are discussed. 9 refs., 68 figs., 33 tabs.

  6. LDRD final report on imaging self-organization of proteins in membranes by photocatalytic nano-tagging.

    SciTech Connect

    Zavadil, Kevin Robert; Shelnutt, John Allen; Sasaki, Darryl Yoshio; Song, Yujiang; Medforth, Craig J.

    2005-11-01

    We have developed a new nanotagging technology for detecting and imaging the self-organization of proteins and other components of membranes at nanometer resolution for the purpose of investigating cell signaling and other membrane-mediated biological processes. We used protein-, lipid-, or drug-bound porphyrin photocatalysts to grow in-situ nanometer-sized metal particles, which reveal the location of the porphyrin-labeled molecules by electron microscopy. We initially used photocatalytic nanotagging to image assembled multi-component proteins and to monitor the distribution of lipids and porphyrin labels in liposomes. For example, by exchanging the heme molecules in hemoproteins with a photocatalytic tin porphyrin, a nanoparticle was grown at each heme site of the protein. The result obtained from electron microscopy for a tagged multi-subunit protein such as hemoglobin is a symmetric constellation of a specific number of nanoparticle tags, four in the case of the hemoglobin tetramer. Methods for covalently linking photocatalytic porphyrin labels to lipids and proteins were also developed to detect and image the self-organization of lipids, protein-protein supercomplexes, and membrane-protein complexes. Procedures for making photocatalytic porphyrin-drug, porphyrin-lipid, and porphyrin-protein hybrids for non-porphyrin-binding proteins and membrane components were pursued and the first porphyrin-labeled lipids was investigated in liposomal membrane models. Our photocatalytic nanotagging technique may ultimately allow membrane self-organization and cell signaling processes to be imaged in living cells. Fluorescence and plasmonic spectra of the tagged proteins might also provide additional information about protein association and membrane organization. In addition, a porphyrin-aspirin or other NSAID hybrid may be used to grow metal nanotags for the pharmacologically important COX enzymes in membranes so that the distribution of the protein can be imaged at the

  7. Development of Novel active transport membrane devices. Phase I. Final report, 31 October 1988--31 January 1994

    SciTech Connect

    Laciak, D.V.; Quinn, R.; Choe, G.S.; Cook, P.J.; Tsai, Fu-Jya

    1994-08-01

    The main objective of this program was to identify and develop a technique for fabricating Active Transport Materials (ATM) into lab-scale membrane devices. Air Products met this objective by applying thin film, multilayer fabrication techniques to support the AT material on a substrate membrane. In Phase IA, spiral-wound hollow fiber membrane modules were fabricated and evaluated. These nonoptimized devices were used to demonstrate the AT-based separation of carbon dioxide from methane, hydrogen sulfide from methane, and ammonia from hydrogen. It was determined that a need exists for a more cost efficient and less energy intensive process for upgrading subquality natural gas. Air Products estimated the effectiveness of ATM for this application and concluded that an optimized ATM system could compete effectively with both conventional acid gas scrubbing technology and current membrane technology. In addition, the optimized ATM system would have lower methane loss and consume less energy than current alternative processes. Air Products made significant progress toward the ultimate goal of commercializing an advanced membrane for upgrading subquality natural gas. The laboratory program focused on developing a high performance hollow fiber substrate and fabricating and evaluating ATM-coated lab-scale hollow fiber membrane modules. Selection criteria for hollow fiber composite membrane supports were developed and used to evaluate candidate polymer compositions. A poly(amide-imide), PAI, was identified for further study. Conditions were identified which produced microporous PAI support membrane with tunable surface porosity in the range 100-1000{Angstrom}. The support fibers exhibited good hydrocarbon resistance and acceptable tensile strength though a higher elongation may ultimately be desirable. ATM materials were coated onto commercial and PAI substrate fiber. Modules containing 1-50 fibers were evaluated for permselectivity, pressure stability, and lifetime.

  8. Oxygen enrichment of air using semipermeable membranes in a magnetic field. Final report, January 15, 1983-January 14, 1985

    SciTech Connect

    Not Available

    1985-01-01

    The use of semipermeable membranes to enrich oxygen from air has recently drawn a great deal of interest, particularly for combustion and medical applications. The maximum possible oxygen enrichment of air using silicone membranes is approximately 50%. By applying a nonuniform magnetic field to the membrane system, the paramagnetic properties of oxygen in theory may be used to achieve increased enrichment. Four magnetic test cells were developed to induce nonuniformity in a magnetic field of 15 Kilogauss. Three membranes were evaluated on these test cells: dimethyl silicone, dimethyl silicone/polycarbonate copolymer (MEM-213), and cellulose acetate. The evaluation consisted of determining the oxygen flux at various pressure differences across the membrane. The tests were run at room temperature and pressure, both in and out of the magnetic field. The 15 Kilogauss magnetic field currently available to us produced negligible increases in the oxygen concentration with all pole pieces. A mathematical model was developed which showed that fields of 200-400 Kilogauss are needed to get enrichments of 0.5% and to overcome the reverse polarization (concentration diffusion) of oxygen built up next to the membrane. Fluxes in this range have been experimentally achieved but are not currently commercially available. This additional oxygen would cost 800 times more than currently available pure oxygen.

  9. Final Technical Report "Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation" Grant number : DE-FG02-86ER13615

    SciTech Connect

    Wayland, B.B.

    2009-08-31

    Title: Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation Grant No. DE-FG02-86ER13615 PI: Wayland, B. B. (wayland@sas.upenn.edu) Abstract Development of new mechanistic strategies and catalyst materials for activation of CO, H2, CH4, C2H4, O2, and related substrates relevant to the conversion of carbon monoxide, alkanes, and alkenes to organic oxygenates are central objectives encompassed by this program. Design and synthesis of metal complexes that manifest reactivity patterns associated with potential pathways for the hydrogenation of carbon monoxide through metallo-formyl (M-CHO), dimetal ketone (M-C(O)-M), and dimetal dionyl (M-C(O)-C(O)-M) species is one major focus. Hydrocarbon oxidation using molecular oxygen is a central goal for methane activation and functionalization as well as regioselective oxidation of olefins. Discovery of new reactivity patterns and control of selectivity are pursued through designing new metal complexes and adjusting reaction conditions. Variation of reaction media promotes distinct reaction pathways that control both reaction rates and selectivities. Dimetalloradical diporphyrin complexes preorganize transition states for substrate reactions that involve two metal centers and manifest large rate increases over mono-metalloradical reactions of hydrogen, methane, and other small molecule substrates. Another broad goal and recurring theme of this program is to contribute to the thermodynamic database for a wide scope of organo-metal transformations in a range of reaction media. One of the most complete descriptions of equilibrium thermodynamics for organometallic reactions in water and methanol is emerging from the study of rhodium porphyrin substrate reactions in aqueous and alcoholic media. Water soluble group nine metalloporphyrins manifest remarkably versatile substrate reactivity in aqueous and alcoholic media which includes producing rhodium formyl (Rh-CHO) and hydroxy methyl (Rh-CH2OH) species. Exploratory

  10. Final Technical Report for DOE Grant, number DE-FG02-05ER15701; Probing Surface Chemistry Under Catalytic Conditions: Olefin Hydrogenation,Cyclization and Functionalization.

    SciTech Connect

    Neurock, Matthew

    2011-05-26

    The specific goal of this work was to understanding the catalytic reactions pathways for the synthesis of vinyl acetate over Pd, Au and PdAu alloys. A combination of both experimental methods (X-ray and Auger spectroscopies, low-energy ion scattering (LEIS), low-energy electron diffraction (LEED) and theory (Density Functional Theory (DFT) calculations and Monte Carlo methods under various different reactions) were used to track the surface chemistry and the influence of alloying. The surface intermediates involved in the various reactions were characterized using reflection-absorption infrared spectroscopy and LEED to identify the nature of the surface species and temperature-programmed desorption (TPD) to follow the decomposition pathways and measure heats of adsorption. These results along with those from density functional theoretical calculations were used determine the kinetics for elementary steps. The results from this work showed that the reaction proceeds via the Samanos mechanism over Pd surfaces whereby the ethylene directly couples with acetate to form an acetoxyethyl intermediate that subsequently undergoes a beta-hydride elimination to form the vinyl acetate monomer. The presence of Au was found to modify the adsorption energies and surface coverages of important surface intermediates including acetate, ethylidyne and ethylene which ultimately influences the critical C-H activation and coupling steps. By controlling the surface alloy composition or structure one can begin to control the steps that control the rate and even the mechanism.

  11. Ceramic oxygen transport membrane array reactor and reforming method

    DOEpatents

    Kelly, Sean M.; Christie, Gervase Maxwell; Robinson, Charles; Wilson, Jamie R.; Gonzalez, Javier E.; Doraswami, Uttam R.

    2016-11-08

    The invention relates to a commercially viable modular ceramic oxygen transport membrane reforming reactor configured using repeating assemblies of oxygen transport membrane tubes and catalytic reforming reactors.

  12. Membrane alterations following toxic chemical insult. Research progress report No. 3 (Final), 15 July 1984-31 January 1988

    SciTech Connect

    Liss, A.

    1988-03-10

    A procaryotic cell system was developed that can be used to determine the toxic action of chemicals acting at the level of the eucaryotic or procaryotic cytoplasmic membrane. Cell wall-less microbes known as mycoplasmas were used. In this current study, two perfluorinated fatty acids (CB and C10) were found to inhibit the growth of the test mycoplasmas. Two apparent activities, cytotoxicity and cytolysis, were observed. At high concentrations (>10 mM), a detergent-like action was noted. At low concentrations (<10 mM), cell death was observed without detectable cell lysis. Altering the cell membrane (the presumed target of the toxic compounds) resulted in altered levels to toxicity. Similar results were obtained when human or murine B-cells were used as the target organism. The toxic action of the perfluorinated fatty acids apparently involves some interaction with the membrane of the cells being treated.

  13. Energy efficient membrane processes for the separation of organic liquids: Part 1: Final report, September 28, 1982--December 31, 1986

    SciTech Connect

    Cabasso, I.; Acharya, H.R.; Korngold, E.; Liu, Z.; Stern, S.A.; Li, W.; Makenzie, T.; Poda, E.

    1987-10-01

    The potential usefulness of two membrane processes, namely, pervaporation and perstraction, for separating azeotropic mixtures of aromatic and aliphatic hydrocarbons was studied theoretically and experimentally. A third membrane process, osmotic phase-separation, was investigated experimentally. The separation of an azeotropic mixture of benzene and cyclohexane was used as an example. Part II of this report will discuss membrane processes for the separation of alcohol/water mixtures. Mathematical models of pervaporation and perstraction were developed for computer simulations of the processes. The perstraction model presented herein is the first of its kind. Additionally, the energy requirements and capital investments costs for the separation of an azeotropic benzene/cyclohexane mixture were determined and compared with those for extractive distillation. 31 refs., 64 figs., 19 tabs.

  14. Characterization and isolation of a light driven sodium pump from membranes of Halobacterium halobium. Final technical progress report

    SciTech Connect

    MacDonald, R.E.

    1982-01-01

    We investigated three aspects of the light driven sodium pump (halorhodopsin, which appear to be crucial to our understanding of the mechanisms employed by Halobacterium halobium and to further investigate this unique system of energy conservation. We characterized the molecular mechanisms of transmembrane sodium transport in vesicles from H. halobium with particular reference to the mechanism of couplins of light energy to net sodium translocation. We develop procedures and techniques for extracting the components of the light driven sodium pump from membranes and incorporating them into artificial membrane systems. We examine the mechanism of conversion of bacteriorhodopsin from an active to an inactive form in membrane vesicles and to relate this alternative state of this pigment to the presence of the light driven sodium pump.

  15. The Kemp elimination in membrane mimetic reaction media. Probing catalytic properties of cationic vesicles formed from a double-tailed amphiphile and linear long-tailed alcohols or alkyl pyranosides.

    PubMed

    Klijn, Jaap E; Engberts, Jan B F N

    2004-06-21

    Vesicles formed from synthetic, double-tailed amphiphiles are often used as mimics for biological membranes. However, biological membranes are a complex mixture of various compounds. In the present paper we describe a first attempt to study the importance of additives on vesicular catalysis. The rate-determining deprotonation of 5-nitrobenzisoxazole (Kemp elimination) by hydroxide ion is efficiently catalysed by vesicles formed from dimethyldi-n-octadecylammonium chloride (C(18)C(18)(+)) as a result of (partial) dehydration of the reactants (especially the hydroxide ion) at the vesicular binding sites. Gradual addition of linear alcohols, such as n-decanol (C(10)OH), n-octadecanol (C(18)OH) and batyl alcohol (C(18)GlyOH) leads to a decrease in the observed catalysis. By contrast, gradual addition of oleyl alcohol, n-dodecyl-beta-glucoside (C(12)Glu) and n-dodecyl-beta-maltoside (C(12)Mal) leads to an increase in the observed catalysis. A detailed kinetic analysis, taking into account substrate binding site polarities, counterion binding percentages and binding affinity of the kinetic probe, suggests that the catalytic changes depend strongly on subtle changes in the structure of the additive. Whereas the C(12)Glu-induced effect can be explained by an increase in the vesicular rate constant, the effect of C(12)Mal can only be explained by an increase in the binding constant of the kinetic probe. However, for these pyranoside-containing vesicles others factors, such as a more extensive dehydration of the hydroxide ion, and micelle formation have to be considered. For the linear alcohols, besides a decrease in the counterion binding, changes in the vesicular rate constant and the binding constant should be taken into account. These two parameters change to a different extent for the different alcohols. The kinetic analysis is supported by differential scanning calorimetry (DSC), E(T)(30) absorbance data and Nile Red, Laurdan, ANS and pyrene fluorescence measurements

  16. Identification of the aspartic proteinases from human erythrocyte membranes and gastric mucosa (slow-moving proteinase) as catalytically equivalent to cathepsin E.

    PubMed Central

    Jupp, R A; Richards, A D; Kay, J; Dunn, B M; Wyckoff, J B; Samloff, I M; Yamamoto, K

    1988-01-01

    Three aspartic proteinases with similar Mr values (approx. 80,000) but from distinct sources (human gastric mucosa, human erythrocyte membranes and rat spleen) were shown to have immunological cross-reactivity and comparable mobilities when subjected to polyacrylamide-gel electrophoresis under non-denaturing conditions. Kinetic parameters (kcat, Km and Ki) were determined for the interactions of the three enzymes with two synthetic chromogenic substrates and five inhibitors (naturally occurring and synthetic). On this basis it would appear that all of the enzymes should be considered equivalent to cathepsin E. pH-activity measurements indicated that the aspartic proteinase that originated from the erythrocyte membranes retained activity at a higher pH value than either of its readily soluble counterparts. Images Fig. 1. Fig. 2. PMID:3058118

  17. Association with the Plasma Membrane Is Sufficient for Potentiating Catalytic Activity of Regulators of G Protein Signaling (RGS) Proteins of the R7 Subfamily.

    PubMed

    Muntean, Brian S; Martemyanov, Kirill A

    2016-03-25

    Regulators of G protein Signaling (RGS) promote deactivation of heterotrimeric G proteins thus controlling the magnitude and kinetics of responses mediated by G protein-coupled receptors (GPCR). In the nervous system, RGS7 and RGS9-2 play essential role in vision, reward processing, and movement control. Both RGS7 and RGS9-2 belong to the R7 subfamily of RGS proteins that form macromolecular complexes with R7-binding protein (R7BP). R7BP targets RGS proteins to the plasma membrane and augments their GTPase-accelerating protein (GAP) activity, ultimately accelerating deactivation of G protein signaling. However, it remains unclear if R7BP serves exclusively as a membrane anchoring subunit or further modulates RGS proteins to increase their GAP activity. To directly answer this question, we utilized a rapidly reversible chemically induced protein dimerization system that enabled us to control RGS localization independent from R7BP in living cells. To monitor kinetics of Gα deactivation, we coupled this strategy with measuring changes in the GAP activity by bioluminescence resonance energy transfer-based assay in a cellular system containing μ-opioid receptor. This approach was used to correlate changes in RGS localization and activity in the presence or absence of R7BP. Strikingly, we observed that RGS activity is augmented by membrane recruitment, in an orientation independent manner with no additional contributions provided by R7BP. These findings argue that the association of R7 RGS proteins with the membrane environment provides a major direct contribution to modulation of their GAP activity.

  18. Catalytic Two-Stage Liquefaction (CTSL{trademark}) process bench studies and PDU scale-up with sub-bituminous coal. Final report

    SciTech Connect

    Comolli, A.G.; Johanson, E.S.; Karolkiewicz, W.F.; Lee, L.K.T.; Stalzer, R.H.; Smith, T.O.

    1993-03-01

    Reported are the details and results of Laboratory and Bench-Scale experiments using sub-bituminous coal conducted at Hydrocarbon Research, Inc., under DOE Contract No. DE-AC22-88PC88818 during the period October 1, 1988 to December 31, 1992. The work described is primarily concerned with testing of the baseline Catalytic Two-Stage Liquefaction (CTSL{trademark}) process with comparisons with other two stage process configurations, catalyst evaluations and unit operations such as solid separation, pretreatments, on-line hydrotreating, and an examination of new concepts. In the overall program, three coals were evaluated, bituminous Illinois No. 6, Burning Star and sub-bituminous Wyoming Black Thunder and New Mexico McKinley Mine seams. The results from a total of 16 bench-scale runs are reported and analyzed in detail. The runs (experiments) concern process variables, variable reactor volumes, catalysts (both supported, dispersed and rejuvenated), coal cleaned by agglomeration, hot slurry treatments, reactor sequence, on-line hydrotreating, dispersed catalyst with pretreatment reactors and CO{sub 2}/coal effects. The tests involving the Wyoming and New Mexico Coals are reported herein, and the tests involving the Illinois coal are described in Topical Report No. 2. On a laboratory scale, microautoclave tests evaluating coal, start-up oils, catalysts, thermal treatment, CO{sub 2} addition and sulfur compound effects were conducted and reported in Topical Report No. 3. Other microautoclave tests are described in the Bench Run sections to which they refer such as: rejuvenated catalyst, coker liquids and cleaned coals. The microautoclave tests conducted for modelling the CTSL{trademark} process are described in the CTSL{trademark} Modelling section of Topical Report No. 3 under this contract.

  19. Zeolite membrane cascade for tritium extraction and recovery systems

    SciTech Connect

    Borisevich, O.; Demange, D.; Lefebvre, X.; Kind, M.

    2015-03-15

    Membrane separation by zeolite membranes has been proposed as a pre-concentration stage for the tritium extraction from the purge helium of the breeding blanket combined with a final recovery by the catalytic membrane reactor PERMCAT. This fully continuous operation improves the tritium management in fusion machines, minimizing the tritium inventory. For the first time, the permeation measurements for H{sub 2} - He mixtures through a MFI-alumina hollow fibre membrane has been measured for different compositions (0.1 - 20% H{sub 2}) and temperatures. Such a highly permeable membrane, although it shows a limited selectivity, appears attractive for tritium recovery in the blanket. This will imply its operation in a membrane cascade, for which simulation work is ongoing. Mathematically the process is modeled using mass balance equations that can be transformed into the matrix form and solved iteratively assuming a permeate concentration on the first step of iteration, until the separation requirements are fulfilled.

  20. Research on degradation product and reaction kinetics of membrane electro-bioreactor (MEBR) with catalytic electrodes for high concentration phenol wastewater treatment.

    PubMed

    Wang, Tao; Zhao, Huanping; Wang, Hui; Liu, Botan; Li, Chunqing

    2016-07-01

    The membrane electro-bioreactor (MEBR) is a novel technology, it treats wastewater by combining membrane filtration, electrokinetic phenomena, and biological processes in one reactor. This paper aims to deal with hard biodegradation and high concentration phenol wastewater. Investigating the influence factors such as initial concentration, voltage, pH value, temperature and mixed liquor suspended solids (MLSS) toward phenol degradation process in electrocatalytic process and membrane bioreactor (MBR), and then apply the optimum conditions in the MEBR system. Results of continuous flow experiments demonstrated that MEBR increased the quality of the treated wastewater than conventional MBR. The above technics followed the zero-order reaction kinetics. The removal efficiency of MEBR was about 11.1% higher for phenol than the sum of the two individual processes. With the help of gas chromatography/mass spectrometry (GC-MS), this qualitative analysis looks at the degradation products of phenol generated in MEBR, through which 2,6-di-tert-butyl-p-benzoquinone was confirmed as the main degradation product. Copyright © 2016. Published by Elsevier Ltd.

  1. Catalytic reforming

    SciTech Connect

    Aldag, A.W. Jr.

    1986-01-28

    This patent describes a process for the catalytic reforming of a feedstock which contains at least one reformable organic compound. The process consists of contacting the feedstock under suitable reforming conditions with a catalyst composition selected from the group consisting of a catalyst. The catalyst essentially consists of zinc oxide and a spinel structure alumina. Another catalyst consists essentially of a physical mixture of zinc titanate and a spinel structure alumina in the presence of sufficient added hydrogen to substantially prevent the formation of coke. Insufficient zinc is present in the catalyst composition for the formation of a bulk zinc aluminate.

  2. DNA-Cu(II) poly(amine) complex membrane as novel catalytic layer for highly sensitive amperometric determination of hydrogen peroxide.

    PubMed

    Gu, Tingting; Hasebe, Yasushi

    2006-05-15

    A novel hydrogen peroxide biosensor was fabricated by using a DNA-Cu(II) complex as a novel electrocatalyst for the reduction of hydrogen peroxide (H2O2). A polyion complex (PIC) membrane composed of DNA and poly(allylamine) (PAA) functioned as a support matrix for immobilization of electrocatalytic element-copper ion. The circular dichroism (CD) spectrum of the DNA-Cu(II)/PAA membrane in wet state showed that the DNA exists in B-like form within the membrane. Electrochemical measurements of the DNA-Cu(II)/PAA membrane-modified glassy carbon (GC) electrode revealed that the copper ion embedded in the DNA/PAA layer exhibits good electrochemical behaviors, and the electrochemical rate constant between the immobilized copper ion and the GC electrode surface was estimated to be 26.4 s(-1). The resulting DNA-Cu(II)/PAA/GC electrode showed an excellent electrocatalytic activity for the H2O2 reduction. The sensitivity of the sensor for the determination of H2O2 was affected by the amount of each component, such as copper ion, DNA and PAA in the DNA-Cu(II)/PAA membrane. Effects of applied potential, pH, temperature, ionic strength and buffer concentrations upon the response currents of the sensor were also investigated for an optimum analytical performance. Even in the presence of dissolved oxygen, the sensor exhibited highly sensitive and rapid (response time, less than 5 s) response to H2O2. The steady-state cathodic current responses of the sensor obtained at -0.2 V versus Ag/AgCl in air-saturated 50 mM phosphate buffer (pH 5.0) increased linearly up to 135 microM with the detection limit of 50 nM. Interference by ascorbic acid and uric acid due to the reduction of Cu(II) was effectively cancelled by further modification of outermost layer of polyion complex film. In addition, the sensor exhibited good reproducibility and stability.

  3. Catalytic reactor

    SciTech Connect

    Aaron, Timothy Mark; Shah, Minish Mahendra; Jibb, Richard John

    2009-03-10

    A catalytic reactor is provided with one or more reaction zones each formed of set(s) of reaction tubes containing a catalyst to promote chemical reaction within a feed stream. The reaction tubes are of helical configuration and are arranged in a substantially coaxial relationship to form a coil-like structure. Heat exchangers and steam generators can be formed by similar tube arrangements. In such manner, the reaction zone(s) and hence, the reactor is compact and the pressure drop through components is minimized. The resultant compact form has improved heat transfer characteristics and is far easier to thermally insulate than prior art compact reactor designs. Various chemical reactions are contemplated within such coil-like structures such that as steam methane reforming followed by water-gas shift. The coil-like structures can be housed within annular chambers of a cylindrical housing that also provide flow paths for various heat exchange fluids to heat and cool components.

  4. Stable Closure of the Cytoplasmic Half-Channel Is Required for Efficient Proton Transport at Physiological Membrane Potentials in the Bacteriorhodopsin Catalytic Cycle

    PubMed Central

    2015-01-01

    The bacteriorhodopsin (BR) Asp96Gly/Phe171Cys/Phe219Leu triple mutant has been shown to translocate protons 66% as efficiently as the wild-type protein. Light-dependent ATP synthesis in haloarchaeal cells expressing the triple mutant is 85% that of the wild-type BR expressing cells. Therefore, the functional activity of BR seems to be largely preserved in the triple mutant despite the observations that its ground-state structure resembles that of the wild-type M state (i.e., the so-called cytoplasmically open state) and that the mutant shows no significant structural changes during its photocycle, in sharp contrast to what occurs in the wild-type protein in which a large structural opening and closing occurs on the cytoplasmic side. To resolve the contradiction between the apparent functional robustness of the triple mutant and the presumed importance of the opening and closing that occurs in the wild-type protein, we conducted additional experiments to compare the behavior of wild-type and mutant proteins under different operational loads. Specifically, we characterized the ability of the two proteins to generate light-driven proton currents against a range of membrane potentials. The wild-type protein showed maximal conductance between −150 and −50 mV, whereas the mutant showed maximal conductance at membrane potentials >+50 mV. Molecular dynamics (MD) simulations of the triple mutant were also conducted to characterize structural changes in the protein and in solvent accessibility that might help to functionally contextualize the current–voltage data. These simulations revealed that the cytoplasmic half-channel of the triple mutant is constitutively open and dynamically exchanges water with the bulk. Collectively, the data and simulations help to explain why this mutant BR does not mediate photosynthetic growth of haloarchaeal cells, and they suggest that the structural closing observed in the wild-type protein likely plays a key role in minimizing

  5. Stable closure of the cytoplasmic half-channel is required for efficient proton transport at physiological membrane potentials in the bacteriorhodopsin catalytic cycle.

    PubMed

    Wang, Ting; Oppawsky, Christoph; Duan, Yong; Tittor, Jörg; Oesterhelt, Dieter; Facciotti, Marc T

    2014-04-15

    The bacteriorhodopsin (BR) Asp96Gly/Phe171Cys/Phe219Leu triple mutant has been shown to translocate protons 66% as efficiently as the wild-type protein. Light-dependent ATP synthesis in haloarchaeal cells expressing the triple mutant is 85% that of the wild-type BR expressing cells. Therefore, the functional activity of BR seems to be largely preserved in the triple mutant despite the observations that its ground-state structure resembles that of the wild-type M state (i.e., the so-called cytoplasmically open state) and that the mutant shows no significant structural changes during its photocycle, in sharp contrast to what occurs in the wild-type protein in which a large structural opening and closing occurs on the cytoplasmic side. To resolve the contradiction between the apparent functional robustness of the triple mutant and the presumed importance of the opening and closing that occurs in the wild-type protein, we conducted additional experiments to compare the behavior of wild-type and mutant proteins under different operational loads. Specifically, we characterized the ability of the two proteins to generate light-driven proton currents against a range of membrane potentials. The wild-type protein showed maximal conductance between -150 and -50 mV, whereas the mutant showed maximal conductance at membrane potentials >+50 mV. Molecular dynamics (MD) simulations of the triple mutant were also conducted to characterize structural changes in the protein and in solvent accessibility that might help to functionally contextualize the current-voltage data. These simulations revealed that the cytoplasmic half-channel of the triple mutant is constitutively open and dynamically exchanges water with the bulk. Collectively, the data and simulations help to explain why this mutant BR does not mediate photosynthetic growth of haloarchaeal cells, and they suggest that the structural closing observed in the wild-type protein likely plays a key role in minimizing substrate

  6. Novel Approaches to Immobilized Heteropoly Acid Systems for High Temperature, Low Relative Humidity Polymer-Type Membranes - Final Report

    SciTech Connect

    Herring, Andrew M; Horan, James L; Aieta, Niccolo V; Sachdeva, Sonny; Kuo, Mei-Chen; Ren, Hui; Lingutla, Anitha; Emery, Michael; Haugen, Gregory M; Yandrasits, Michael A; Sharma, Neeraj; Coggio, William D; Hamrock, Steven J; Frey, Matthew H

    2012-05-20

    Original research was carried out at the CSM and the 3M Company from March 2007 through September 2011. The research was aimed at developing new to the world proton electrolyte materials for use in hydrogen fuel cells, in particular with high proton conductivity under hot and dry conditions (>100mS/cm at 120°C and 50%RH). Broadly stated, the research at 3M and between 3M and CSM that led to new materials took place in two phases: In the first phase, hydrocarbon membranes that could be formed by photopolymerization of monomer mixtures were developed for the purpose of determining the technical feasibility of achieving the program's Go/No-Go decision conductivity target of >100mS/cm at 120°C and 50%RH. In the second phase, attempts were made to extend the achieved conductivity level to fluorinated material systems with the expectation that durability and stability would be improved (over the hydrocarbon material). Highlights included: Multiple lots of an HPA-immobilized photocurable terpolymer derived from di-vinyl-silicotungstic acid (85%), n-butyl acrylate, and hexanediol diacrylate were prepared at 3M and characterized at 3M to exhibit an initial conductivity of 107mS/cm at 120°C and 47%RH (PolyPOM85v) using a Bekktech LLC sample fixture and TestEquity oven. Later independent testing by Bekktech LLC, using a different preheating protocol, on the same material, yielded a conductivity value of approximately 20mS/cm at 120°C and 50%RH. The difference in measured values is likely to have been the result of an instability of properties for the material or a difference in the measurement method. A dispersed catalyst fuel cell was fabricated and tested using a 150¼m thick HPA-based photocurable membrane (above, PolyPOM75v), exhibiting a current density of greater than 300mA/cm2 at 0.5V (H2/Air 800/1800sccm 70°C/75%RH ambient outlet pressure). Multiple lots of a co-polymer based on poly-trifluorovinylether (TFVE) derived HPA were synthesized and fabricated into

  7. A mechanistic study of molecular sieving inorganic membranes for gas separations. Final report, [August 1, 1992--July 31, 1993

    SciTech Connect

    Way, J.D.

    1993-05-03

    The permeability of gases with kinetic diameters of 2.89 {Angstrom} to 3.9 {Angstrom} were measured through microporous silica hollow fiber membranes at 298 K to 473 K at 20 atm feed gas pressure. Permeabilities ranged from 0.01 Barrer to 1000 Barrer and were inversely proportional to the kinetic diameter of the penetrant. Linear Arrhenius plots were obtained from permeability data activation energies ranged from 7.5 to 13.5 kcal/mole. The activation energies for the hollow Tiber membranes were consistent with literature data for diffusion of hydrocarbons in zeolites. High separation factors were obtained for O{sub 2}/N{sub 2} and CO{sub 2}/CH{sub 2} mixtures. The mixture separation factors for O{sub 2}/N{sub 2} decreased from 11.5 at 298 K to 4.6 at 423 K. Over the same temperature range, CO{sub 2}/CH{sub 2} separation factors decreased from 186 to 22.3. Separation factors for O{sub 2}/N{sub 2} mixtures were up to 20% larger than the values obtained from pure gas measurements below 373 K. A similar effect was seen for CO{sub 2}/CH{sub 2} mixtures after the membrane had been heated to at least 398 K and then cooled in inert gas flow. Differences between separation factors and ideal gas values is attributed to a competitive adsorption effect where the more strongly interacting gases (O{sub 2}, CO{sub 2}) saturate the surface and block the transport of weakly interacting gases (N{sub 2}, CH{sub 4}).

  8. High-temperature membranes for H{sub 2}S and SO{sub 2} separations. Final report

    SciTech Connect

    Winnick, J.

    1995-01-01

    Electrochemical cells which separate H{sub 2}S and S0{sub 2} from hot gas streams have two important materials issues that limit their successful industrial application: (1) membranes and (2) electrodes. These were the focus of the present study. For the H{sub 2}S work, experimental analysis incorporated several membrane and electrode materials; densified zirconia provided the best matrices for entrainment of electrolytic species, ionic mobility, and a process-gas barricade hindering the capabilities of gas cross-over, alternate reactions. Electrode materials of lithiated Ni converted to NiO in-situ were successful in polishing applications; however H{sub 2}S levels >100 ppM converted the NiO cathode to a molten nickel sulfide necessitating the use of Co. Lithiated NiO for the anode material remained morphologically stable and conductive in all experimentation. High temperature electrochemical removal of H{sub 2}S from coal gasification streams has been shown on the bench scale level at the Georgia Institute of Technology utilizing the aforementioned materials. Experimental removals from 1000 ppM to 100 ppM H{sub 2}S and 100 ppM to 10 ppM H{sub 2}S proved over 90% removal with applied current was economically feasible due to high current efficiencies ({approximately}100%) and low polarizations. For the S0{sub 2}work, an extensive search was conducted for a suitable membrane material for use in the S0{sub 2} removal system. The most favorable material found was Si{sub 3}N{sub 4}, proven to be more efficient than other possible materials. New lithiated NiO electrodes were also developed and characterized, proving more stable than previously used pervoskite electrodes. The combination of these new components led to 90% removal at near 100% current efficiency over a wide range of current densities.

  9. The Investigation and Development of Low Cost Hardware Components for Proton-Exchange Membrane Fuel Cells - Final Report

    SciTech Connect

    George A. Marchetti

    1999-12-15

    Proton exchange membrane (PEM) fuel cell components, which would have a low-cost structure in mass production, were fabricated and tested. A fuel cell electrode structure, comprising a thin layer of graphite (50 microns) and a front-loaded platinum catalyst layer (600 angstroms), was shown to produce significant power densities. In addition, a PEM bipolar plate, comprising flexible graphite, carbon cloth flow-fields and an integrated polymer gasket, was fabricated. Power densities of a two-cell unit using this inexpensive bipolar plate architecture were shown to be comparable to state-of-the-art bipolar plates.

  10. Deashing of coal liquids with ceramic membrane microfiltration and diafiltration. Final technical report, August 4, 1992--September 30, 1995

    SciTech Connect

    1996-03-01

    Removal of mineral matter from liquid hydrocarbons derived from the direct liquefaction of coal is required for product acceptability. Current methods include critical solvent Deashing and filtration, both of which produce an ash reject stream containing up to 15% of the liquid hydrocarbon product. This program was directed towards development of an improved process for deashing and recovery of coal-derived residual oil: the use of ceramic membranes for high-temperature microfiltration and diafiltration. Using laboratory scale ceramic membrane modules, samples of a coal-derived residual oil containing ash were processed by crossflow microfiltration, followed by solvent addition and refiltration (diafiltration). Excellent recovery of deashed residual oil was demonstrated. Data from this program were used to develop preliminary estimates for production system capital and operating costs that will be used to assess economic feasibility. The first objective of this program was to demonstrate technical feasibility of crossflow microfiltration (MF) for removal of mineral matter from a coal derived residual oil. A second objective was to demonstrate technical feasibility of diafiltration of W concentrate using a hydrocarbon diluent.

  11. Clean hydrogen generation through the electrocatalytic oxidation of ethanol in a Proton Exchange Membrane Electrolysis Cell (PEMEC): Effect of the nature and structure of the catalytic anode

    NASA Astrophysics Data System (ADS)

    Lamy, Claude; Jaubert, Thomas; Baranton, Stève; Coutanceau, Christophe

    2014-01-01

    The electrocatalytic oxidation of ethanol was investigated in a Proton Exchange Membrane Electrolysis Cell (PEMEC) working at low temperature (20°C) on several Pt-based catalysts (Pt/C, PtSn/C, PtSnRu/C) in order to produce very clean hydrogen by electrolysis of a biomass compound. The electrocatalytic activity was determined by cyclic voltammetry and the rate of hydrogen evolution was measured for each catalyst at different current densities. The cell voltages UEtOH were recorded as a function of time for each current density. At 100 mA cm-2, i.e. 0.5 A with the 5 cm2 surface area PEMEC used, the cell voltage did not exceed 0.9 V for an evolution rate of about 220 cm3 of hydrogen per hour and the electrical energy consumed was less than 2.3 kWh (Nm3)-1, i.e. less than one half of the energy needed for water electrolysis (4.7 kWh (Nm3)-1 at UH2O = 2 V). This result is valid for the decomposition of any organic compound, particularly those originated from biomass resource, provided that their electro-oxidation rate is sufficient (>100 mA cm-2) at a relatively low cell voltage (Ucell < 1 V) which necessitates the development of efficient electrocatalysts for the electrochemical decomposition of this compound.

  12. Retinal degeneration 3 (RD3) protein inhibits catalytic activity of retinal membrane guanylyl cyclase (RetGC) and its stimulation by activating proteins.

    PubMed

    Peshenko, Igor V; Olshevskaya, Elena V; Azadi, Seifollah; Molday, Laurie L; Molday, Robert S; Dizhoor, Alexander M

    2011-11-08

    Retinal membrane guanylyl cyclase (RetGC) in the outer segments of vertebrate photoreceptors is controlled by guanylyl cyclase activating proteins (GCAPs), responding to light-dependent changes of the intracellular Ca(2+) concentrations. We present evidence that a different RetGC binding protein, retinal degeneration 3 protein (RD3), is a high-affinity allosteric modulator of the cyclase which inhibits RetGC activity at submicromolar concentrations. It suppresses the basal activity of RetGC in the absence of GCAPs in a noncompetitive manner, and it inhibits the GCAP-stimulated RetGC at low intracellular Ca(2+) levels. RD3 opposes the allosteric activation of the cyclase by GCAP but does not significantly change Ca(2+) sensitivity of the GCAP-dependent regulation. We have tested a number of mutations in RD3 implicated in human retinal degenerative disorders and have found that several mutations prevent the stable expression of RD3 in HEK293 cells and decrease the affinity of RD3 for RetGC1. The RD3 mutant lacking the carboxy-terminal half of the protein and associated with Leber congenital amaurosis type 12 (LCA12) is unable to suppress the activity of the RetGC1/GCAP complex. Furthermore, the inhibitory activity of the G57V mutant implicated in cone-rod degeneration is strongly reduced. Our results suggest that inhibition of RetGC by RD3 may be utilized by photoreceptors to block RetGC activity during its maturation and/or incorporation into the photoreceptor outer segment rather than participate in dynamic regulation of the cyclase by Ca(2+) and GCAPs.

  13. Final Report of a CRADA Between Pacific Northwest National Laboratory and the General Motors Company (CRADA No. PNNL/271): “Degradation Mechanisms of Urea Selective Catalytic Reduction Technology”

    SciTech Connect

    Kim, Do Heui; Lee, Jong H.; Peden, Charles HF; Howden, Ken; Kim, Chang H.; Oh, Se H.; Schmieg, Steven J.; Wiebenga, Michelle H.

    2011-12-13

    Diesel engines can offer substantially higher fuel efficiency, good driving performance characteristics, and reduced carbon dioxide (CO2) emission compared to stoichiometric gasoline engines. Despite the increasing public demand for higher fuel economy and reduced dependency on imported oil, however, meeting the stringent emission standards with affordable methods has been a major challenge for the wide application of these fuel-efficient engines in the US market. The selective catalytic reduction of NOx by urea (urea-SCR) is one of the most promising technologies for NOx emission control for diesel engine exhausts. To ensure successful NOx emission control in the urea-SCR technology, both a diesel oxidation catalyst (DOC) and a urea-SCR catalyst with high activity and durability are critical for the emission control system. Because the use of this technology for light-duty diesel vehicle applications is new, the relative lack of experience makes it especially challenging to satisfy the durability requirements. Of particular concern is being able to realistically simulate actual field aging of the catalyst systems under laboratory conditions, which is necessary both as a rapid assessment tool for verifying improved performance and certifiability of new catalyst formulations. In addition, it is imperative to develop a good understanding of deactivation mechanisms to help develop improved catalyst materials. In this CRADA program, General Motors Company and PNNL have investigated fresh, laboratory- and vehicle-aged DOC and SCR catalysts. The studies have led to a better understanding of various aging factors that impact the long-term performance of catalysts used in the urea-SCR technology, and have improved the correlation between laboratory and vehicle aging for reduced development time and cost. This Final Report briefly highlights many of the technical accomplishments and documents the productivity of the program in terms of peer-reviewed scientific publications

  14. Raney nickel catalytic device

    DOEpatents

    O'Hare, Stephen A.

    1978-01-01

    A catalytic device for use in a conventional coal gasification process which includes a tubular substrate having secured to its inside surface by expansion a catalytic material. The catalytic device is made by inserting a tubular catalytic element, such as a tubular element of a nickel-aluminum alloy, into a tubular substrate and heat-treating the resulting composite to cause the tubular catalytic element to irreversibly expand against the inside surface of the substrate.

  15. Research and development of proton-exchange membrane (PEM) fuel cell system for transportation applications. Phase I final report

    SciTech Connect

    1996-01-01

    Objective during Phase I was to develop a methanol-fueled 10-kW fuel cell power source and evaluate its feasibility for transportation applications. This report documents research on component (fuel cell stack, fuel processor, power source ancillaries and system sensors) development and the 10-kW power source system integration and test. The conceptual design study for a PEM fuel cell powered vehicle was documented in an earlier report (DOE/CH/10435-01) and is summarized herein. Major achievements in the program include development of advanced membrane and thin-film low Pt-loaded electrode assemblies that in reference cell testing with reformate-air reactants yielded performance exceeding the program target (0.7 V at 1000 amps/ft{sup 2}); identification of oxidation catalysts and operating conditions that routinely result in very low CO levels ({le} 10 ppm) in the fuel processor reformate, thus avoiding degradation of the fuel cell stack performance; and successful integrated operation of a 10-kW fuel cell stack on reformate from the fuel processor.

  16. Alkaline fuel cell with nitride membrane

    NASA Astrophysics Data System (ADS)

    Sun, Shen-Huei; Pilaski, Moritz; Wartmann, Jens; Letzkus, Florian; Funke, Benedikt; Dura, Georg; Heinzel, Angelika

    2017-06-01

    The aim of this work is to fabricate patterned nitride membranes with Si-MEMS-technology as a platform to build up new membrane-electrode-assemblies (MEA) for alkaline fuel cell applications. Two 6-inch wafer processes based on chemical vapor deposition (CVD) were developed for the fabrication of separated nitride membranes with a nitride thickness up to 1 μm. The mechanical stability of the perforated nitride membrane has been adjusted in both processes either by embedding of subsequent ion implantation step or by optimizing the deposition process parameters. A nearly 100% yield of separated membranes of each deposition process was achieved with layer thickness from 150 nm to 1 μm and micro-channel pattern width of 1μm at a pitch of 3 μm. The process for membrane coating with electrolyte materials could be verified to build up MEA. Uniform membrane coating with channel filling was achieved after the optimization of speed controlled dip-coating method and the selection of dimethylsulfoxide (DMSO) as electrolyte solvent. Finally, silver as conductive material was defined for printing a conductive layer onto the MEA by Ink-Technology. With the established IR-thermography setup, characterizations of MEAs in terms of catalytic conversion were performed successfully. The results of this work show promise for build up a platform on wafer-level for high throughput experiments.

  17. Development of a membrane-based process for the treatment of oily waste waters. Final report, March 4, 1992--March 5, 1994

    SciTech Connect

    McCray, S.B.

    1994-05-25

    This is a final report from Bend Research, Inc., (BRI) to the U.S. Department of Energy (DOE) for work performed under Contract No. DE-AC22-92MT92005, titled {open_quotes}Development of a Membrane-Based Process for the Treatment of Oily Waste Waters.{close_quotes} This report covers the period from March 4, 1992, to March 5, 1994. The overall goal of this program was to develop an economical oily-water treatment system based on reverse osmosis (RO). The RO system would be used to (1) reduce oil production costs by reducing the volume of waste water that must be disposed of, (2) form the basis of a generic waste-water treatment system that can easily be integrated into oil-field operations, especially at production facilities that are small or in remote locations; and (3) produce water clean enough to meet existing and anticipated environmental regulations. The specific focus of this program was the development of a hollow-fiber membrane module capable of treating oily waste waters.

  18. Loss of autoinhibition of the plasma membrane Ca(2+) pump by substitution of aspartic 170 by asparagin. A ctivation of plasma membrane calcium ATPase 4 without disruption of the interaction between the catalytic core and the C-terminal regulatory domain.

    PubMed

    Bredeston, Luis M; Adamo, Hugo P

    2004-10-01

    The plasma membrane calcium ATPase (PMCA) actively transports Ca(2+) from the cytosol to the extra cellular space. The C-terminal segment of the PMCA functions as an inhibitory domain by interacting with the catalytic core. Ca(2+)-calmodulin binds to the C-terminal segment and stops inhibition. Here we showed that residue Asp(170), in the putative "A" domain of human PMCA isoform 4xb, plays a critical role in autoinhibition. In the absence of calmodulin a PMCA containing a site-specific mutation of D170N had 80% of the maximum activity of the calmodulin-activated PMCA and a similar high affinity for Ca(2+). The mutation did not change the activation of the PMCA by ATP. Deletion of the C-terminal segment further downstream of the calmodulin-binding site led to an additional increase in the maximal activity of the mutant, which suggests that the mutation did not affect the inhibition because of this portion of the C-terminal segment. The calmodulin-activated PMCA was more sensitive to vanadate inhibition than the autoinhibited enzyme. In contrast, inhibition of the D170N mutant required higher concentrations of vanadate and was not affected by calmodulin. Despite its higher basal activity, the mutant had an apparent affinity for calmodulin similar to that of the wild type enzyme, and its rate of proteolysis at the C-terminal segment was still calmodulin-dependent. Altogether these results suggest that activation by mutation D170N does not involve the displacement of the calmodulin-binding autoinhibitory domain from the catalytic core and may arise directly from changes in the accessibility to the calcium-binding residues of the pump.

  19. Demonstration of selective catalytic reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers. Draft final report

    SciTech Connect

    1996-06-14

    The primary goal of this project was to demonstrate the use of Selective Catalytic Reduction (SCR) to reduce NO{sub x} emissions from pulverized-coal utility boilers using medium- to high-sulfur US coal. The prototype SCR facility, built in and around the ductwork of Plant Crist Unit 5, consisted of three large SCR reactor units (Reactors A, B, and C), each with a design capacity of 5,000 standard cubic feet per minute (scfm) of flue gas, and six smaller reactors (Reactors D through J), each with a design capacity of 400 scfm of flue gas. The three large reactors contained commercially available SCR catalysts as offered by SCR catalyst suppliers. These reactors were coupled with small-scale air preheaters to evaluate (1) the long-term effects of SCR reaction chemistry on air preheater deposit formation and (2) the impact of these deposits on the performance of air preheaters. The small reactors were used to test additional varieties of commercially available catalysts. The demonstration project was organized into three phases: (1) Permitting, Environmental Monitoring Plan (EMP) Preparation, and Preliminary Engineering; (2) Detail Design Engineering and Construction; and (3) Operation, Testing, Disposition, and Final Report Preparation. Section 2 discusses the planned and actual EMP monitoring for gaseous, aqueous, and solid streams over the course of the SCR demonstration project; Section 3 summarizes sampling and analytical methods and discusses exceptions from the methods specified in the EMP; Section 4 presents and discusses the gas stream monitoring results; Section 5 presents and discusses the aqueous stream monitoring results; Section 6 presents and discusses the solid stream monitoring results; Section 7 discusses EMP-related quality assurance/quality control activities performed during the demonstration project; Section 8 summarizes compliance monitoring reporting activities; and Section 9 presents conclusions based on the EMP monitoring results.

  20. Switchable catalytic DNA catenanes.

    PubMed

    Hu, Lianzhe; Lu, Chun-Hua; Willner, Itamar

    2015-03-11

    Two-ring interlocked DNA catenanes are synthesized and characterized. The supramolecular catenanes show switchable cyclic catalytic properties. In one system, the catenane structure is switched between a hemin/G-quadruplex catalytic structure and a catalytically inactive state. In the second catenane structure the catenane is switched between a catalytically active Mg(2+)-dependent DNAzyme-containing catenane and an inactive catenane state. In the third system, the interlocked catenane structure is switched between two distinct catalytic structures that include the Mg(2+)- and the Zn(2+)-dependent DNAzymes.

  1. Development of Batch and Flow Immobilized Catalytic Systems with High Catalytic Activity and Reusability.

    PubMed

    Yamada, Yoichi M A

    2017-01-01

    My mission in catalysis research is to develop highly active and reusable supported catalytic systems in terms of fundamental chemistry and industrial application. For this purpose, I developed three types of highly active and reusable supported catalytic systems. The first type involves polymeric base-supported metal catalysts: Novel polymeric imidazole-Pd and Cu complexes were developed that worked at the mol ppm level for a variety of organic transformations. The second involves catalytic membrane-installed microflow reactors: Membranous polymeric palladium and copper complex/nanoparticle catalysts were installed at the center of a microtube to produce novel catalytic membrane-immobilized flow microreactor devices. These catalytic devices mediated a variety of organic transformations to afford the corresponding products in high yield within 1-38 s. The third is a silicon nanowire array-immobilized palladium nanoparticle catalyst. This device promoted a variety of organic transformations as a heterogeneous catalyst. The Mizoroki-Heck reaction proceeded with 280 mol ppb (0.000028 mol%) of the catalyst, affording the corresponding products in high yield.

  2. NASA In-step: Permeable Membrane Experiment

    NASA Technical Reports Server (NTRS)

    1992-01-01

    Viewgraphs on the Permeable Membrane Experiment are presented. An experiment overview is given. The Membrane Phase Separation Experiment, Membrane Diffusion Interference Experiment, and Membrane Wetting Experiment are described. Finally, summary and conclusions are discussed.

  3. Rich catalytic injection

    SciTech Connect

    Veninger, Albert

    2008-12-30

    A gas turbine engine includes a compressor, a rich catalytic injector, a combustor, and a turbine. The rich catalytic injector includes a rich catalytic device, a mixing zone, and an injection assembly. The injection assembly provides an interface between the mixing zone and the combustor. The injection assembly can inject diffusion fuel into the combustor, provides flame aerodynamic stabilization in the combustor, and may include an ignition device.

  4. Two stage catalytic combustor

    NASA Technical Reports Server (NTRS)

    Alvin, Mary Anne (Inventor); Bachovchin, Dennis (Inventor); Smeltzer, Eugene E. (Inventor); Lippert, Thomas E. (Inventor); Bruck, Gerald J. (Inventor)

    2010-01-01

    A catalytic combustor (14) includes a first catalytic stage (30), a second catalytic stage (40), and an oxidation completion stage (49). The first catalytic stage receives an oxidizer (e.g., 20) and a fuel (26) and discharges a partially oxidized fuel/oxidizer mixture (36). The second catalytic stage receives the partially oxidized fuel/oxidizer mixture and further oxidizes the mixture. The second catalytic stage may include a passageway (47) for conducting a bypass portion (46) of the mixture past a catalyst (e.g., 41) disposed therein. The second catalytic stage may have an outlet temperature elevated sufficiently to complete oxidation of the mixture without using a separate ignition source. The oxidation completion stage is disposed downstream of the second catalytic stage and may recombine the bypass portion with a catalyst exposed portion (48) of the mixture and complete oxidation of the mixture. The second catalytic stage may also include a reticulated foam support (50), a honeycomb support, a tube support or a plate support.

  5. Supported ionic liquid membrane in membrane reactor

    NASA Astrophysics Data System (ADS)

    Makertihartha, I. G. B. N.; Zunita, M.; Dharmawijaya, P. T.; Wenten, I. G.

    2017-01-01

    Membrane reactor is a device that integrates membrane based separation and (catalytic) chemical reaction vessel in a single device. Ionic liquids, considered to be a relatively recent magical chemical due to their unique properties, have a large variety of applications in all areas of chemical industries. Moreover, the ionic liquid can be used as membrane separation layer and/or catalytically active site. This paper will review utilization of ionic liquid in membrane reactor related applications especially Fischer-Tropsch, hydrogenation, and dehydrogenation reaction. This paper also reviews about the capability of ionic liquid in equilibrium reaction that produces CO2 product so that the reaction will move towards the product. Water gas shift reaction in ammonia production also direct Dimethyl Ether (DME) synthesis that produces CO2 product will be discussed. Based on a review of numerous articles on supported ionic liquid membrane (SILM) indicate that ionic liquids have the potential to support the process of chemical reaction and separation in a membrane reactor.

  6. Glutathione peroxidase 4-catalyzed reduction of lipid hydroperoxides in membranes: The polar head of membrane phospholipids binds the enzyme and addresses the fatty acid hydroperoxide group toward the redox center.

    PubMed

    Cozza, Giorgio; Rossetto, Monica; Bosello-Travain, Valentina; Maiorino, Matilde; Roveri, Antonella; Toppo, Stefano; Zaccarin, Mattia; Zennaro, Lucio; Ursini, Fulvio

    2017-07-12

    GPx4 is a monomeric glutathione peroxidase, unique in reducing the hydroperoxide group (-OOH) of fatty acids esterified in membrane phospholipids. This reaction inhibits lipid peroxidation and accounts for enzyme's vital role. Here we investigated the interaction of GPx4 with membrane phospholipids. A cationic surface near the GPx4 catalytic center interacts with phospholipid polar heads. Accordingly, SPR analysis indicates cardiolipin as the phospholipid with maximal affinity to GPx4. Consistent with the electrostatic nature of the interaction, KCl increases the KD. Molecular dynamic (MD) simulation shows that a -OOH posed in the core of the membrane as 13 - or 9 -OOH of tetra-linoleoyl cardiolipin or 15 -OOH stearoyl-arachidonoyl-phosphaphatidylcholine moves to the lipid-water interface. Thereby, the -OOH groups are addressed toward the GPx4 redox center. In this pose, however, the catalytic site facing the membrane would be inaccessible to GSH, but the consecutive redox processes facilitate access of GSH, which further primes undocking of the enzyme, because GSH competes for the binding residues implicated in docking. During the final phase of the catalytic cycle, while GSSG is produced, GPx4 is disconnected from the membrane. The observation that GSH depletion in cells induces GPx4 translocation to the membrane, is in agreement with this concept. Copyright © 2017. Published by Elsevier Inc.

  7. Alcohol recovery and carbon dioxide purification in alcohol plants using semipermeable membranes. Final technical report, September 1, 1981-August 31, 1982

    SciTech Connect

    Klei, H.E.; Sundstrom, D.W.

    1983-02-01

    The fermentation of sugars to ethanol produces carbon dioxide gas, which can carry appreciable quantities of alcohol vapor from the system. This project examined the use of commercially available membranes to separate a gaseous mixture into alcohol rich and carbon dioxide rich streams. The performance of silicone and cellulose acetate membranes in separating alcohol-carbon dioxide mixtures was studied with a single stage test cell. The cellulose acetate membrane passed the alcohol vapor preferentially and gave a better separation than the silicone membranes. The permeabilities of alcohol and carbon dioxide for the cellulose acetate membrane were used to design a continuous membrane column, which makes it possible to achieve a high degree of separation with membranes giving only modest enrichment in a single stage. For a 25 x 10/sup 6/ gal/yr alcohol plant, a computer simulation indicated that 200 continuous membrane columns with areas of 93 m/sup 2/ each would be needed to recover about 75% of the alcohol and to produce a byproduct stream containing 99.5% carbon dioxide.

  8. Catalytic distillation structure

    DOEpatents

    Smith, Jr., Lawrence A.

    1984-01-01

    Catalytic distillation structure for use in reaction distillation columns, a providing reaction sites and distillation structure and consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and being present with the catalyst component in an amount such that the catalytic distillation structure consist of at least 10 volume % open space.

  9. Deashing of coal liquids with ceramic membrane microfiltration and diafiltration. Final quarterly technical progress report, January 1, 1995--March 31, 1995

    SciTech Connect

    1995-12-01

    Removal of mineral matter from liquid hydrocarbons derived from the direct liquefaction of coal is required for product acceptability. Current methods include critical solvent de-ashing and filtration, both of which produce an ash reject stream containing up to 15% of the liquid hydrocarbon product. This program is directed towards development of an improved process for de-ashing and recovery of coal-derived residual oil: the use of ceramic membranes for high-temperature microfiltration and diafiltration. Using laboratory-scale ceramic membrane modules, samples of a coal-derived residual oil containing ash will be processed by crossflow microfiltration, followed by solvent addition and refiltration (diafiltration). Recovery of de-ashed residual oil will be demonstrated. Data from this program will be used to develop a preliminary engineering design and cost estimate for a demonstration pilot plant incorporating full-scale membrane modules. In addition, estimates for production system capital and operating costs will be developed to assess process economic feasibility. The five program tasks include (1) ceramic membrane fabrication, (2) membrane test system assembly, (3) testing of the ceramic membranes, (4) design of a demonstration system using full scale membrane modules, and (5) development of estimates for microfiltration capital and operating costs and assessment of process economic feasibility.

  10. Turning goals into results: the power of catalytic mechanisms.

    PubMed

    Collins, J

    1999-01-01

    Most executives have a big, hairy, audacious goal. They write vision statements, formalize procedures, and develop complicated incentive programs--all in pursuit of that goal. In other words, with the best of intentions, they install layers of stultifying bureaucracy. But it doesn't have to be that way. In this article, Jim Collins introduces the catalytic mechanism, a simple yet powerful managerial tool that helps translate lofty aspirations into concrete reality. Catalytic mechanisms are the crucial link between objectives and performance; they are a galvanizing, nonbureaucratic means to turn one into the other. What's the difference between catalytic mechanisms and most traditional managerial controls? Catalytic mechanisms share five characteristics. First, they produce desired results in unpredictable ways. Second, they distribute power for the benefit of the overall system, often to the discomfort of those who traditionally hold power. Third, catalytic mechanisms have teeth. Fourth, they eject "viruses"--those people who don't share the company's core values. Finally, they produce an ongoing effect. Catalytic mechanisms are just as effective for reaching individual goals as they are for corporate ones. To illustrate how catalytic mechanisms work, the author draws on examples of individuals and organizations that have relied on such mechanisms to achieve their goals. The same catalytic mechanism that works in one organization, however, will not necessarily work in another. Catalytic mechanisms must be tailored to specific goals and situations. To help readers get started, the author offers some general principles that support the process of building catalytic mechanisms effectively.

  11. Evolution of catalytic function

    NASA Technical Reports Server (NTRS)

    Joyce, G. F.

    1993-01-01

    An RNA-based evolution system was constructed in the laboratory and used to develop RNA enzymes with novel catalytic function. By controlling the nature of the catalytic task that the molecules must perform in order to survive, it is possible to direct the evolving population toward the expression of some desired catalytic behavior. More recently, this system has been coupled to an in vitro translation procedure, raising the possibility of evolving protein enzymes in the laboratory to produce novel proteins with desired catalytic properties. The aim of this line of research is to reduce darwinian evolution, the fundamental process of biology, to a laboratory procedure that can be made to operate in the service of organic synthesis.

  12. Evolution of catalytic function

    NASA Technical Reports Server (NTRS)

    Joyce, G. F.

    1993-01-01

    An RNA-based evolution system was constructed in the laboratory and used to develop RNA enzymes with novel catalytic function. By controlling the nature of the catalytic task that the molecules must perform in order to survive, it is possible to direct the evolving population toward the expression of some desired catalytic behavior. More recently, this system has been coupled to an in vitro translation procedure, raising the possibility of evolving protein enzymes in the laboratory to produce novel proteins with desired catalytic properties. The aim of this line of research is to reduce darwinian evolution, the fundamental process of biology, to a laboratory procedure that can be made to operate in the service of organic synthesis.

  13. Catalytic distillation process

    DOEpatents

    Smith, L.A. Jr.

    1982-06-22

    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  14. Catalytic distillation process

    DOEpatents

    Smith, Jr., Lawrence A.

    1982-01-01

    A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  15. Catalytic site identification--a web server to identify catalytic site structural matches throughout PDB.

    PubMed

    Kirshner, Daniel A; Nilmeier, Jerome P; Lightstone, Felice C

    2013-07-01

    The catalytic site identification web server provides the innovative capability to find structural matches to a user-specified catalytic site among all Protein Data Bank proteins rapidly (in less than a minute). The server also can examine a user-specified protein structure or model to identify structural matches to a library of catalytic sites. Finally, the server provides a database of pre-calculated matches between all Protein Data Bank proteins and the library of catalytic sites. The database has been used to derive a set of hypothesized novel enzymatic function annotations. In all cases, matches and putative binding sites (protein structure and surfaces) can be visualized interactively online. The website can be accessed at http://catsid.llnl.gov.

  16. Catalytic distillation structure

    DOEpatents

    Smith, L.A. Jr.

    1984-04-17

    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  17. Clean catalytic combustor program

    NASA Technical Reports Server (NTRS)

    Ekstedt, E. E.; Lyon, T. F.; Sabla, P. E.; Dodds, W. J.

    1983-01-01

    A combustor program was conducted to evolve and to identify the technology needed for, and to establish the credibility of, using combustors with catalytic reactors in modern high-pressure-ratio aircraft turbine engines. Two selected catalytic combustor concepts were designed, fabricated, and evaluated. The combustors were sized for use in the NASA/General Electric Energy Efficient Engine (E3). One of the combustor designs was a basic parallel-staged double-annular combustor. The second design was also a parallel-staged combustor but employed reverse flow cannular catalytic reactors. Subcomponent tests of fuel injection systems and of catalytic reactors for use in the combustion system were also conducted. Very low-level pollutant emissions and excellent combustor performance were achieved. However, it was obvious from these tests that extensive development of fuel/air preparation systems and considerable advancement in the steady-state operating temperature capability of catalytic reactor materials will be required prior to the consideration of catalytic combustion systems for use in high-pressure-ratio aircraft turbine engines.

  18. Double-Side Co-Catalytic Activation of Anodic TiO2 Nanotube Membranes with Sputter-Coated Pt for Photocatalytic H2 Generation from Water/Methanol Mixtures.

    PubMed

    Cha, Gihoon; Altomare, Marco; Truong Nguyen, Nhat; Taccardi, Nicola; Lee, Kiyoung; Schmuki, Patrik

    2017-02-01

    Self-standing TiO2 nanotube layers in the form of membranes are fabricated by self-organizing anodization of Ti metal and a potential shock technique. The membranes are then decorated by sputtering different Pt amounts i) only at the top, ii) only at the bottom or iii) at both top and bottom of the tube layers. The Pt-decorated membranes are transferred either in tube top-up or in tube top-down configuration onto FTO slides and are investigated, after crystallization, as photocatalysts for H2 generation using either front or back-side light irradiation. Double-side Pt-decoration of the tube membranes leads to higher H2 generation rates (independently of tube and light-irradiation configuration) compared to membranes decorated at only one side with similar overall Pt amounts. The results suggest that this effect cannot be only ascribed to the overall amount of Pt co-catalyst as such but also to its distribution at both tube extremities. This leads to optimized light absorption and electron diffusion/transfer dynamics: the central part of the membranes acts as light-harvesting zone and electrons therein generated can diffuse towards the Pt/TiO2 active zones (tube extremities) where they can react with the environment and generate H2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Component Development to Accelerate Commercial Implementation of Ultra-Low Emissions Catalytic Combustion

    SciTech Connect

    McCarty, Jon; Berry, Brian; Lundberg, Kare; Anson, Orris

    2003-03-31

    This final report describes a 2000-2003 program for the development of components and processes to enhance the commercialization of ultra-low emissions catalytic combustion in industrial gas turbines. The range of project tasks includes: development of more durable, lower-cost catalysts and catalytic combustor components; development and design of a catalytic pre-burner and a catalytic pilot burner for gas turbines, and on-site fuel conversion processing for utilization of liquid fuel.

  20. Catalytic activity for oxygen reduction reaction on platinum-based core-shell nanoparticles: all-electron density functional theory.

    PubMed

    Shin, Jungho; Choi, Jung-Hae; Cha, Pil-Ryung; Kim, Seong Keun; Kim, Inho; Lee, Seung-Cheol; Jeong, Doo Seok

    2015-10-14

    Pt nanoparticles (NPs) in a proton exchange membrane fuel cell as a catalyst for an oxygen reduction reaction (ORR) fairly overbind oxygen and/or hydroxyl to their surfaces, causing a large overpotential and thus low catalytic activity. Realizing Pt-based core-shell NPs (CSNPs) is perhaps a workaround for the weak binding of oxygen and/or hydroxyl without a shortage of sufficient oxygen molecule dissociation on the surface. Towards the end, we theoretically examined the catalytic activity of NPs using density functional theory; each NP consists of one of 12 different 3d-5d transition metal cores (groups 8-11) and a Pt shell. The calculation results evidently suggest the enhancement of catalytic activity of CSNPs in particular when 3d transition metal cores are in use. The revealed trends in activity change upon the core metal were discussed with respect to the thermodynamic and electronic structural aspects of the NPs in comparison with the general d-band model. The disparity between the CSNP and the corresponding bilayer catalyst, which is the so-called size effect, was remarkable; therefore, it perhaps opens up the possibility of size-determined catalytic activity. Finally, the overpotential for all CSNPs was evaluated in an attempt to choose promising combinations of CSNP materials.

  1. The Non-catalytic “Cap Domain” of a Mycobacterial Metallophosphoesterase Regulates Its Expression and Localization in the Cell*

    PubMed Central

    Matange, Nishad; Podobnik, Marjetka; Visweswariah, Sandhya S.

    2014-01-01

    Despite highly conserved core catalytic domains, members of the metallophosphoesterase (MPE) superfamily perform diverse and crucial functions ranging from nucleotide and nucleic acid metabolism to phospholipid hydrolysis. Unique structural elements outside of the catalytic core called “cap domains” are thought to provide specialization to these enzymes; however, no directed study has been performed to substantiate this. The cap domain of Rv0805, an MPE from Mycobacterium tuberculosis, is located C-terminal to its catalytic domain and is dispensable for the catalytic activity of this enzyme in vitro. We show here that this C-terminal extension (CTE) mediates in vivo localization of the protein to the cell membrane and cell wall as well as modulates expression levels of Rv0805 in mycobacteria. We also demonstrate that Rv0805 interacts with the cell wall of mycobacteria, possibly with the mycolyl-arabinogalactan-peptidoglycan complex, by virtue of its C terminus, a hitherto unknown property of this MPE. Using a panel of mutant proteins, we identify interactions between active site residues of Rv0805 and the CTE that determine its association with the cell wall. Finally, we show that Rv0805 and a truncated mutant devoid of the CTE produce different phenotypic effects when expressed in mycobacteria. Our study thus provides a detailed dissection of the functions of the cap domain of an MPE and suggests that the repertoire of cellular functions of MPEs cannot be understood without exploring the modulatory effects of these subdomains. PMID:24970891

  2. FINAL REPORT

    SciTech Connect

    Horn, Mark W; McDaniel, Anthony; Schweighardt, Frank K

    2003-05-23

    In this program the teams at Penn State University (PSU), Sandia National Laboratories (SNL), DCH Technology (DCHT), and Air Products and Chemicals Inc. (APCI), have aggressively pursued engineering solutions to eliminate barriers to solid-state chemiresistor hydrogen sensor technology. The metallurgical effects of alloying palladium with nickel have been shown to prevent phase transitions in the thin films at high H2 overpressures, making the devices more suitable for IOF process conditions. We investigated the use of thin, semi-permeable membranes that protect the catalytic surface from poisoning or other undesirable surface reactions that would otherwise reduce sensitivity or operability in harsh IOF process environments. The results of this project have provided new insight into the effects of metallurgy and protective coatings on device behavior, and open new avenues for research in this field. Commercialization of this sensor technology could be easily achieved, although not yet realized. The benefits to society, once this technology is commercialized, is a dramatic cost and energy savings to the industry, which employs these sensors. In addition, the fundamental understandings gained in this program could have an impact on both cost and safety in the future hydrogen economy utilizing hydrogen fuel cells and hydrogen storage.

  3. Functional nanofibers and membranes by electrospinning

    NASA Astrophysics Data System (ADS)

    Formo, Eric Victor

    This research focuses on advances in the fabrication of functional membranes through the process of electrospinning to either alter the arrangement or composition of nanofiber arrays. To control nanofiber arrangement, easily reconfigurable collectors were constructed that could direct the deposition over large areas (>50 cm2) and pattern the membranes into various designs, including parallel, fan-out, and spiral arrays. Subsequently, the composition of electrospun membranes was modified using the sol-gel method to yield fibers composed of TiO2 (anatase and rutile) and ZrO 2 (tetragonal) phases. Implementing the polyol reduction method, these nanofiber surfaces were coated with Pt, Pd, and Rh nanoparticles of 2-5 nm or Pt nanowires with lengths up to 125 nm. Interestingly, by calcining the ZrO2 at a lower temperature, the nanofibers could mediate the growth of Pt nanostars or Pt nanowires by adjusting the Pt precursor concentration in the polyol reduction bath. The anatase membranes could also be modified through the self-assembly of various silanes to give either thiol or amine surface groups. The functionalized membranes were then tested for a number of applications associated with the catalysis field. Specifically, anatase fiber membranes coated with Pt and Pd nanoparticles were used as catalysts in a continuous flow reactor for either hydrogenation or cross-coupling reactions, respectively, which was proven to operate with a high yield, a rapid flow rate, and were readily recyclable. The effects of both the coverage and morphology of the Pt-decorated anatase fibers on the methanol oxidation reaction were then studied. Nanofibers with a submonolayer of Pt nanoparticles or Pt nanowires were found to display improved catalytic durability over commercial Pt/C as determined by chronoamperometry. Further, by utilizing the oxygen reduction reaction, results showed that the Pt nanostars had superior electrochemical properties in comparison to Pt black. Finally, the

  4. Cellulosic Biomass Sugars to Advantage Jet Fuel: Catalytic Conversion of Corn Stover to Energy Dense, Low Freeze Point Paraffins and Naphthenes: Cooperative Research and Development Final Report, CRADA Number CRD-12-462

    SciTech Connect

    Elander, Rick

    2015-08-04

    NREL will provide scientific and engineering support to Virent Energy Systems in three technical areas: Process Development/Biomass Deconstruction; Catalyst Fundamentals; and Technoeconomic Analysis. The overarching objective of this project is to develop the first fully integrated process that can convert a lignocellulosic feedstock (e.g., corn stover) efficiently and cost effectively to a mix of hydrocarbons ideally suited for blending into jet fuel. The proposed project will investigate the integration of Virent Energy System’s novel aqueous phase reforming (APR) catalytic conversion technology (BioForming®) with deconstruction technologies being investigated by NREL at the 1-500L scale. Corn stover was chosen as a representative large volume, sustainable feedstock.

  5. Design and development of a self-regenerative contained-liquid membrane process for combined SO{sub x} and NO{sub x} removal. Final report

    SciTech Connect

    Varanasi, S.; LeBlanc, S.E.

    1992-11-01

    The lack of an efficient, cost effective process for the removal of sulfur compounds from gas streams (either gasified coal or flue gases resulting from coal combustion) is a major obstacle to the economic utilization of high sulfur Ohio coal. The most economically favorable processes for the desulfurization of flue gases are the regenerable processes as opposed to the `throwaway` processes. In addition, recovery of sulfur from these gases in the form of elemental sulfur or H{sub 2}SO{sub 4} does seem to be an essential step in the economic utilization of high sulfur coal. n light of these observations, a recently proposed FGD process which regenerates the scrubbing liquor ``in-situ`` as well as recovering a concentrated S0{sub 2} stream for use in sulfuric acid production, is quite promising. Conventional processes, presently in operation, employ large packed tower scrubbers for S0{sub 2} absorption which results in very high capital expenditures and operating costs. Recent developments in membrane technology can now provide us with an alternative to these large packed towers for stack gas cleanup. In this research we have investigated the use of novel membrane contactors for replacing more conventional packed absorbers. Contained-liquid membranes, exploiting carrier mediated transpose, enable the scrubbing liquid to be regenerated ``in-site,`` in a single process unit. Microporous single-ply polymeric membranes have recently been used in gas-liquid and liquid-liquid contactors. These membranes are fashioned into a tubular shape (i.e. long, thin fibers) for use in mass transfer contactors.

  6. Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction. Final technical report, Volume 1 - effects of solvents, catalysts and temperature conditions on conversion and structural changes of low-rank coals

    SciTech Connect

    Huang, Lili; Schobert, Harold H.; Song, Chunshan

    1998-01-01

    The main objectives of this project were to study the effects of low-temperature pretreatments on coal structure and their impacts on subsequent liquefaction. The effects of pretreatment temperatures, catalyst type, coal rank, and influence of solvent were examined. Specific objectives were to identify the basic changes in coal structure induced by catalytic and thermal pretreatments, and to determine the reactivity of the catalytically and thermally treated coals for liquefaction. In the original project management plan it was indicated that six coals would be used for the study. These were to include two each of bituminous, subbituminous, and lignite rank. For convenience in executing the experimental work, two parallel efforts were conducted. The first involved the two lignites and one subbituminous coal; and the second, the two bituminous coals and the remaining subbituminous coal. This Volume presents the results of the first portion of the work, studies on two lignites and one subbituminous coal. The remaining work accomplished under this project will be described and discussed in Volume 2 of this report. The objective of this portion of the project was to determine and compare the effects of solvents, catalysts and reaction conditions on coal liquefaction. Specifically, the improvements of reaction conversion, product distribution, as well as the structural changes in the coals and coal-derived products were examined. This study targeted at promoting hydrogenation of the coal-derived radicals, generated during thermal cleavage of chemical bonds, by using a good hydrogen donor-solvent and an effective catalyst. Attempts were also made in efforts to match the formation and hydrogenation of the free radicals and thus to prevent retrogressive reaction.

  7. Geometry of membrane fission.

    PubMed

    Frolov, Vadim A; Escalada, Artur; Akimov, Sergey A; Shnyrova, Anna V

    2015-01-01

    Cellular membranes define the functional geometry of intracellular space. Formation of new membrane compartments and maintenance of complex organelles require division and disconnection of cellular membranes, a process termed membrane fission. Peripheral membrane proteins generally control membrane remodeling during fission. Local membrane stresses, reflecting molecular geometry of membrane-interacting parts of these proteins, sum up to produce the key membrane geometries of fission: the saddle-shaped neck and hour-glass hemifission intermediate. Here, we review the fundamental principles behind the translation of molecular geometry into membrane shape and topology during fission. We emphasize the central role the membrane insertion of specialized protein domains plays in orchestrating fission in vitro and in cells. We further compare individual to synergistic action of the membrane insertion during fission mediated by individual protein species, proteins complexes or membrane domains. Finally, we describe how local geometry of fission intermediates defines the functional design of the protein complexes catalyzing fission of cellular membranes. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  8. Reactor process using metal oxide ceramic membranes

    DOEpatents

    Anderson, Marc A.

    1994-01-01

    A reaction vessel for use in photoelectrochemical reactions includes as its reactive surface a metal oxide porous ceramic membrane of a catalytic metal such as titanium. The reaction vessel includes a light source and a counter electrode. A provision for applying an electrical bias between the membrane and the counter electrode permits the Fermi levels of potential reaction to be favored so that certain reactions may be favored in the vessel. The electrical biasing is also useful for the cleaning of the catalytic membrane. Also disclosed is a method regenerating a porous metal oxide ceramic membrane used in a photoelectrochemical catalytic process by periodically removing the reactants and regenerating the membrane using a variety of chemical, thermal, and electrical techniques.

  9. Reactor process using metal oxide ceramic membranes

    DOEpatents

    Anderson, M.A.

    1994-05-03

    A reaction vessel for use in photoelectrochemical reactions includes as its reactive surface a metal oxide porous ceramic membrane of a catalytic metal such as titanium. The reaction vessel includes a light source and a counter electrode. A provision for applying an electrical bias between the membrane and the counter electrode permits the Fermi levels of potential reaction to be favored so that certain reactions may be favored in the vessel. The electrical biasing is also useful for the cleaning of the catalytic membrane. Also disclosed is a method regenerating a porous metal oxide ceramic membrane used in a photoelectrochemical catalytic process by periodically removing the reactants and regenerating the membrane using a variety of chemical, thermal, and electrical techniques. 2 figures.

  10. Membrane Innovation in Dialysis.

    PubMed

    Boschetti-de-Fierro, Adriana; Beck, Werner; Hildwein, Helmut; Krause, Bernd; Storr, Markus; Zweigart, Carina

    2017-01-01

    Despite advances in renal replacement therapy, the adequate removal of uremic toxins over a broad molecular weight range remains one of the unmet needs in hemodialysis. Therefore, membrane innovation is currently directed towards enhanced removal of uremic toxins and increased membrane permeability. This chapter presents a variety of opportunities where innovation is brought into dialysis membranes. It covers the membrane formation from solution, describing different approaches to control the phase inversion process through additives that either swell in the polymer solution or influence the pore shrinkage during the membrane drying process. Additionally, large-scale manufacturing is described, and the influence of raw materials, spinning, and drying processes on membrane selectivity are presented. Finally, new characterization methods developed for the latest innovations around the application of membranes in dialysis are discussed, which allow the membrane performance for removal of a broad range of uremic toxins and the expected albumin loss in clinical use. © 2017 S. Karger AG, Basel.

  11. Catalytic hydrotreating process

    DOEpatents

    Karr, Jr., Clarence; McCaskill, Kenneth B.

    1978-01-01

    Carbonaceous liquids boiling above about 300.degree. C such as tars, petroleum residuals, shale oils and coal-derived liquids are catalytically hydrotreated by introducing the carbonaceous liquid into a reaction zone at a temperature in the range of 300.degree. to 450.degree. C and a pressure in the range of 300 to 4000 psig for effecting contact between the carbonaceous liquid and a catalytic transition metal sulfide in the reaction zone as a layer on a hydrogen permeable transition metal substrate and then introducing hydrogen into the reaction zone by diffusing the hydrogen through the substrate to effect the hydrogenation of the carbonaceous liquid in the presence of the catalytic sulfide layer.

  12. Energy efficient membrane processes for the separation of organic liquids: Part 3 (Supplement report): Final report, September 28, 1982--December 31, 1986

    SciTech Connect

    Cabasso, I.; Acharya, H.R.; Korngold, E.; Liu, Z.; Stern, S.A.; Li, W.; Makenzie, T.; Poda, E.

    1987-10-01

    In this supplemental report, two pilot plants are described. The first is air purge pervaporation (or air sweep pervaporation hollow fiber system) for the separation of azeotropic aqueous liquids. The second describes pilot plant construction and operation for the perstraction process. Several configurations for the air purge pervaporation process were studied and were shown to yield high purity products e.g., isopropanol from the azeotropic mixture with water was enriched to 99.9%. Parallel and U-module configuration were used and durability experiments up to 120 days were carried out successfully. The report describes the first successful low scale pilot plant unit and elements for perstraction process. The conclusion and outcome of this study are two fold. First, membrane systems in a pilot plant unit proved to be very efficient in upgrading nonpermeable components in a membrane system and especially when dealing with azeotropic mixtures. For example, more than 99% isopropanol can be produced from a feed liquid which is 88% i-PrOH (azeotropic mixture with water). The membrane system proved to be durable within the time limit of the experiments (120 days). Second, all parameters including the various configurations of the pilot plants (which are still being studied) are available for chemical, petroleum, and other US industries. 3 refs., 22 figs., 2 tabs.

  13. Efficient process for previous metal recovery from cell membrane electrode assemblies

    DOEpatents

    Shore, Lawrence; Matlin, Ramail; Heinz, Robert

    2010-05-04

    A method is provided for recovering a catalytic element from a fuel cell membrane electrode assembly. The method includes grinding the membrane electrode assembly into a powder, extracting the catalytic element by forming a slurry comprising the powder and an acid leachate adapted to dissolve the catalytic element into a soluble salt, and separating the slurry into a depleted powder and a supernatant containing the catalytic element salt. The depleted powder is washed to remove any catalytic element salt retained within pores in the depleted powder and the catalytic element is purified from the salt.

  14. Steam reformer with catalytic combustor

    DOEpatents

    Voecks, Gerald E.

    1990-03-20

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  15. Steam reformer with catalytic combustor

    NASA Technical Reports Server (NTRS)

    Voecks, Gerald E. (Inventor)

    1990-01-01

    A steam reformer is disclosed having an annular steam reforming catalyst bed formed by concentric cylinders and having a catalytic combustor located at the center of the innermost cylinder. Fuel is fed into the interior of the catalytic combustor and air is directed at the top of the combustor, creating a catalytic reaction which provides sufficient heat so as to maintain the catalytic reaction in the steam reforming catalyst bed. Alternatively, air is fed into the interior of the catalytic combustor and a fuel mixture is directed at the top. The catalytic combustor provides enhanced radiant and convective heat transfer to the reformer catalyst bed.

  16. Nanocarbons for Catalytic Desulfurization.

    PubMed

    Gu, Qingqing; Lin, Yangming; Heumann, Saskia; Su, Dangsheng

    2017-08-24

    Nanocarbon catalysts are green and sustainable alternatives to the metal-based catalysts for numerous catalytic transformations. The application of nanocarbons for environmental catalysis is an emerging research discipline and has undergone rapid development in recent years. In this focus review, we provide a critical analysis on the state-of-the-art nanocarbon catalysts for three different catalytic desulfurization processes. And the focus is on the advantage and limitation as well as the reaction mechanism of the nanocarbon catalysts at molecular level. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Catalytic cracking process

    SciTech Connect

    Aufdembrink, B.A.; Degnan, T.F.; Kresge, C.T.

    1990-01-23

    This patent describes a process for catalytically cracking a petroleum fraction to lighter hydrocarbons. The process comprises providing a feedstock containing a petroleum fraction and then contacting the feedstock with a catalyst under catalytic cracking conditions. The catalyst composition includes a titanometallate layered metal oxide material comprising a layered metal oxide material comprising a layered metal oxide and pillars of a chalcogenide of at least one element selected from Groups IB, IIB, IIIA, IIIB, IVB, VA, VB, VIA, VIIA and VIIIA of the Periodic Table of Elements separating the layers of the metal oxides.

  18. Catalytic efficiency of designed catalytic proteins

    PubMed Central

    Korendovych, Ivan V; DeGrado, William F

    2014-01-01

    The de novo design of catalysts that mimic the affinity and specificity of natural enzymes remains one of the Holy Grails of chemistry. Despite decades of concerted effort we are still unable to design catalysts as efficient as enzymes. Here we critically evaluate approaches to (re)design of novel catalytic function in proteins using two test cases: Kemp elimination and ester hydrolysis. We show that the degree of success thus far has been modest when the rate enhancements seen for the designed proteins are compared with the rate enhancements by small molecule catalysts in solvents with properties similar to the active site. Nevertheless, there are reasons for optimism: the design methods are ever improving and the resulting catalyst can be efficiently improved using directed evolution. PMID:25048695

  19. Catalytic coal liquefaction process

    DOEpatents

    Garg, D.; Sunder, S.

    1986-12-02

    An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids. 1 fig.

  20. Catalytic coal liquefaction process

    DOEpatents

    Garg, Diwakar; Sunder, Swaminathan

    1986-01-01

    An improved process for catalytic solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a solvent comprises using as catalyst a mixture of a 1,2- or 1,4-quinone and an alkaline compound, selected from ammonium, alkali metal, and alkaline earth metal oxides, hydroxides or salts of weak acids.

  1. Final report on LDRD project : elucidating performance of proton-exchange-membrane fuel cells via computational modeling with experimental discovery and validation.

    SciTech Connect

    Wang, Chao Yang (Pennsylvania State University, University Park, PA); Pasaogullari, Ugur (Pennsylvania State University, University Park, PA); Noble, David R.; Siegel, Nathan P.; Hickner, Michael A.; Chen, Ken Shuang

    2006-11-01

    In this report, we document the accomplishments in our Laboratory Directed Research and Development project in which we employed a technical approach of combining experiments with computational modeling and analyses to elucidate the performance of hydrogen-fed proton exchange membrane fuel cells (PEMFCs). In the first part of this report, we document our focused efforts on understanding water transport in and removal from a hydrogen-fed PEMFC. Using a transparent cell, we directly visualized the evolution and growth of liquid-water droplets at the gas diffusion layer (GDL)/gas flow channel (GFC) interface. We further carried out a detailed experimental study to observe, via direct visualization, the formation, growth, and instability of water droplets at the GDL/GFC interface using a specially-designed apparatus, which simulates the cathode operation of a PEMFC. We developed a simplified model, based on our experimental observation and data, for predicting the onset of water-droplet instability at the GDL/GFC interface. Using a state-of-the-art neutron imaging instrument available at NIST (National Institute of Standard and Technology), we probed liquid-water distribution inside an operating PEMFC under a variety of operating conditions and investigated effects of evaporation due to local heating by waste heat on water removal. Moreover, we developed computational models for analyzing the effects of micro-porous layer on net water transport across the membrane and GDL anisotropy on the temperature and water distributions in the cathode of a PEMFC. We further developed a two-phase model based on the multiphase mixture formulation for predicting the liquid saturation, pressure drop, and flow maldistribution across the PEMFC cathode channels. In the second part of this report, we document our efforts on modeling the electrochemical performance of PEMFCs. We developed a constitutive model for predicting proton conductivity in polymer electrolyte membranes and compared

  2. Final technical report. A sodium-cycle based organism with improved membrane resistance aimed at increasing the efficiency of energy biotransformations

    SciTech Connect

    Lewis, Kim

    2001-06-01

    The aim of the project was to express in E. coli components that would allow a formation of oxidative phosphorylation based on a sodium cycle. This would improve the resistance of cells to organic solvents, detergents and other toxins. The author cloned and expressed the nqr operon from H. influenzae in E. coli. Experiments with membrane vesicles indicated the presence of the functional recombinant sodium pumping NADH dehydrogenase. A gene for a hybrid E. coli/P.modestum ATPase was constructed which will enable one to co-express a sodium ATPsynthase together with a sodium NADH dehydrogenase.

  3. Architecture and function of metallopeptidase catalytic domains

    PubMed Central

    Cerdà-Costa, Núria; Gomis-Rüth, Francesc Xavier

    2014-01-01

    The cleavage of peptide bonds by metallopeptidases (MPs) is essential for life. These ubiquitous enzymes participate in all major physiological processes, and so their deregulation leads to diseases ranging from cancer and metastasis, inflammation, and microbial infection to neurological insults and cardiovascular disorders. MPs cleave their substrates without a covalent intermediate in a single-step reaction involving a solvent molecule, a general base/acid, and a mono-or dinuclear catalytic metal site. Most monometallic MPs comprise a short metal-binding motif (HEXXH), which includes two metal-binding histidines and a general base/acid glutamate, and they are grouped into the zincin tribe of MPs. The latter divides mainly into the gluzincin and metzincin clans. Metzincins consist of globular ∼130–270-residue catalytic domains, which are usually preceded by N-terminal pro-segments, typically required for folding and latency maintenance. The catalytic domains are often followed by C-terminal domains for substrate recognition and other protein–protein interactions, anchoring to membranes, oligomerization, and compartmentalization. Metzincin catalytic domains consist of a structurally conserved N-terminal subdomain spanning a five-stranded β-sheet, a backing helix, and an active-site helix. The latter contains most of the metal-binding motif, which is here characteristically extended to HEXXHXXGXX(H,D). Downstream C-terminal subdomains are generally shorter, differ more among metzincins, and mainly share a conserved loop—the Met-turn—and a C-terminal helix. The accumulated structural data from more than 300 deposited structures of the 12 currently characterized metzincin families reviewed here provide detailed knowledge of the molecular features of their catalytic domains, help in our understanding of their working mechanisms, and form the basis for the design of novel drugs. PMID:24596965

  4. Innovative Clean Coal Technology (ICCT). Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers: Volume 3, Appendices O--T. Final report

    SciTech Connect

    1996-10-01

    Volume 3 contains the following appendices: Appendix O, Second Series-Manual APH Tests; Appendix P, Third Series-Manual APH Tests; Appendix Q, ABB Analysis of Air Preheaters-Final Report; Appendix R, ABB Corrosion Analysis Study; Appendix S, SRI Waste Stream Impacts Study; and Appendix T, Economic Evaluation.

  5. Final report on proposal to develop and test a membrane sampling module for the extraction of volatile organic compounds from water

    SciTech Connect

    Cooks, R.G.

    1993-06-29

    A new technique is describe for the direct detection of volatile organic compounds in aqueous solutions at levels in the parts per trillion range. The sample is enriched in analyte in two consecutive stages, one utilizes a semi-permeable membrane interface and the other a jet separator. The analyte solution is sampled as it flows coaxially over a semi-permeable capillary membrane, the interior of which is continuously purged by helium. The permeate is pneumatically transported to the mass spectrometer via a jet separator, which is used to remove excess helium and water from the analyte vapor stream. Data are reported for an ion trap mass spectrometer used in conjunction with a conventional fixed-gap quartz jet separator. Typical analyte response times are 2-5 minutes and flow injection methods are used for sample delivery. Detection limits in the range 30 to parts per billion are observed for selected volatile organic compounds and the response is linear over 3 orders of magnitude. Details of the construction of the interface are provided.

  6. Innovative Clean Coal Technology (ICCT). Demonstration of Selective Catalytic Reduction (SCR) technology for the control of nitrogen oxide (NO{sub x}) emissions from high-sulfur coal-fired boilers: Volume 1. Final report

    SciTech Connect

    1996-10-01

    The objective of this project is to demonstrate and evaluate commercially available Selective Catalytic Reduction (SCR) catalysts from U.S., Japanese and European catalyst suppliers on a high-sulfur U.S. coal-fired boiler. SCR is a post-combustion nitrogen oxide (NO.) control technology that involves injecting ammonia into the flue gas generated from coal combustion in an electric utility boiler. The flue gas containing ammonia is then passed through a reactor that contains a specialized catalyst. In the presence of the catalyst, the ammonia reacts with NO. to convert it to nitrogen and water vapor. Although SCR is widely practiced in Japan and Europe on gas-, oil-, and low-sulfur coal- fired boilers, there are several technical uncertainties associated with applying SCR to U.S. coals. These uncertainties include: 1) potential catalyst deactivation due to poisoning by trace metal species present in U.S. coals that are not present in other fuels. 2) performance of the technology and effects on the balance-of- plant equipment in the presence of high amounts of SO{sub 2} and SO{sub 3}. 3) performance of a wide variety of SCR catalyst compositions, geometries and methods of manufacturer under typical high-sulfur coal-fired utility operating conditions. These uncertainties were explored by operating nine small-scale SCR reactors and simultaneously exposing different SCR catalysts to flue gas derived from the combustion of high sulfur U.S. coal. In addition, the test facility operating experience provided a basis for an economic study investigating the implementation of SCR technology.

  7. Fuel cell using novel electrolyte membrane

    SciTech Connect

    Polak, A.J.; Beuhler, A.J.

    1986-06-10

    An apparatus is described for producing electricity from a fuel gas having a gaseous component which is capable, in the presence of a catalytic agent, of dissociating to yield hydrogen ions comprising: (a) a thin film organic-inorganic membrane which comprises a single phase blend from about 1% to about 70% by weight of a heteropoly acid and salts; (b) a membrane housing comprising a fuel gas chamber and an oxidant gas chamber separated by a substantially imporous partition comprising the membrane defined in element (a), the membrane having a first surface in communication with the fuel gas chamber and a second surface in communication with the oxidant gas chamber; (c) two separate portions of catalytic agent effective to promote dissociation and combination, one portion in contact with the first surface of the membrane and one portion in contact with the second surface of the membrane; and, (d) means for forming electrical connection in operative contact with the catalytic agent in contact with the first surface of the membrane and in operative contact with the catalytic agent in contact with the second surface of the membrane.

  8. Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System

    PubMed Central

    Buonomo, Joseph A; Aldrich, Courtney C

    2015-01-01

    The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi’s azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction. PMID:26347115

  9. Transport in a Microfluidic Catalytic Reactor

    SciTech Connect

    Park, H G; Chung, J; Grigoropoulos, C P; Greif, R; Havstad, M; Morse, J D

    2003-04-30

    A study of the heat and mass transfer, flow, and thermodynamics of the reacting flow in a catalytic microreactor is presented. Methanol reforming is utilized in the fuel processing system driving a micro-scale proton exchange membrane fuel cell. Understanding the flow and thermal transport phenomena as well as the reaction mechanisms is essential for improving the efficiency of the reforming process as well as the quality of the processed fuel. Numerical studies have been carried out to characterize the transport in a silicon microfabricated reactor system. On the basis of these results, optimized conditions for fuel processing are determined.

  10. Reactor vessel using metal oxide ceramic membranes

    DOEpatents

    Anderson, Marc A.; Zeltner, Walter A.

    1992-08-11

    A reaction vessel for use in photoelectrochemical reactions includes as its reactive surface a metal oxide porous ceramic membrane of a catalytic metal such as titanium. The reaction vessel includes a light source and a counter electrode. A provision for applying an electrical bias between the membrane and the counter electrode permits the Fermi levels of potential reaction to be favored so that certain reactions may be favored in the vessel. The electrical biasing is also useful for the cleaning of the catalytic membrane.

  11. Possible involvement of membrane lipids peroxidation and oxidation of catalytically essential thiols of the cerebral transmembrane sodium pump as component mechanisms of iron-mediated oxidative stress-linked dysfunction of the pump's activity.

    PubMed

    Omotayo, T I; Akinyemi, G S; Omololu, P A; Ajayi, B O; Akindahunsi, A A; Rocha, J B T; Kade, I J

    2015-01-01

    The precise molecular events defining the complex role of oxidative stress in the inactivation of the cerebral sodium pump in radical-induced neurodegenerative diseases is yet to be fully clarified and thus still open. Herein we investigated the modulation of the activity of the cerebral transmembrane electrogenic enzyme in Fe(2+)-mediated in vitro oxidative stress model. The results show that Fe(2+) inhibited the transmembrane enzyme in a concentration dependent manner and this effect was accompanied by a biphasic generation of aldehydic product of lipid peroxidation. While dithiothreitol prevented both Fe(2+) inhibitory effect on the pump and lipid peroxidation, vitamin E prevented only lipid peroxidation but not inhibition of the pump. Besides, malondialdehyde (MDA) inhibited the pump by a mechanism not related to oxidation of its critical thiols. Apparently, the low activity of the pump in degenerative diseases mediated by Fe(2+) may involve complex multi-component mechanisms which may partly involve an initial oxidation of the critical thiols of the enzyme directly mediated by Fe(2+) and during severe progression of such diseases; aldehydic products of lipid peroxidation such as MDA may further exacerbate this inhibitory effect by a mechanism that is likely not related to the oxidation of the catalytically essential thiols of the ouabain-sensitive cerebral electrogenic pump.

  12. Catalytic thermal barrier coatings

    DOEpatents

    Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh

    2009-06-02

    A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

  13. Catalytic, hollow, refractory spheres

    NASA Technical Reports Server (NTRS)

    Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

    1987-01-01

    Improved, heterogeneous, refractory catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitable formed of a shell (12) of refractory such as alumina having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be itself catalytic or a catalytically active material coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

  14. High temperature ceramic membrane reactors for coal liquid upgrading

    SciTech Connect

    Tsotsis, T.T.

    1992-06-19

    In this project we well evaluate the performance of Sel-Gel alumina membranes in coal liquid upgrading processes under realistic temperature and pressure conditions and investigate the feasibility of using such membranes in a membrane reactor based coal liquid upgrading process. In addition, the development of novel ceramic membranes with enhanced catalytic activity for coal-liquid upgrading applications, such as carbon-coated alumina membranes, will be also investigated. (VC)

  15. Catalytic reforming catalyst

    SciTech Connect

    Buss, W.C.; Kluksdahl, H.E.

    1980-12-09

    An improved catalyst, having a reduced fouling rate when used in a catalytic reforming process, said catalyst comprising platinum disposed on an alumina support wherein the alumina support is obtained by removing water from aluminum hydroxide produced as a by-product from a ziegler higher alcohol synthesis reaction, and wherein the alumina is calcined at a temperature of 1100-1400/sup 0/F so as to have a surface area of 165 to 215 square meters per gram.

  16. Quenched catalytic cracking process

    SciTech Connect

    Krambeck, F.J.; Penick, J.E.; Schipper, P.H.

    1990-12-18

    This paper describes improvement in a fluidized catalytic cracking process wherein a fluidizable catalyst cracking catalyst and a hydrocarbon feed are charged to a reactor riser at catalytic riser cracking conditions to form catalytically cracked vapor product and spent catalyst which are discharged into a reactor vessel having a volume via a riser reactor outlet equipped with a separation means to produce a catalyst lean phase. It comprises: a majority of the cracked product, and a catalyst rich phase comprising a majority of the spend catalyst. The the catalyst rich phase is discharged into a dense bed of catalyst maintained below the riser outlet and the catalyst lean phase is discharged into the vessel for a time, and at a temperature, which cause unselective thermal cracking of the cracked product in the reactor volume before product is withdrawn from the vessel via a vessel outlet. The improvement comprises: addition, after riser cracking is completed, and after separation of cracked products from catalyst, of a quenching stream into the vessel above the dense bed of catalyst, via a quench stream addition point which allows the quench stream to contact at least a majority of the volume of the vessel above the dense bed.

  17. Viral membrane fusion

    PubMed Central

    Harrison, Stephen C.

    2015-01-01

    Membrane fusion is an essential step when enveloped viruses enter cells. Lipid bilayer fusion requires catalysis to overcome a high kinetic barrier; viral fusion proteins are the agents that fulfill this catalytic function. Despite a variety of molecular architectures, these proteins facilitate fusion by essentially the same generic mechanism. Stimulated by a signal associated with arrival at the cell to be infected (e.g., receptor or co-receptor binding, proton binding in an endosome), they undergo a series of conformational changes. A hydrophobic segment (a “fusion loop” or “fusion peptide”) engages the target-cell membrane and collapse of the bridging intermediate thus formed draws the two membranes (virus and cell) together. We know of three structural classes for viral fusion proteins. Structures for both pre- and postfusion conformations of illustrate the beginning and end points of a process that can be probed by single-virion measurements of fusion kinetics. PMID:25866377

  18. Final Report for DE-FG02-04ER15626: P-type ATPases in Plants – Role of Lipid Flippases in Membrane Biogenesis

    SciTech Connect

    Harper, Jeffrey F.

    2015-02-24

    The long-range goal of the research is to understand the structure and biological functions of different P-type ATPases (ion pumps) in plant cells, and to use that knowledge to enhance the production of bioenergy from plants, or plant-research inspired technologies. Ptype ATPases include ion pumps that specifically transport H+, Ca2+, Zn2+, Cu2+, K+, or Na+, as well as at least one unusual subfamily that appears to function as lipid flippases, flipping specific lipids from one side of a membrane bilayer to the other. As a group, P-type ATPases are thought to consume more than 1/3 of the cellular ATP in typical eukaryotic cells. Recent research in the Harper lab focused on understanding the biochemical and biological functions of P-type ATPases that flip lipids. These flippases belong to the P4 subfamily of P-type ATPases. The activity of lipid flippases is thought to induce membrane curvature and/or create an asymmetry in which certain lipid head groups are preferential exposed to one surface or the other. In Arabidopsis thaliana there are 12 members of this family referred to as Aminophospholipid ATPase (ALA) 1 to ALA12. Using genetic knockouts, the Harper lab has established that this unusual subfamily of P-type ATPases are critical for plants to cope with even modest changes in temperature (e.g., down to 15°C, or up to 30°C). In addition, members of one subclade are critical for cell expansion, and loss of function mutants result in severe dwarfism. Other members of this same sub-clade are critical for pollen tube growth, and loss of function mutants are sterile under conditions of hot days and cold nights. While the cellular processes that depend on lipid flippases are still unclear, the genetic analysis of loss of function mutants clearly show they are of fundamental importance to plant growth and response to the environment.

  19. Solubilization of trace organics in block copolymer micelles for environmental separation using membrane extraction principles. Final report, May 1, 1992--April 30, 1995

    SciTech Connect

    Hatton, T.A.

    1998-09-01

    The solubilization of a range of polycyclic aromatic hydrocarbons in block copolymer micelles has been studied as a function of polymer composition, architecture, and temperature. Micelle formation is favored at high temperatures, leading to significant enhancements in solubilization capacity. At low temperatures, however, micelles do not form and the solubilization capacity of the block copolymer solution for the organics is low; this provides a convenient method for the regeneration of micellar solutions used as solvents in the treatment of contaminated feed streams using membrane extraction principles. Other experiments and analysis point to the effectiveness of block copolymer micellar solutions as water-based adsorbents for the removal of trace organics from air streams. Theoretical calculations of the structure of block copolymer micelles in the presence and absence of solutes using self-consistent mean-field lattice theories and lattice Monte Carlo methods have successfully captured the trends observed with changing polymer composition and architecture, often quantitatively. The temperature and composition dependence of the micellar properties were determined by allowing the individual polymer segments to assume both polar and non-polar conformations.

  20. Catalytic oxidation for treatment of ECLSS and PMMS waste streams

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Jolly, Clifford D.

    1991-01-01

    It is shown that catalytic oxidation is an effective technique for the removal of trace organic contaminants in a multifiltration potable processor's effluent. Essential elements of this technology are devices that deliver oxygen to the influent, and remove gaseous reaction byproducts from the effluent, via hollow-tube, gas-permeable membranes. Iodine, which poisons existing catalysis, is removed by a small deiodination bed prior to catalytic reactor entrance. The catalyst used is a mixture of Pt and Ru deposited on carbon, operating at 125-160 C and 39-90 psi pressures.

  1. Catalytic oxidation for treatment of ECLSS and PMMS waste streams

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Jolly, Clifford D.

    1991-01-01

    It is shown that catalytic oxidation is an effective technique for the removal of trace organic contaminants in a multifiltration potable processor's effluent. Essential elements of this technology are devices that deliver oxygen to the influent, and remove gaseous reaction byproducts from the effluent, via hollow-tube, gas-permeable membranes. Iodine, which poisons existing catalysis, is removed by a small deiodination bed prior to catalytic reactor entrance. The catalyst used is a mixture of Pt and Ru deposited on carbon, operating at 125-160 C and 39-90 psi pressures.

  2. Solid-state NMR spectroscopy of the HIV gp41 membrane fusion protein supports intermolecular antiparallel β sheet fusion peptide structure in the final six-helix bundle state.

    PubMed

    Sackett, Kelly; Nethercott, Matthew J; Zheng, Zhaoxiong; Weliky, David P

    2014-03-06

    The HIV gp41 protein catalyzes fusion between viral and target cell membranes. Although the ~20-residue N-terminal fusion peptide (FP) region is critical for fusion, the structure of this region is not well characterized in large gp41 constructs that model the gp41 state at different times during fusion. This paper describes solid-state NMR (SSNMR) studies of FP structure in a membrane-associated construct (FP-Hairpin), which likely models the final fusion state thought to be thermostable trimers with six-helix bundle structure in the region C-terminal of the FP. The SSNMR data show that there are populations of FP-Hairpin with either α helical or β sheet FP conformation. For the β sheet population, measurements of intermolecular (13)C-(13)C proximities in the FP are consistent with a significant fraction of intermolecular antiparallel β sheet FP structure with adjacent strand crossing near L7 and F8. There appears to be negligible in-register parallel structure. These findings support assembly of membrane-associated gp41 trimers through interleaving of N-terminal FPs from different trimers. Similar SSNMR data are obtained for FP-Hairpin and a construct containing the 70 N-terminal residues of gp41 (N70), which is a model for part of the putative pre-hairpin intermediate state of gp41. FP assembly may therefore occur at an early fusion stage. On a more fundamental level, similar SSNMR data are obtained for FP-Hairpin and a construct containing the 34 N-terminal gp41 residues (FP34) and support the hypothesis that the FP is an autonomous folding domain.

  3. Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

    NASA Technical Reports Server (NTRS)

    Salazar, Giovanni; Amar, Adam; Hyatt, Andrew; Rezin, Marc D.

    2016-01-01

    This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

  4. Catalytic Activation of Nitrogen Dioxide for Selective Synthesis of Nitroorganics

    DTIC Science & Technology

    2015-01-15

    AFRL-OSR-VA-TR-2015-0035 Catalytic activation of nitrogen dioxide for selective synthesis SETH BROWN UNIVERSITY OF NOTRE DAME DU LAC Final Report 01...8-98) v Prescribed by ANSI Std. Z39.18 12-01-2015 Final 15 Aug 2011 - 14 Aug 2014 Catalytic activation of nitrogen dioxide for selective synthesis...reductive elimination of the nitroarene has not. Nitrogen dioxide can be used as a source of the nitro group in reactions with arylboronic acids or their

  5. Catalytic reforming process

    SciTech Connect

    Absil, R.P.; Huss, A. Jr.; McHale, W.D.; Partridge, R.D.

    1989-06-13

    This patent describes a catalytic reforming process which comprises contacting a naphtha range feed with a low acidity extrudate comprising an intermediate and/or a large pore acidic zeolite bound with a low acidity refractory oxide under reforming conditions to provide a reaction product of increased aromatic content, the extrudate having been prepared with at least an extrusion-facilitating amount of a low acidity refractory oxide in colloidal form and containing at least one metal species selected from the platinum group metals.

  6. Catalytic reforming methods

    DOEpatents

    Tadd, Andrew R; Schwank, Johannes

    2013-05-14

    A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

  7. Membrane stabilizer

    DOEpatents

    Mingenbach, William A.

    1988-01-01

    A device is provided for stabilizing a flexible membrane secured within a frame, wherein a plurality of elongated arms are disposed radially from a central hub which penetrates the membrane, said arms imposing alternately against opposite sides of the membrane, thus warping and tensioning the membrane into a condition of improved stability. The membrane may be an opaque or translucent sheet or other material.

  8. Viral membrane fusion

    SciTech Connect

    Harrison, Stephen C.

    2015-05-15

    Membrane fusion is an essential step when enveloped viruses enter cells. Lipid bilayer fusion requires catalysis to overcome a high kinetic barrier; viral fusion proteins are the agents that fulfill this catalytic function. Despite a variety of molecular architectures, these proteins facilitate fusion by essentially the same generic mechanism. Stimulated by a signal associated with arrival at the cell to be infected (e.g., receptor or co-receptor binding, proton binding in an endosome), they undergo a series of conformational changes. A hydrophobic segment (a “fusion loop” or “fusion peptide”) engages the target-cell membrane and collapse of the bridging intermediate thus formed draws the two membranes (virus and cell) together. We know of three structural classes for viral fusion proteins. Structures for both pre- and postfusion conformations of illustrate the beginning and end points of a process that can be probed by single-virion measurements of fusion kinetics. - Highlights: • Viral fusion proteins overcome the high energy barrier to lipid bilayer merger. • Different molecular structures but the same catalytic mechanism. • Review describes properties of three known fusion-protein structural classes. • Single-virion fusion experiments elucidate mechanism.

  9. Polyethersulfone hollow fiber modified with poly(styrenesulfonate) and Pd nanoparticles for catalytic reaction

    NASA Astrophysics Data System (ADS)

    Emin, C.; Gu, Y.; Remigy, J.-C.; Lahitte, J.-F.

    2015-07-01

    The aim of this work is the synthesis of polymer-stabilized Pd nanoparticles (PdNP) inside a functionalized polymeric porous membrane in order to develop hybrid catalytic membrane reactors and to test them in model metal-catalyzed organic reactions. For this goal, a polymeric membrane support (Polyethersulfone hollow fiber-shaped) was firstly functionalized with an ionogenic polymer (i.e. poly(styrenesulfonate) capable to retain PdNP precursors using an UV photo-grafting method. PdNP were then generated inside the polymeric matrix by chemical reduction of precursor salts (intermatrix synthesis). The catalytic performance of the PdNP catalytic membranes was evaluated using reduction of nitrophenol by sodium borohydride (NaBH4) in water.

  10. The use of ozonation and catalytic ozonation combined with ultrafiltration for the control of natural organic matter (NOM) and disinfection by-products (DBPs) in drinking water

    NASA Astrophysics Data System (ADS)

    Karnik, Bhavana Sushilkumar

    Commercially available titania membranes, with a molecular weight cut-off of 15, 5, 1 kD were used in a ozonation/membrane system that was fed with water from Lake Lansing. The effects of ozonation on permeate flux recovery and membrane fouling was investigated. In addition the effects of ozonation/membrane filtration hybrid process on the removal of the natural organic matter (NOM) and the formation of disinfection by-products (DBPS) were monitored. The commercial membrane (CeRAM Inside, Tami North America, St. Laurent, Quebec, Canada) was coated with iron oxide nanoparticles (4--6 nm in diameter) using a layer-by-layer technique and sintered in air for 30 minutes. Surface characterization was carried out using electron microscopy techniques and atomic force microscopy, to study the changes in structure and surface morphology of the membranes. The removal and survival of bacteria in the process was also evaluated using fluorescence microscopy and microbial assays. Finally the surface catalytic reaction was investigated to propose the mechanism responsible for the improved performance of the hybrid process. The permeate flux through a titania coated ceramic membrane was significantly affected by ozonation. A minimum threshold ozone concentration (2.5 g/m 3) could achieve complete recovery of permeate flux after fouling. Ozonation/filtration decreased the concentration of chlorinated disinfection by-products up to 80%. With catalyst coated membranes, the concentration of dissolved organic carbon was reduced by >85% and the concentrations of disinfection by-products decreased by up to 90%. Furthermore with the coated membrane, the concentrations of ozonation by-products in the permeate were reduced by >50% as compared to that obtained with the uncoated membranes, thus reducing the risk of potential regrowth of bacteria in the distribution system. Application of the hybrid process lead to greater than 7 log removal of bacteria. Surface characterization showed that

  11. [Studies on photo-electron-chemical catalytic degradation of the malachite green].

    PubMed

    Li, Ming-yu; Diao, Zeng-hui; Song, Lin; Wang, Xin-le; Zhang, Yuan-ming

    2010-07-01

    A novel two-compartment photo-electro-chemical catalytic reactor was designed. The TiO2/Ti thin film electrode thermally formed was used as photo-anode, and graphite as cathode and a saturated calomel electrode (SCE) as the reference electrode in the reactor. The anode compartment and cathode compartment were connected with the ionic exchange membrane in this reactor. Effects of initial pH, initial concentration of malachite green and connective modes between the anode compartment and cathode compartment on the decolorization efficiency of malachite green were investigated. The degradation dynamics of malachite green was studied. Based on the change of UV-visible light spectrum, the degradation process of malachite green was discussed. The experimental results showed that, during the time of 120 min, the decolouring ratio of the malachite green was 97.7% when initial concentration of malachite green is 30 mg x L(-1) and initial pH is 3.0. The catalytic degradation of malachite green was a pseudo-first order reaction. In the degradation process of malachite green the azo bond cleavage and the conjugated system of malachite green were attacked by hydroxyl radical. Simultaneity, the aromatic ring was oxidized. Finally, malachite green was degraded into other small molecular compounds.

  12. Zeolite membrane application in hydrocarbon processing

    SciTech Connect

    Suzuki, H.

    1988-06-01

    Zeolites are of great importance in hydrocarbon processing either as adsorbents or catalysts. This paper presents a research since 1973 about the transformation of zeolite into membrane zeolite, that dramatically contributes to the free world of peace and prosperity. Commercial and organic membranes are of two categories: anisotropic membrane, e.g. cellulose acetate, and composite membrane, e.g. plasma {und in}-{und situ} polymerization on polysulfone support. Zeolite membrane belongs to the latter category, zeolite {und in}-{und situ} hydrothermalization on porous glass. Basically zeolite membrane is consisted of three groups: (1) eight-oxygen ring window, zeolite A, (2) ten-oxygen ring window, Pentasil, and (3) twelve-oxygen ring window, Faujasite. The technology of zeolite membrane synthesis and subsequent treatment is almost transferred from the one applied to powder zeolites. Zeolite membrane is expected to play a major role in the field of hydrocarbon processing, that is, PSA, Distillation/Extraction, and Catalytic Reactions.

  13. Mitsunobu Reactions Catalytic in Phosphine and a Fully Catalytic System.

    PubMed

    Buonomo, Joseph A; Aldrich, Courtney C

    2015-10-26

    The Mitsunobu reaction is renowned for its mild reaction conditions and broad substrate tolerance, but has limited utility in process chemistry and industrial applications due to poor atom economy and the generation of stoichiometric phosphine oxide and hydrazine by-products that complicate purification. A catalytic Mitsunobu reaction using innocuous reagents to recycle these by-products would overcome both of these shortcomings. Herein we report a protocol that is catalytic in phosphine (1-phenylphospholane) employing phenylsilane to recycle the catalyst. Integration of this phosphine catalytic cycle with Taniguchi's azocarboxylate catalytic system provided the first fully catalytic Mitsunobu reaction. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

  14. Kinetic modelling of heterogeneous catalytic systems

    NASA Astrophysics Data System (ADS)

    Stamatakis, Michail

    2015-01-01

    The importance of heterogeneous catalysis in modern life is evidenced by the fact that numerous products and technologies routinely used nowadays involve catalysts in their synthesis or function. The discovery of catalytic materials is, however, a non-trivial procedure, requiring tedious trial-and-error experimentation. First-principles-based kinetic modelling methods have recently emerged as a promising way to understand catalytic function and aid in materials discovery. In particular, kinetic Monte Carlo (KMC) simulation is increasingly becoming more popular, as it can integrate several sources of complexity encountered in catalytic systems, and has already been used to successfully unravel the underlying physics of several systems of interest. After a short discussion of the different scales involved in catalysis, we summarize the theory behind KMC simulation, and present the latest KMC computational implementations in the field. Early achievements that transformed the way we think about catalysts are subsequently reviewed in connection to latest studies of realistic systems, in an attempt to highlight how the field has evolved over the last few decades. Present challenges and future directions and opportunities in computational catalysis are finally discussed.

  15. Bifunctional catalytic electrode

    NASA Technical Reports Server (NTRS)

    Cisar, Alan (Inventor); Murphy, Oliver J. (Inventor); Clarke, Eric (Inventor)

    2005-01-01

    The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

  16. ``OPTICAL Catalytic Nanomotors''

    NASA Astrophysics Data System (ADS)

    Rosary-Oyong, Se, Glory

    D. Kagan, et.al, 2009:'' a motion-based chemical sensing involving fuel-driven nanomotors is demonstrated. The new protocol relies on the use of an optical microscope for tracking charge in the speed of nanowire motors in the presence of target analyte''. Synthetic nanomotors are propelled by catalytic decomposition of .. they do not require external electric, magnetic or optical fields as energy... Accompanying Fig 2.6(a) of optical micrograph of a partial monolayer of silica microbeads [J.Gibbs, 2011 ] retrieves WF Paxton:''rods were characterized by transmission electron & dark-field optical microscopy..'' & LF Valadares:''dimer due to the limited resolution of optical microscopy, however the result..'. Acknowledged to HE. Mr. Prof. SEDIONO M.P. TJONDRONEGORO.

  17. Catalytic hollow spheres

    NASA Technical Reports Server (NTRS)

    Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

    1986-01-01

    The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

  18. Catalytic hollow spheres

    NASA Technical Reports Server (NTRS)

    Wang, Taylor G. (Inventor); Elleman, Daniel D. (Inventor); Lee, Mark C. (Inventor); Kendall, Jr., James M. (Inventor)

    1989-01-01

    The improved, heterogeneous catalysts are in the form of gas-impervious, hollow, thin-walled spheres (10) suitably formed of a shell (12) of metal such as aluminum having a cavity (14) containing a gas at a pressure greater than atmospheric pressure. The wall material may be, itself, catalytic or the catalyst can be coated onto the sphere as a layer (16), suitably platinum or iron, which may be further coated with a layer (18) of activator or promoter. The density of the spheres (30) can be uniformly controlled to a preselected value within .+-.10 percent of the density of the fluid reactant such that the spheres either remain suspended or slowly fall or rise through the liquid reactant.

  19. Catalytic cracking of hydrocarbons

    SciTech Connect

    Absil, R.P.L.; Bowes, E.; Green, G.J.; Marler, D.O.; Shihabi, D.S.; Socha, R.F.

    1992-02-04

    This patent describes an improvement in a catalytic cracking process in which a hydrocarbon feed is cracked in a cracking zone in the absence of added hydrogen and in the presence of a circulating inventory of solid acidic cracking a catalyst which acquires a deposit of coke that contains chemically bound nitrogen while the cracking catalyst is in the cracking zone, the coke catalyst being circulated to t regeneration zone to convert the coke catalyst to a regenerated catalyst with the formation of a flue gas comprising nitrogen oxides: the improvement comprises incorporating into the circulating catalyst inventory an amount of additive particles comprising a synthetic porous crystalline material containing copper metal or cations, to reduce the content of nitrogen oxides in the flue gas.

  20. Amylosucrase from Neisseria polysaccharea: novel catalytic properties.

    PubMed

    Potocki de Montalk, G; Remaud-Simeon, M; Willemot, R M; Sarçabal, P; Planchot, V; Monsan, P

    2000-04-14

    Amylosucrase is a glucosyltransferase that synthesises an insoluble alpha-glucan from sucrose. The catalytic properties of the highly purified amylosucrase from Neisseria polysaccharea were characterised. Contrary to previously published results, it was demonstrated that in the presence of sucrose alone, several reactions are catalysed, in addition to polymer synthesis: sucrose hydrolysis, maltose and maltotriose synthesis by successive transfers of the glucosyl moiety of sucrose onto the released glucose, and finally turanose and trehalulose synthesis - these two sucrose isomers being obtained by glucosyl transfer onto fructose. The effect of initial sucrose concentration on initial activity demonstrated a non-Michaelian profile never previously described.

  1. Evolution of random catalytic networks

    SciTech Connect

    Fraser, S.M.; Reidys, C.M. |

    1997-06-01

    In this paper the authors investigate the evolution of populations of sequences on a random catalytic network. Sequences are mapped into structures, between which are catalytic interactions that determine their instantaneous fitness. The catalytic network is constructed as a random directed graph. They prove that at certain parameter values, the probability of some relevant subgraphs of this graph, for example cycles without outgoing edges, is maximized. Populations evolving under point mutations realize a comparatively small induced subgraph of the complete catalytic network. They present results which show that populations reliably discover and persist on directed cycles in the catalytic graph, though these may be lost because of stochastic effects, and study the effect of population size on this behavior.

  2. Membrane stabilizer

    DOEpatents

    Mingenbach, W.A.

    1988-02-09

    A device is provided for stabilizing a flexible membrane secured within a frame, wherein a plurality of elongated arms are disposed radially from a central hub which penetrates the membrane, said arms imposing alternately against opposite sides of the membrane, thus warping and tensioning the membrane into a condition of improved stability. The membrane may be an opaque or translucent sheet or other material. 10 figs.

  3. Catalytic Microtube Rocket Igniter

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.; Deans, Matthew C.

    2011-01-01

    Devices that generate both high energy and high temperature are required to ignite reliably the propellant mixtures in combustion chambers like those present in rockets and other combustion systems. This catalytic microtube rocket igniter generates these conditions with a small, catalysis-based torch. While traditional spark plug systems can require anywhere from 50 W to multiple kW of power in different applications, this system has demonstrated ignition at less than 25 W. Reactants are fed to the igniter from the same tanks that feed the reactants to the rest of the rocket or combustion system. While this specific igniter was originally designed for liquid methane and liquid oxygen rockets, it can be easily operated with gaseous propellants or modified for hydrogen use in commercial combustion devices. For the present cryogenic propellant rocket case, the main propellant tanks liquid oxygen and liquid methane, respectively are regulated and split into different systems for the individual stages of the rocket and igniter. As the catalyst requires a gas phase for reaction, either the stored boil-off of the tanks can be used directly or one stream each of fuel and oxidizer can go through a heat exchanger/vaporizer that turns the liquid propellants into a gaseous form. For commercial applications, where the reactants are stored as gases, the system is simplified. The resulting gas-phase streams of fuel and oxidizer are then further divided for the individual components of the igniter. One stream each of the fuel and oxidizer is introduced to a mixing bottle/apparatus where they are mixed to a fuel-rich composition with an O/F mass-based mixture ratio of under 1.0. This premixed flow then feeds into the catalytic microtube device. The total flow is on the order of 0.01 g/s. The microtube device is composed of a pair of sub-millimeter diameter platinum tubes connected only at the outlet so that the two outlet flows are parallel to each other. The tubes are each

  4. Indoleacetic Acid Oxidase: A Dual Catalytic Enzyme?

    PubMed Central

    Hoyle, M. C.

    1972-01-01

    The isolation of a unique enzyme capable of oxidizing indoleacetic acid, but devoid of peroxidase activity, has been reported for preparations from tobacco roots and commercial horseradish peroxidase. Experiments were made to verify these results using enzyme obtained from Betula leaves and commercial horseradish peroxidase. Both indoleacetic acid oxidase and guaiacol peroxidase activity appeared at 2.5 elution volumes from sulfoethyl-Sephadex. These results were obtained with both sources of enzyme. In no case was a separate peak of indoleacetic acid oxidase activity obtained at 5.4 elution volumes as reported for the tobacco enzyme using the same chromatographic system. Both types of activity, from both sources of enzyme, also eluted together during gel filtration. Successful column chromatography of Betula enzyme was dependent upon previous purification by membrane ultrafiltration. These results indicate indoleacetic acid oxidase activity and guaiacol peroxidase activity are dual catalytic functions of a single enzyme. PMID:16658111

  5. Catalytic multi-stage liquefaction (CMSL). Final report

    SciTech Connect

    1996-11-01

    The 17-day bench run CMSL-6 (227-83), on Black Thunder Mine subbituminous coal and with an approximate space velocity of 481 kg/hr/m{sup 3} (30 lb/hr/ft{sup 3}), tested the performance of a dispersed slurry catalyst in powdered form added to the first stage thermal reactor. This catalyst, based on molybdenum-containing sulfated iron oxide prepared at HTI, had about 15% moisture, 43% Fe and 7% Mo with a BET surface area of about 40 m{sup 2}/g. The second stage reactor had a partially deactivated Shell S-317 catalyst (initial age=520 kg-coal/kg-catalyst) to make the effects of the slurry catalyst more apparent and to attain a realistic equilibrium catalyst age sooner. An in-line hydrotreater was successfully employed during this run to treat atmospheric still overhead and separator overhead products. No interstage product separator was utilized in this run. For the first run condition, the catalyst additive rate was 1400-4300 ppm (of coal) Fe with 200-700 ppm Mo using a slurrying oil recycle consisting of 60% of filtered product slurry and 40% of ashy recycle (unfiltered product slurry) at a relatively low severity with first and second stage temperatures of 427{degrees}C and 413{degrees}C (800{degrees}F and 775{degrees}F), respectively. After that the additive rate was lowered to 700 ppm Fe with 100 ppm of Mo and the severity was increased with first and second stage temperatures of 441{degrees}C and 427{degrees}C (825{degrees}F and 800{degrees}F) respectively. The proportion of ashy recycle was maintained at 40% in Condition 2, and it was lowered to 25% in Condition 3. In Condition 4, the proportion of ashy recycle was set at 50%, but, because of slowing of the product slurry filtration, vacuum distillate recycle (and makeup oil) was substituted for the filtered liquid constituent of the recycled oil. With the changes of the proportion of ashy recycle the total slurry catalyst in the system (added and recycled) ranged from 860 to 6345 ppm Fe with 140 to 1030 ppm Mo.

  6. Control of catalytic hydrotreating selectivity with ammonia. Final technical report

    SciTech Connect

    Satterfield, C.N.; Lee, C.; Gultekin, S.

    1993-11-01

    The purpose of this study was to explore the possibility of control of product selectivity in the hydroprocessing of coal liquids and related substances by adding small amounts of ammonia. Quinoline was used in this study and in many others as representative of heterocyclic N compounds found in coal liquids. Coal liquids also contain hydroxy pyridines, but by studies with 8-OH quinoline, a representative compound (Part I), we demonstrated that the OH group was rapidly removed at the beginning of reaction to form quinoline, which reacted in the same manner as quinoline fed as such. In Part II we showed that in a mixture of naphthalene and quinoline, with the addition of ammonia there is an operating region in which complete HDN of quinoline can be achieved, but with greater conversion of naphthalene to tetralin instead of to decalin than was the case in the absence of added ammonia. This is of some significance to coal liquefaction since tetralin is a good hydrogen donor, but decalin is not. In Part III we showed that NH{sub 3} addition to a mixture of quinoline and phenanthrene provides an operating region where complete HDN of quinoline can be achieved with reduced formation of hydrogenated phenanthrenes and cracking to biphenyl. Part IV, a study of the hydrodeoxygenation (DHO) of dibenzofuran in the presence of naphthalene, showed that NH{sub 3} strongly inhibits HDO reactions and its effects on naphthalene here were much the same as in Part II. In Part V it was demonstrated that in the hydrotreating of propylbenzene, the addition of ammonia increased the selectivity towards ring hydrogenation (generally desired for reformulated motor fuels) and away from dealkylation (generally undesired), but the overall reaction rate at a fixed temperature drops substantially.

  7. Zeolite membranes from kaolin

    SciTech Connect

    Karle, B.G.; Brinker, C.J. |; Phillips, M.L.F.

    1996-07-01

    Zeolite films are sought as components of molecular sieve membranes. Different routes used to prepare zeolite composite membranes include growing zeolite layers from gels on porous supports, depositing oriented zeolites on supports, and dispersing zeolites in polymeric membranes. In most cases, it is very difficult to control and avoid the formation of cracks and/or pinholes. The approach to membrane synthesis is based on hydrothermally converting films of layered aluminosilicates into zeolite films. The authors have demonstrated this concept by preparing zeolite A membranes on alumina supports from kaolin films. The authors have optimized the process parameters not only for desired bulk properties, but also for preparing thin (ca. 5 {micro}m), continuous zeolite A films. Scanning electron microscopy shows highly intergrown zeolite A crystals over most of the surface area of the membrane, but gas permeation experiments indicate existence of mesoporous defects and/or intercrystalline gaps. It has been demonstrated that the thickness of the final zeolite A membrane can be controlled by limiting the amount of precursor kaolin present in the membrane.

  8. Catalytic gasification of biomass

    NASA Astrophysics Data System (ADS)

    Robertus, R. J.; Mudge, L. K.; Sealock, L. J., Jr.; Mitchell, D. H.; Weber, S. L.

    1981-12-01

    Methane and methanol synthesis gas can be produced by steam gasification of biomass in the presence of appropriate catalysts. This concept is to use catalysts in a fluidized bed reactor which is heated indirectly. The objective is to determine the technical and economic feasibility of the concept. Technically the concept has been demonstrated on a 50 lb per hr scale. Potential advantages over conventional processes include: no oxygen plant is needed, little tar is produced so gas and water treatment are simplified, and yields and efficiencies are greater than obtained by conventional gasification. Economic studies for a plant processing 2000 T/per day dry wood show that the cost of methanol from wood by catalytic gasification is competitive with the current price of methanol. Similar studies show the cost of methane from wood is competitive with projected future costs of synthetic natural gas. When the plant capacity is decreased to 200 T per day dry wood, neither product is very attractive in today's market.

  9. Catalytic cracking process

    SciTech Connect

    Chiang, R.L.; Perigard, R.G.; Rabo, J.A.

    1989-08-08

    This patent describes a process for catalytic cracking of hydrocarbon feedstocks. It comprises contacting the hydrocarbon feedstock under conditions effective to crack the feedstock with a catalyst. The catalyst is prepared by a process comprising the following step: contacting a fluid mixture of a large pore zeolite having a SiO/sub 2/Al/sub 2/O/sub 3/ ratio of about 3.5 to less than about 20 and an inorganic oxide matrix, with a fluoro salt of the formula A/sub (n-m)/(MF/sub n/)/sub z/. Wherein A is an organic or inorganic ionic moiety; (MF/sub n/)/sub z/ is a fluoroanion moiety comprising the element M; M is an element selected from the group of elements for Groups VB, VIB, VII, IIIA, IVA and VA of the Periodic Table of Elements; n is the coordination number of M; m is the valence of M and z is the valence or charge associated with A, at an effective pH value greater than about 3, at effective conditions of temperature and time to produce a catalyst product, whereby the cracking activity of the zeolite is enhanced.

  10. Photobiodegradation of chlorinated water pollutants by a combined TiO{sub 2}-polyaniline-enzyme catalytic system

    SciTech Connect

    Campanella, L.; Crescentini, G.; Militerno, S.

    1995-12-31

    The removal of xenobiotic compounds, such as chlorophenols and pesticides, from municipal and industrial wastewaters is an important task because of the toxicity and the tendency to bioaccumulation of these compounds. Among the several methods proposed, photodegradation catalyzed by suspended inorganic semiconductors (i.e. TiO{sub 2}) has lately received wide attention because this process is fast, leads to non-toxic final products and shows a high degradation efficiency. In this work, the results obtained in the photodegradation of monochlorophenols using a new catalyst, made of TiO{sub 2} and polyaniline both immobilized on a polyvinylchloride (PVC) membrane, in presence (and in absence) of an enzyme are presented. Different enzymes have been tested by adding 5, 10 or 15 U/mL to 50 mL of aqueous solution (1{times}10{sup {minus}4} mol/L) of o-chlorophenol containing the catalytic membrane. The samples were irradiated using a QUV Panel Accelerated Weathering Tester, which simulates very well the solar radiation up to {lambda}=400 nm and HPLC was used to measure the variation of the compounds concentration with the time. While some enzymes (i.e. peroxidase) do not improve the photodegradation process since they do to survive under the irradiation conditions used, some of them show a marked effect both in terms of rate of degradation and time required to reach the total degradation of the compound examined. For example, the addition of Laccase reduces the 100% degradation time for 35 hrs to about 20 hrs. Attempts to immobilize the enzyme on the catalytic membrane (by adsorption) have been carried out and the performance of the catalyst with non-immobilized and immobilized enzyme has been studied.

  11. Photobiodegradation of chlorinated water pollutants by a combined TiO2-polyaniline-enzyme catalytic system

    NASA Astrophysics Data System (ADS)

    Campanella, Luigi; Crescentini, G.; Militerno, S.

    1995-10-01

    The removal of xenobiotic compounds, such as chlorophenols and pesticides, from municipal and industrial wastewaters is an important task because of the toxicity and the tendency to bioaccumulation of these compounds. Among the several methods proposed, photodegradation catalyzed by suspended inorganic semiconductors (i.e. TiO2) has lately received wide attention because this process is fast, leads to non-toxic final products and shows a high degradation efficiency. In this work, the results obtained in the photodegradation of monochlorophenols using a new catalyst, made of TiO2 and polyaniline both immobilized on a polyvinylchloride (PVC) membrane, in presence (and in absence) of an enzyme are presented. Different enzymes have been tested by adding 5, 10 or 15 U/mL to 50 mL of aqueous solution (1 multiplied by 10-4 mol/L) of o-chloro-phenol containing the catalytic membrane. The samples were irradiated using a QUV panel accelerated weathering tester, which simulates very well the solar radiation up to lambda equals 400 nm and HPLC was used to measure the variation of the compound's concentration with the time. While some enzymes (i.e., peroxidase) do not improve the photodegradation process since they do not survive under the irradiation conditions used, some of them show marked effect both in terms of rate degradation and time required to reach the total degradation of the compound examined. For example, the addition of Laccase reduces the 100% degradation time from 35 hrs to about 20 hrs. Attempts to immobilize the enzyme on the catalytic membrane (by adsorption) have been carried out and the performance of the catalyst with non-immobilized and immobilized enzyme has been studied.

  12. Palladium and its alloys as membrane catalysts

    SciTech Connect

    Gryaznov, V.M.

    1983-05-01

    Possibilities have been examined for the use of selective transport of hydrogen through palladium alloy membranes in order to increase the efficiency of hydrogen recovery from gas mixtures and catalytic reactions in which hydrogen is consumed or formed. By varying the hydrogen concentration in the bulk and on the surface of a palladium alloy, it becomes possible to increase the selectivity of hydrogenation reactions. Continuous and semicontinuous methods have been developed for obtaining valuable products on membrane catalysts.

  13. Upgrading of Intermediate Bio-Oil Produced by Catalytic Pyrolysis

    SciTech Connect

    Abdullah, Zia; Chadwell, Brad; Taha, Rachid; Hindin, Barry; Ralston, Kevin

    2015-06-30

    The objectives of this project were to (1) develop a process to upgrade catalytic pyrolysis bio-oil, (2) investigate new upgrading catalysts suited for upgrading catalytic pyrolysis bio-oil, (3) demonstrate upgrading system operation for more than 1,000 hours using a single catalyst charge, and (4) produce a final upgraded product that can be blended to 30 percent by weight with petroleum fuels or that is compatible with existing petroleum refining operations. This project has, to the best of our knowledge, for the first time enabled a commercially viable bio-oil hydrotreatment process to produce renewable blend stock for transportation fuels.

  14. The Catalytic Machinery of Rhomboid Proteases: Combined MD and QM Simulations.

    PubMed

    Uritsky, Neta; Shokhen, Michael; Albeck, Amnon

    2012-11-13

    Rhomboid proteases are a ubiquitous family of intramembrane serine proteases in prokaryotic and eukaryotic organisms that cleave membrane proteins in their transmembrane region. Their catalytic activity is centered at a His-Ser catalytic dyad. We applied molecular dynamics and quantum mechanics calculations in order to clarify the protonation state of the catalytic residues of E. coli GlpG rhomboid protease and how it is affected by the immersion of the enzyme in the membrane. We identified (Nε)H150(dpr)_H254(dpr)_S201(pr) as the protonation (and H150 tautomeric) state of free GlpG in both lipid-solubilized and membrane environments. We used our MD-QM/SCRF(VS) computational protocol to rationalize and predict the trend of pKa change caused by the decrease of water exposure of the active site of GlpG due to ligand binding. The catalytic diad of lipid-solubilized GlpG exists as an H254(+)_S201(-) ion pair at the Michaelis complex stage, with Ser201 ready for nucleophilic attack on the substrate. Therefore, deprotonation of S201 does not contribute to the activation barrier of covalent tetrahedral complex formation. In contrast, both catalytic residues, H254 and S201, are neutral in the Michaelis complex of GlpG in the membrane. Therefore, S201 deprotonation by H254 general base catalysis should contribute to the activation barrier of the covalent tetrahedral complex formation.

  15. Catalytic reforming of naphtha fractions

    SciTech Connect

    Bishop, K.C.; Vorhis, F.H.

    1980-09-16

    Production of motor gasoline and a btx-enriched reformate by fractionating a naphtha feedstock into a mid-boiling btxprecursor fraction, a relatively high-boiling fraction and a relatively low-boiling fraction; catalytically reforming the btxprecursor fraction in a first reforming zone; combining the relatively high-boiling and low-boiling fractions and catalytically reforming the combined fractions in a second reforming zone.

  16. Radiation/Catalytic Augmented Combustion.

    DTIC Science & Technology

    1982-05-01

    VUV wavelengths 157 nm (F2) and 193 nm (ArF). Radiative ignitions were achieved with the fluorine laser and not with the argon fluoride laser, even...enhanced combustion processes, utilizing pulsed and continuous VUV light-serces. Similarly, the catalytic technique has provided efficient combustion...ignited fuel-air mixtures, and has enhanced combustion processes, utilizing pulsed and continuous VUV light sources. Similarly, the catalytic technique has

  17. Chlorine Resistant PBI RO Permselective Membranes.

    DTIC Science & Technology

    1981-02-01

    Reverse Osmosis Desalination Membranes . Final report; Contract No. 14-30-2810, U. S. Department of the Interior, Office...of Saline Water, Washington, DC, July, 1972. NTIS Order No. PB 218055. (3) Seawater Desalination with PBI Hollow Fiber Reverse Osmosis Membranes . Final...Polymer Sci., C. 19, 49 (1967). (7) High Flux PBI Reverse Osmosis Membranes for Desalination and Water Reuse. Final report, Contract No. 14-34-001- 7527,

  18. Kinetic evidence against partitioning of the ubiquinone pool and the catalytic relevance of respiratory-chain supercomplexes

    PubMed Central

    Blaza, James N.; Serreli, Riccardo; Jones, Andrew J. Y.; Mohammed, Khairunnisa; Hirst, Judy

    2014-01-01

    In mitochondria, four respiratory-chain complexes drive oxidative phosphorylation by sustaining a proton-motive force across the inner membrane that is used to synthesize ATP. The question of how the densely packed proteins of the inner membrane are organized to optimize structure and function has returned to prominence with the characterization of respiratory-chain supercomplexes. Supercomplexes are increasingly accepted structural entities, but their functional and catalytic advantages are disputed. Notably, substrate “channeling” between the enzymes in supercomplexes has been proposed to confer a kinetic advantage, relative to the rate provided by a freely accessible, common substrate pool. Here, we focus on the mitochondrial ubiquinone/ubiquinol pool. We formulate and test three conceptually simple predictions of the behavior of the mammalian respiratory chain that depend on whether channeling in supercomplexes is kinetically important, and on whether the ubiquinone pool is partitioned between pathways. Our spectroscopic and kinetic experiments demonstrate how the metabolic pathways for NADH and succinate oxidation communicate and catalyze via a single, universally accessible ubiquinone/ubiquinol pool that is not partitioned or channeled. We reevaluate the major piece of contrary evidence from flux control analysis and find that the conclusion of substrate channeling arises from the particular behavior of a single inhibitor; we explain why different inhibitors behave differently and show that a robust flux control analysis provides no evidence for channeling. Finally, we discuss how the formation of respiratory-chain supercomplexes may confer alternative advantages on energy-converting membranes. PMID:25331896

  19. Kinetic evidence against partitioning of the ubiquinone pool and the catalytic relevance of respiratory-chain supercomplexes.

    PubMed

    Blaza, James N; Serreli, Riccardo; Jones, Andrew J Y; Mohammed, Khairunnisa; Hirst, Judy

    2014-11-04

    In mitochondria, four respiratory-chain complexes drive oxidative phosphorylation by sustaining a proton-motive force across the inner membrane that is used to synthesize ATP. The question of how the densely packed proteins of the inner membrane are organized to optimize structure and function has returned to prominence with the characterization of respiratory-chain supercomplexes. Supercomplexes are increasingly accepted structural entities, but their functional and catalytic advantages are disputed. Notably, substrate "channeling" between the enzymes in supercomplexes has been proposed to confer a kinetic advantage, relative to the rate provided by a freely accessible, common substrate pool. Here, we focus on the mitochondrial ubiquinone/ubiquinol pool. We formulate and test three conceptually simple predictions of the behavior of the mammalian respiratory chain that depend on whether channeling in supercomplexes is kinetically important, and on whether the ubiquinone pool is partitioned between pathways. Our spectroscopic and kinetic experiments demonstrate how the metabolic pathways for NADH and succinate oxidation communicate and catalyze via a single, universally accessible ubiquinone/ubiquinol pool that is not partitioned or channeled. We reevaluate the major piece of contrary evidence from flux control analysis and find that the conclusion of substrate channeling arises from the particular behavior of a single inhibitor; we explain why different inhibitors behave differently and show that a robust flux control analysis provides no evidence for channeling. Finally, we discuss how the formation of respiratory-chain supercomplexes may confer alternative advantages on energy-converting membranes.

  20. Hybrid Amyloid Membranes for Continuous Flow Catalysis.

    PubMed

    Bolisetty, Sreenath; Arcari, Mario; Adamcik, Jozef; Mezzenga, Raffaele

    2015-12-29

    Amyloid fibrils are promising nanomaterials for technological applications such as biosensors, tissue engineering, drug delivery, and optoelectronics. Here we show that amyloid-metal nanoparticle hybrids can be used both as efficient active materials for wet catalysis and as membranes for continuous flow catalysis applications. Initially, amyloid fibrils generated in vitro from the nontoxic β-lactoglobulin protein act as templates for the synthesis of gold and palladium metal nanoparticles from salt precursors. The resulting hybrids possess catalytic features as demonstrated by evaluating their activity in a model catalytic reaction in water, e.g., the reduction of 4-nitrophenol into 4-aminophenol, with the rate constant of the reduction increasing with the concentration of amyloid-nanoparticle hybrids. Importantly, the same nanoparticles adsorbed onto fibrils surface show improved catalytic efficiency compared to the same unattached particles, pointing at the important role played by the amyloid fibril templates. Then, filter membranes are prepared from the metal nanoparticle-decorated amyloid fibrils by vacuum filtration. The resulting membranes serve as efficient flow catalysis active materials, with a complete catalytic conversion achieved within a single flow passage of a feeding solution through the membrane.

  1. Membrane electrode assembly for a fuel cell

    NASA Technical Reports Server (NTRS)

    Prakash, Surya (Inventor); Narayanan, Sekharipuram R. (Inventor); Atti, Anthony (Inventor); Olah, George (Inventor); Smart, Marshall C. (Inventor)

    2006-01-01

    A catalyst ink for a fuel cell including a catalytic material and poly(vinylidene fluoride). The ink may be applied to a substrate to form an electrode, or bonded with other electrode layers to form a membrane electrode assembly (MEA).

  2. Synthesis of catalytic materials in flames: opportunities and challenges.

    PubMed

    Koirala, Rajesh; Pratsinis, Sotiris E; Baiker, Alfons

    2016-05-31

    The proven capacity of flame aerosol technology for rapid and scalable synthesis of functional nanoparticles makes it ideal for the manufacture of an array of heterogeneous catalysts. Capitalizing on the high temperature environment, rapid cooling and intimate component mixing at either atomic or nano scale, novel catalysts with unique physicochemical properties have been made using flame processes. This tutorial review covers the main features of flame synthesis and illustrates how the physical and chemical properties of as-synthesized solid catalytic materials can be controlled by proper choice of the process parameters. Gas phase particle formation mechanisms and the effect of synthesis conditions (reactor configuration, precursor and dispersion gas flow rates, temperature and concentration fields) on the structural, chemical and catalytic properties of as-prepared materials are discussed. Finally, opportunities and challenges offered by flame synthesis of catalytic materials are addressed.

  3. Ultra Low NOx Catalytic Combustion for IGCC Power Plants

    SciTech Connect

    Shahrokh Etemad; Benjamin Baird; Sandeep Alavandi; William Pfefferle

    2008-03-31

    In order to meet DOE's goals of developing low-emissions coal-based power systems, PCI has further developed and adapted it's Rich-Catalytic Lean-burn (RCL{reg_sign}) catalytic reactor to a combustion system operating on syngas as a fuel. The technology offers ultra-low emissions without the cost of exhaust after-treatment, with high efficiency (avoidance of after-treatment losses and reduced diluent requirements), and with catalytically stabilized combustion which extends the lower Btu limit for syngas operation. Tests were performed in PCI's sub-scale high-pressure (10 atm) test rig, using a two-stage (catalytic then gas-phase) combustion process for syngas fuel. In this process, the first stage consists of a fuel-rich mixture reacting on a catalyst with final and excess combustion air used to cool the catalyst. The second stage is a gas-phase combustor, where the air used for cooling the catalyst mixes with the catalytic reactor effluent to provide for final gas-phase burnout and dilution to fuel-lean combustion products. During testing, operating with a simulated Tampa Electric's Polk Power Station syngas, the NOx emissions program goal of less than 0.03 lbs/MMBtu (6 ppm at 15% O{sub 2}) was met. NOx emissions were generally near 0.01 lbs/MMBtu (2 ppm at 15% O{sub 2}) (PCI's target) over a range on engine firing temperatures. In addition, low emissions were shown for alternative fuels including high hydrogen content refinery fuel gas and low BTU content Blast Furnace Gas (BFG). For the refinery fuel gas increased resistance to combustor flashback was achieved through preferential consumption of hydrogen in the catalytic bed. In the case of BFG, stable combustion for fuels as low as 88 BTU/ft{sup 3} was established and maintained without the need for using co-firing. This was achieved based on the upstream catalytic reaction delivering a hotter (and thus more reactive) product to the flame zone. The PCI catalytic reactor was also shown to be active in ammonia

  4. MULTI-POLLUTANT CONTROL USING MEMBRANE--BASED UP-FLOW WET ELECTROSTATIC PRECIPITATION

    SciTech Connect

    James Reynolds

    2004-10-29

    This is the Final Report of the ''Multi-Pollutant Control Using Membrane-Based Up-flow Wet Electrostatic Precipitation'' project funded by the US Department of Energy's National Energy Technology Laboratory under DOE Award No. DE-FC26-02NT41592 to Croll-Reynolds Clean Air Technologies (CRCAT). In this 18 month project, CRCAT and its team members conducted detailed emission tests of metallic and new membrane collection material within a wet electrostatic precipitator (WESP) at First Energy's Penn Power's Bruce Mansfield (BMP) plant in Shippingport, Pa. The Membrane WESP was designed to be as similar as the metallic WESP in terms of collection area, air-flow, and electrical characteristics. Both units are two-field units. The membrane unit was installed during the 2nd and 3rd quarters of 2003. Testing of the metallic unit was performed to create a baseline since the Mansfield plant had installed selective catalytic reduction equipment for NOx control and a sodium bisulfate injection system for SO3 control during the spring of 2003. Tests results on the metallic WESP were consistent with previous testing for PM2.5, SO3 mist and mercury. Testing on the membrane WESP demonstrated no adverse impact and equivalent removal efficiencies as that of the metallic WESP. Testing on both units was performed at 8,000 acfm and 15,000 acfm. Summary results are shown.

  5. Catalytic Hydroxylation of Polyethylenes

    PubMed Central

    2017-01-01

    Polyolefins account for 60% of global plastic consumption, but many potential applications of polyolefins require that their properties, such as compatibility with polar polymers, adhesion, gas permeability, and surface wetting, be improved. A strategy to overcome these deficiencies would involve the introduction of polar functionalities onto the polymer chain. Here, we describe the Ni-catalyzed hydroxylation of polyethylenes (LDPE, HDPE, and LLDPE) in the presence of mCPBA as an oxidant. Studies with cycloalkanes and pure, long-chain alkanes were conducted to assess precisely the selectivity of the reaction and the degree to which potential C–C bond cleavage of a radical intermediate occurs. Among the nickel catalysts we tested, [Ni(Me4Phen)3](BPh4)2 (Me4Phen = 3,4,7,8,-tetramethyl-1,10-phenanthroline) reacted with the highest turnover number (TON) for hydroxylation of cyclohexane and the highest selectivity for the formation of cyclohexanol over cyclohexanone (TON, 5560; cyclohexanol/(cyclohexanone + ε-caprolactone) ratio, 10.5). The oxidation of n-octadecane occurred at the secondary C–H bonds with 15.5:1 selectivity for formation of an alcohol over a ketone and 660 TON. Consistent with these data, the hydroxylation of various polyethylene materials by the combination of [Ni(Me4Phen)3](BPh4)2 and mCPBA led to the introduction of 2.0 to 5.5 functional groups (alcohol, ketone, alkyl chloride) per 100 monomer units with up to 88% selectivity for formation of alcohols over ketones or chloride. In contrast to more classical radical functionalizations of polyethylene, this catalytic process occurred without significant modification of the molecular weight of the polymer that would result from chain cleavage or cross-linking. Thus, the resulting materials are new compositions in which hydroxyl groups are located along the main chain of commercial, high molecular weight LDPE, HDPE, and LLDPE materials. These hydroxylated polyethylenes have improved wetting

  6. Catalytic combustion with steam injection

    NASA Technical Reports Server (NTRS)

    Anderson, D. N.; Tacina, R. R.

    1982-01-01

    The effects of steam injection on (1) catalytic combustion performance, and (2) the tendency of residual fuel to burn in the premixing duct upstream of the catalytic reactor were determined. A petroleum residual, no. 2 diesel, and a blend of middle and heavy distillate coal derived fuels were tested. Fuel and steam were injected together into the preheated airflow entering a 12 cm diameter catalytic combustion test section. The inlet air velocity and pressure were constant at 10 m/s and 600 kPa, respectively. Steam flow rates were varied from 24 percent to 52 percent of the air flow rate. The resulting steam air mixture temperatures varied from 630 to 740 K. Combustion temperatures were in the range of 1200 to 1400 K. The steam had little effect on combustion efficiency or emissions. It was concluded that the steam acts as a diluent which has no adverse effect on catalytic combustion performance for no. 2 diesel and coal derived liquid fuels. Tests with the residual fuel showed that upstream burning could be eliminated with steam injection rates greater than 30 percent of the air flow rate, but inlet mixture temperatures were too low to permit stable catalytic combustion of this fuel.

  7. Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing

    DOEpatents

    Van Calcar, Pamela; Mackay, Richard; Sammells, Anthony F.

    2002-01-01

    The invention relates to mixed phase materials for the preparation of catalytic membranes which exhibit ionic and electronic conduction and which exhibit improved mechanical strength compared to single phase ionic and electronic conducting materials. The mixed phase materials are useful for forming gas impermeable membranes either as dense ceramic membranes or as dense thin films coated onto porous substrates. The membranes and materials of this invention are useful in catalytic membrane reactors in a variety of applications including synthesis gas production. One or more crystalline second phases are present in the mixed phase material at a level sufficient to enhance the mechanical strength of the mixture to provide membranes for practical application in CMRs.

  8. Catalytic bioreactors and methods of using same

    DOEpatents

    Worden, Robert Mark; Liu, Yangmu Chloe

    2017-07-25

    Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

  9. Viral membrane fusion.

    PubMed

    Harrison, Stephen C

    2015-05-01

    Membrane fusion is an essential step when enveloped viruses enter cells. Lipid bilayer fusion requires catalysis to overcome a high kinetic barrier; viral fusion proteins are the agents that fulfill this catalytic function. Despite a variety of molecular architectures, these proteins facilitate fusion by essentially the same generic mechanism. Stimulated by a signal associated with arrival at the cell to be infected (e.g., receptor or co-receptor binding, proton binding in an endosome), they undergo a series of conformational changes. A hydrophobic segment (a "fusion loop" or "fusion peptide") engages the target-cell membrane and collapse of the bridging intermediate thus formed draws the two membranes (virus and cell) together. We know of three structural classes for viral fusion proteins. Structures for both pre- and postfusion conformations of illustrate the beginning and end points of a process that can be probed by single-virion measurements of fusion kinetics. Copyright © 2015 The Author. Published by Elsevier Inc. All rights reserved.

  10. Catalytic decomposition of petroleum into natural gas

    SciTech Connect

    Mango, F.D.; Hightower, J.

    1997-12-01

    Petroleum is believed to be unstable in the earth, decomposing to lighter hydrocarbons at temperatures > 150{degrees}C. Oil and gas deposits support this view: gas/oil ratios and methane concentrations tend to increase with depth above 150{degrees}C. Although oil cracking is suggested and receives wide support, laboratory pyrolysis does not give products resembling natural gas. Moreover, it is doubtful that the light hydrocarbons in wet gas (C{sub 2}-C{sub 4}) could decompose over geologic time to dry gas (>95% methane) without catalytic assistance. We now report the catalytic decomposition of crude oil to a gas indistinguishable from natural gas. Like natural gas in deep basins, it becomes progressively enriched in methane: initially 90% (wet gas) to a final composition of 100% methane (dry gas). To our knowledge, the reaction is unprecedented and unexpectedly robust (conversion of oil to gas is 100% in days, 175{degrees}C) with significant implications regarding the stability of petroleum in sedimentary basins. The existence or nonexistence of oil in the deep subsurface may not depend on the thermal stability of hydrocarbons as currently thought. The critical factor could be the presence of transition metal catalysts which destabilize hydrocarbons and promote their decomposition to natural gas.

  11. ULTRA LOW NOx CATALYTIC COMBUSTION FOR IGCC POWER PLANTS

    SciTech Connect

    Lance L. Smith

    2004-03-01

    Tests were performed in PCI's sub-scale high-pressure (10 atm) test rig, using PCI's two-stage (catalytic / gas-phase) combustion process for syngas fuel. In this process, the first stage is a Rich-Catalytic Lean-burn (RCL{trademark}) catalytic reactor, wherein a fuel-rich mixture contacts the catalyst and reacts while final and excess combustion air cool the catalyst. The second stage is a gas-phase combustor, wherein the catalyst cooling air mixes with the catalytic reactor effluent to provide for final gas-phase burnout and dilution to fuel-lean combustion products. During the reporting period, PCI successfully achieved NOx = 0.011 lbs/MMBtu at 10 atm pressure (corresponding to 2.0 ppm NOx corrected to 15% O{sub 2} dry) with near-zero CO emissions, surpassing the project goal of < 0.03 lbs/MMBtu NOx. These emissions levels were achieved at scaled (10 atm, sub-scale) baseload conditions corresponding to Tampa Electric's Polk Power Station operation on 100% syngas (no co-firing of natural gas).

  12. Expression studies of catalytic antibodies

    SciTech Connect

    Ulrich, H.D.; Patten, P.A.; Yang, P.L.

    1995-12-05

    We have examined the positive influence of human constant regions on the folding and bacterial expression of active soluble mouse immunoglobulin variable domains derived form a number of catalytic antibodies. Expression yields of eight hybridoma-and myeloma-derived chimeric Fab fragments are compared in both shake flasks and high-density fermentation. In addition the usefulness of this system for the generation of in vivo expression libraries is examined by constructing and expressing combinations of heavy and light chain variable regions that were not selected as a pair during an immune response. A mutagenesis study of one of the recombinant catalytic Fab fragments reveals that single amino acid substitutions can have dramatic effects on the expression yield. This system should be generally applicable to the production of Fab fragments of catalytic and other hybridoma-derived antibodies for crystallographic and structure-function studies. 41 refs., 4 figs., 1 tab.

  13. Catalytic distillation water recovery subsystem

    NASA Technical Reports Server (NTRS)

    Budininkas, P.; Rasouli, F.

    1985-01-01

    An integrated engineering breadboard subsystem for the recovery of potable water from untreated urine based on the vapor phase catalytic ammonia removal was designed, fabricated and tested. Unlike other evaporative methods, this process catalytically oxidizes ammonia and volatile hydrocarbons vaporizing with water to innocuous products; therefore, no pretreatment of urine is required. Since the subsystem is fabricated from commercially available components, its volume, weight and power requirements are not optimized; however, it is suitable for zero-g operation. The testing program consists of parametric tests, one month of daily tests and a continuous test of 168 hours duration. The recovered water is clear, odorless, low in ammonia and organic carbon, and requires only an adjustment of its pH to meet potable water standards. The obtained data indicate that the vapor phase catalytic ammonia removal process, if further developed, would also be competitive with other water recovery systems in weight, volume and power requirements.

  14. Transient Numerical Modeling of Catalytic Channels

    NASA Technical Reports Server (NTRS)

    Struk, Peter M.; Dietrich, Daniel L.; Miller, Fletcher J.; T'ien, James S.

    2007-01-01

    first case. Finally, the results show that different initial surface-species distribution leads to different steady-states under certain conditions. These results demonstrate the utility of a lumped two-phase model of a transient catalytic combustor with detailed chemistry.

  15. Perfluoropolyalkylether decomposition on catalytic aluminas

    NASA Technical Reports Server (NTRS)

    Morales, Wilfredo

    1994-01-01

    The decomposition of Fomblin Z25, a commercial perfluoropolyalkylether liquid lubricant, was studied using the Penn State Micro-oxidation Test, and a thermal gravimetric/differential scanning calorimetry unit. The micro-oxidation test was conducted using 440C stainless steel and pure iron metal catalyst specimens, whereas the thermal gravimetric/differential scanning calorimetry tests were conducted using catalytic alumina pellets. Analysis of the thermal data, high pressure liquid chromatography data, and x-ray photoelectron spectroscopy data support evidence that there are two different decomposition mechanisms for Fomblin Z25, and that reductive sites on the catalytic surfaces are responsible for the decomposition of Fomblin Z25.

  16. Superhydrophobic Membrane Contactor for Acid Gas Removal

    NASA Astrophysics Data System (ADS)

    Faiqotul Himma, Nurul; Gede Wenten, I.

    2017-07-01

    Gas-liquid membrane contactor has gained a great attention as an alternative to conventional absorption columns in acid gas removal from natural gas or post-combustion. The membrane contactor offers high mass transfer area and excellent operational flexibility. However, hydrophobic microporous membranes commonly used are still susceptible to wetting by liquid absorbents, leading to the deterioration of absorption performance in long-term operation. Therefore, many studies were recently directed to improve the membrane wetting resistant by endowing superhydrophobicity. This article then presents a review on superhydrophobic membrane development and its application for acid gas removal using membrane contactor. An overview of gas-liquid membrane contactor is firstly presented, followed by the preparation of superhydrophobic membranes. The performances of superhydrophobic membranes in acid gas absorption are then discussed, and the recommendation for future research is finally outlined. This review may provide an insight into the further development of superhydrophobic membrane contactor.

  17. Multicomponent membranes

    DOEpatents

    Kulprathipanja, Santi; Kulkarni, Sudhir S.; Funk, Edward W.

    1988-01-01

    A multicomponent membrane which may be used for separating various components which are present in a fluid feed mixture comprises a mixture of a plasticizer such as a glycol and an organic polymer cast upon a porous organic polymer support. The membrane may be prepared by casting an emulsion or a solution of the plasticizer and polymer on the porous support, evaporating the solvent and recovering the membrane after curing.

  18. Catalytic oxidation of cyanide-contaminated wastewaters

    SciTech Connect

    1995-03-01

    Cyanide-contaminated wastewaters are commonly generated in the chemical, mining, electroplating, and hydrogen cyanide production industries. Although alkaline chlorination and a number of other techniques are currently used to treat such waste streams, researchers at the UOP Research Center in Des Plains, Illinois are developing a catalytic oxidation process that may result in favorable economics and more environmentally benign end products. Laboratory and pilot-scale test results indicate that cyanide conversions of up to 99.9% are possible with less than 0.1 ppmw cyanide remaining in the effluent. Metal-complexed cyanides, which are the most difficult to treat, are also amendable to treatment in this process. Finally, organic constituents in the wastewaters are oxidized by the process before they have a chance to foul or poison the catalyst. 1 ref., 2 figs.

  19. Membrane-electrode assemblies for electrochemical cells

    DOEpatents

    Swathirajan, Sundararajan; Mikhail, Youssef M.

    1993-01-01

    A combination, unitary, membrane and electrode assembly with a solid polymer electrolyte membrane, and first and second electrodes at least partially embedded in opposed surfaces of the membrane. The electrodes each comprise a respective group of finely divided carbon particles, very finely divided catalytic particles supported on internal and external surfaces of the carbon particles and a proton conductive material intermingled with the catalytic and carbon particles. A first group of finely divided carbon particles forming the first electrode has greater water attraction and retention properties, and is more hydrophilic than a second group of carbon particles forming the second electrode. In a preferred method, the membrane electrode assembly of the invention is prepared by forming a slurry of proton conductive material and at least one group of the carbon and catalyst particles. The slurry is applied to the opposed surfaces of the membrane and heated while being pressed to the membrane for a time and at a temperature and compressive load sufficient to embed at least a portion of the particles into the membrane.

  20. Catalytically enhanced packed tower scrubbing

    SciTech Connect

    Stitt, E.H.; Taylor, F.J.; Kelly, K.

    1996-12-31

    An enhanced wet scrubbing process for the treatment of gas streams containing odours and low level VOC`s is presented. It comprises essentially a single scrubbing column and a fixed bed catalytic reactor through which the dilute alkaline bleach scrubbing liquor is recirculated. The process has significant cost advantages over conventional chemical scrubbing technology, and copes well with peaks in odour levels. Traditional bleach scrubbing, and the improvements in process chemistry and the flowsheet afforded by inclusion of the catalyst, are discussed. The catalyst enables many of the well known problems associated with bleach scrubbing to be overcome, and facilitates odour removal efficiencies of greater than 99% in a single column. Pilot plant data from trials on sewage treatment works are presented. These show clearly the ability of the catalytically enhanced process to achieve sulphide and odour removals in excess of 99% in the single column. Case studies of some of the existing commercial installations are given, indicating the wide range of applications, industries and scale of the installed units. Comparative data are presented, measured on a commercial unit for the conventional operation of a bleach scrubber, and with the retrofitted catalyst in use. These data show clearly the benefits of the catalytic process in terms of removal efficiencies; and hence by inference also in equipment size and costs. The catalytic process is also shown to achieve very high removal efficiencies of organo-sulphides in a single column. 8 refs., 3 figs., 10 tabs.

  1. Catalytic oxidation of waste materials

    NASA Technical Reports Server (NTRS)

    Jagow, R. B.

    1977-01-01

    Aqueous stream of human waste is mixed with soluble ruthenium salts and is introduced into reactor at temperature where ruthenium black catalyst forms on internal surfaces of reactor. This provides catalytically active surface to convert oxidizable wastes into breakdown products such as water and carbon dioxide.

  2. Simple, Chemoselective, Catalytic Olefin Isomerization

    PubMed Central

    2015-01-01

    Catalytic amounts of Co(SaltBu,tBu)Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated. PMID:25398144

  3. Catalytic Asymmetric Bromocyclization of Polyenes.

    PubMed

    Samanta, Ramesh C; Yamamoto, Hisashi

    2017-02-01

    The first catalytic asymmetric bromonium ion-induced polyene cyclization has been achieved by using a chiral BINOL-derived thiophosphoramide catalyst and 1,3-dibromo-5,5-dimethylhydantoin as an electrophilic bromine source. Bromocyclization products are obtained in high yields, with good enantiomeric ratios and high diastereoselectivity, and are abundantly found as scaffolds in natural products.

  4. Carbon Cloth Supports Catalytic Electrodes

    NASA Technical Reports Server (NTRS)

    Lu, W. T. P.; Ammon, R. L.

    1983-01-01

    Carbon cloth is starting material for promising new catalytic electrodes. Carbon-cloth electrodes are more efficient than sintered-carbon configuration previously used. Are also chemically stable and require less catalyst--an important economic advantage when catalyst is metal such as platinum.

  5. Heterogeneous catalytic alcoholysis of benzonitrile

    SciTech Connect

    Kagarlitskii, A.D.; Dmumakaev, K.Kh.; Bekova, N.S.

    1986-04-01

    The authors investigate the possibility of the direct heterogeneous catalytic synthesis of ethylbenzoate from benzonitrile. The catalysts tested were oxides of aluminium, titanium, and vanadium. The main conversion product detected chromatographically was ethylbenzoate; benzaldehyde, benzamide, and benzanilide were also identified. Aluminium oxide was found to be the most effective catalyst.

  6. Catalytic Conversion of Biomass to Fuels and Chemicals Using Ionic Liquids

    SciTech Connect

    Liu, Wei; Zheng, Richard; Brown, Heather; Li, Joanne; Holladay, John; Cooper, Alan; Rao, Tony

    2012-04-13

    This project provides critical innovations and fundamental understandings that enable development of an economically-viable process for catalytic conversion of biomass (sugar) to 5-hydroxymethylfurfural (HMF). A low-cost ionic liquid (Cyphos 106) is discovered for fast conversion of fructose into HMF under moderate reaction conditions without any catalyst. HMF yield from fructose is almost 100% on the carbon molar basis. Adsorbent materials and adsorption process are invented and demonstrated for separation of 99% pure HMF product and recovery of the ionic liquid from the reaction mixtures. The adsorbent material appears very stable in repeated adsorption/regeneration cycles. Novel membrane-coated adsorbent particles are made and demonstrated to achieve excellent adsorption separation performances at low pressure drops. This is very important for a practical adsorption process because ionic liquids are known of high viscosity. Nearly 100% conversion (or dissolution) of cellulose in the catalytic ionic liquid into small molecules was observed. It is promising to produce HMF, sugars and other fermentable species directly from cellulose feedstock. However, several gaps were identified and could not be resolved in this project. Reaction and separation tests at larger scales are needed to minimize impacts of incidental errors on the mass balance and to show 99.9% ionic liquid recovery. The cellulose reaction tests were troubled with poor reproducibility. Further studies on cellulose conversion in ionic liquids under better controlled conditions are necessary to delineate reaction products, dissolution kinetics, effects of mass and heat transfer in the reactor on conversion, and separation of final reaction mixtures.

  7. 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.

  8. Final Report

    SciTech Connect

    Taylor, Philip L.

    2012-11-11

    Our research program was aimed at elucidating the nature of proton transport in ionomer membranes by means of a combination of analytical theory and molecular modeling. There were two broad thrusts. The first of these was directed towards understanding the equilibrium structure of Nafion and related polymers at various levels of hydration. The second thrust was concerned with the transport of protons through a membrane of this type. The research on structure proceeded by building on existing work, but with the introduction of some novel techniques, among which is a hybrid Molecular Dynamics--Monte Carlo approach. This method permits rapid computations by temporarily decoupling the motion of the polar side chains from that of the perfluorinated backbone, while still retaining the essential aspects of the constraint that phase separation can only continue to a very limited degree. Competition between an elastic energy due to this constraint and the tendency to phase separation lead to the equilibrium structure, which turns out to be qualitatively different at different levels of hydration. The use of a carefully formulated dielectric function was necessary to achieve accurate results. The work on transport of protons in Nafion-like membranes also involved a combination of theory and simulation. Atomistic molecular-dynamics simulations were employed to determine some of the characteristic parameters for the diffusion of hydronium in hydrated membranes. These results were used in a theoretical model of non-linear diffusion to predict transport coefficients. Among our results was the discovery that treatment with strong electric fields may enhance the properties of the polymer membranes. Our computer simulations showed that the vigorous application of a stretching force or an electric field can modify the structure of the ionomer that lies at the heart of a polymer-electrolyte-membrane fuel cell. If these predictions are verified experimentally, then it should be

  9. Molecular Physiology of Membrane Guanylyl Cyclase Receptors.

    PubMed

    Kuhn, Michaela

    2016-04-01

    cGMP controls many cellular functions ranging from growth, viability, and differentiation to contractility, secretion, and ion transport. The mammalian genome encodes seven transmembrane guanylyl cyclases (GCs), GC-A to GC-G, which mainly modulate submembrane cGMP microdomains. These GCs share a unique topology comprising an extracellular domain, a short transmembrane region, and an intracellular COOH-terminal catalytic (cGMP synthesizing) region. GC-A mediates the endocrine effects of atrial and B-type natriuretic peptides regulating arterial blood pressure/volume and energy balance. GC-B is activated by C-type natriuretic peptide, stimulating endochondral ossification in autocrine way. GC-C mediates the paracrine effects of guanylins on intestinal ion transport and epithelial turnover. GC-E and GC-F are expressed in photoreceptor cells of the retina, and their activation by intracellular Ca(2+)-regulated proteins is essential for vision. Finally, in the rodent system two olfactorial GCs, GC-D and GC-G, are activated by low concentrations of CO2and by peptidergic (guanylins) and nonpeptidergic odorants as well as by coolness, which has implications for social behaviors. In the past years advances in human and mouse genetics as well as the development of sensitive biosensors monitoring the spatiotemporal dynamics of cGMP in living cells have provided novel relevant information about this receptor family. This increased our understanding of the mechanisms of signal transduction, regulation, and (dys)function of the membrane GCs, clarified their relevance for genetic and acquired diseases and, importantly, has revealed novel targets for therapies. The present review aims to illustrate these different features of membrane GCs and the main open questions in this field.

  10. Reversible catalytic dehydrogenation of alcohols for energy storage

    DOE PAGES

    Bonitatibus, Jr., Peter J.; Chakraborty, Sumit; Doherty, Mark D.; ...

    2015-01-14

    Reversibility of a dehydrogenation/hydrogenation catalytic reaction has been an elusive target for homogeneous catalysis. In this paper, reversible acceptorless dehydrogenation of secondary alcohols and diols on iron pincer complexes and reversible oxidative dehydrogenation of primary alcohols/reduction of aldehydes with separate transfer of protons and electrons on iridium complexes are shown. Finally, this reactivity suggests a strategy for the development of reversible fuel cell electrocatalysts for partial oxidation (dehydrogenation) of hydroxyl-containing fuels.

  11. Thermodynamics of membrane insertion and refolding of the diphtheria toxin T-domain

    PubMed Central

    Vargas-Uribe, Mauricio; Rodnin, Mykola V.; Öjemalm, Karin; Holgado, Aurora; Kyrychenko, Alexander; Nilsson, IngMarie; Posokhov, Yevgen O.; Makhatadze, George; von Heijne, Gunnar; Ladokhin, Alexey S.

    2014-01-01

    The diphtheria toxin translocation (T) domain inserts into the endosomal membrane in response to the endosomal acidification and enables the delivery of the catalytic domain into the cell. The insertion pathway consists of a series of conformational changes that occur in solution and in the membrane and leads to the conversion of a water-soluble state into a transmembrane state. In this work, we utilize various biophysical techniques to characterize the insertion pathway from the thermodynamic perspective. Thermal and chemical unfolding measured by differential scanning calorimetry, circular dichroism and tryptophan fluorescence reveal that the free energy of unfolding of the T-domain at neutral and mildly acidic pH differ by 3–5 kcal/mol, depending on the experimental conditions. Fluorescence correlation spectroscopy measurements show that the free energy change from the membrane-competent state to the interfacial state is approximately −8 kcal/mol and is pH-independent, while that from the membrane-competent state to the transmembrane state ranges between −9.5 to −12 kcal/mol, depending on the membrane lipid composition and pH. Finally, the thermodynamics of transmembrane insertion of individual helices was tested using an in vitro assay that measures the translocon-assisted integration of test sequences into the microsomal membrane. These experiments suggest that even the most hydrophobic helix TH8 has only a small favorable free energy of insertion. The free energy for the insertion of the consensus insertion unit TH8-TH9 is slightly more favorable, yet less favorable than that measured for the entire protein, suggesting a cooperative effect for the membrane insertion of the helices of the T-domain. PMID:25281329

  12. [Epiretinal membranes].

    PubMed

    Dupas, B; Tadayoni, R; Gaudric, A

    2015-11-01

    Idiopathic epiretinal membranes represent a common condition, and are present in approximately 10% of people over the age of 70 years. They are idiopathic in 80% of cases, or may be secondary to various conditions such as a prior retinal detachment, or vascular or inflammatory retinal diseases. The main symptoms are visual loss and metamorphopsia. The diagnosis of epiretinal membrane is currently facilitated by OCT, which provides prognostic and therapeutic decision-making assistance. Surgery for epiretinal membranes is currently well codified through sutureless vitrectomy and dyes. Dissection of the membrane (with or without associated peeling of the internal limiting membrane) ensures good anatomical and functional results, while being relatively minimally invasive. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  13. Inorganic membranes and solid state sciences

    NASA Astrophysics Data System (ADS)

    Cot, Louis; Ayral, André; Durand, Jean; Guizard, Christian; Hovnanian, Nadine; Julbe, Anne; Larbot, André

    2000-05-01

    The latest developments in inorganic membranes are closely related to recent advances in solid state science. Sol-gel processing, plasma-enhanced chemical vapor deposition and hydrothermal synthesis are methods that can be used for inorganic membrane preparation. Innovative concepts from material science (templating effect, nanophase materials, growing of continuous zeolite layers, hybrid organic-inorganic materials) have been applied by our group to the preparation of inorganic membrane materials. Sol-gel-derived nanophase ceramic membranes are presented with current applications in nanofiltration and catalytic membrane reactors. Silica membranes with an ordered porosity, due to liquid crystal phase templating effect, are described with potential application in pervaporation. Defect-free and thermally stable zeolite membranes can be obtained through an original synthesis method, in which zeolite crystals are grown inside the pores of a support. Hybrid organic-inorganic materials with permselective properties for gas separation and facilitated transport of solutes in liquid media, have been successfully adapted to membrane applications. Potential membrane developments offered by CVD deposition techniques are also illustrated through several examples related to the preparation of purely inorganic and hybrid organic-inorganic membrane materials.

  14. Zwitterionic materials for antifouling membrane surface construction.

    PubMed

    He, Mingrui; Gao, Kang; Zhou, Linjie; Jiao, Zhiwei; Wu, Mengyuan; Cao, Jialin; You, Xinda; Cai, Ziyi; Su, Yanlei; Jiang, Zhongyi

    2016-08-01

    Membrane separation processes are often perplexed by severe and ubiquitous membrane fouling. Zwitterionic materials, keeping electric neutrality with equivalent positive and negative charged groups, are well known for their superior antifouling properties and have been broadly utilized to construct antifouling surfaces for medical devices, biosensors and marine coatings applications. In recent years, zwitterionic materials have been more and more frequently utilized for constructing antifouling membrane surfaces. In this review, the antifouling mechanisms of zwitterionic materials as well as their biomimetic prototypes in cell membranes will be discussed, followed by the survey of common approaches to incorporate zwitterionic materials onto membrane surfaces including surface grafting, surface segregation, biomimetic adhesion, surface coating and so on. The potential applications of these antifouling membranes are also embedded. Finally, we will present a brief perspective on the future development of zwitterionic materials modified antifouling membranes. Membrane fouling is a severe problem hampering the application of membrane separation technology. The properties of membrane surfaces play a critical role in membrane fouling and antifouling behavior/performance. Antifouling membrane surface construction has evolved as a hot research issue for the development of membrane processes. Zwitterionic modification of membrane surfaces has been recognized as an effective strategy to resist membrane fouling. This review summarizes the antifouling mechanisms of zwitterionic materials inspired by cell membranes as well as the popular approaches to incorporate them onto membrane surfaces. It can help form a comprehensive knowledge about the principles and methods of modifying membrane surfaces with zwitterionic materials. Finally, we propose the possible future research directions of zwitterionic materials modified antifouling membranes. Copyright © 2016 Acta Materialia Inc

  15. Method for low temperature catalytic production of hydrogen

    DOEpatents

    Mahajan, Devinder

    2003-07-22

    The invention provides a process for the catalytic production of a hydrogen feed by exposing a hydrogen feed to a catalyst which promotes a base-catalyzed water-gas-shift reaction in a liquid phase. The hydrogen feed can be provided by any process known in the art of making hydrogen gas. It is preferably provided by a process that can produce a hydrogen feed for use in proton exchange membrane fuel cells. The step of exposing the hydrogen feed takes place preferably from about 80.degree. C. to about 150.degree. C.

  16. Using ceramic membranes for the separation of hydrogen produced by dehydrogenation of perhydro- m-terphenyl

    NASA Astrophysics Data System (ADS)

    Kalenchuk, A. N.; Bogdan, V. I.; Kustov, L. M.

    2015-01-01

    The efficiency of a variety of ceramic membranes for the purification of hydrogen obtained by dehydrogenation of perhydro- m-terphenyl in a catalytic flow reactor from vapors of initial hydrocarbons and dehydrogenation products is investigated.

  17. Mechanisms of Ras membrane organization and signaling

    PubMed Central

    Abankwa, Daniel; Gorfe, Alemayehu A.; Hancock, John F.

    2009-01-01

    Understanding the signalling function of Ras GTPases has been the focus of much research for over 20 years. Both the catalytic domain and the membrane anchoring C terminal hypervariable region (HVR) of Ras are necessary for its cellular function. However, while the highly conserved catalytic domain has been characterized in atomic detail, the structure of the full-length membrane-bound Ras has remained elusive. Lack of structural knowledge on the full-length protein limited our understanding of Ras signalling. For example, structures of the Ras catalytic domain solved in complex with effectors do not provide a basis for the functional specificity of different Ras isoforms. Recent molecular dynamics simulations in combination with biophysical and cell biological experiments have shown that the HVR and parts of the G domain cofunction with the lipid tails to anchor H-ras to the plasma membrane. In the GTP-bound state, H-ras adopts an orientation that allows read out by Ras effectors and translation into corresponding MAPK signalling. Here we discuss details of an analysis that suggests a novel balance model for Ras functioning. The balance model rationalizes Ras membrane orientation and may help explain isoform specific interactions of Ras with its effectors and modulators. PMID:18758236

  18. Crystalline Membranes

    NASA Technical Reports Server (NTRS)

    Tsapatsis, Michael (Inventor); Lai, Zhiping (Inventor)

    2008-01-01

    In certain aspects, the invention features methods for forming crystalline membranes (e.g., a membrane of a framework material, such as a zeolite) by inducing secondary growth in a layer of oriented seed crystals. The rate of growth of the seed crystals in the plane of the substrate is controlled to be comparable to the rate of growth out of the plane. As a result, a crystalline membrane can form a substantially continuous layer including grains of uniform crystallographic orientation that extend through the depth of the layer.

  19. Chemical Imaging of Catalytic Solids with Synchrotron Radiation

    SciTech Connect

    A Beale; S Jacques; B Weckhuysen

    2011-12-31

    Heterogeneous catalysis is a term normally used to describe a group of catalytic processes, yet it could equally be employed to describe the catalytic solid itself. A better understanding of the chemical and structural variation within such materials is thus a pre-requisite for the rationalising of structure-function relationships and ultimately to the design of new, more sustainable catalytic processes. The past 20 years has witnessed marked improvements in technologies required for analytical measurements at synchrotron sources, including higher photon brightness, nano-focusing, rapid, high resolution data acquisition and in the handling of large volumes of data. It is now possible to image materials using the entire synchrotron radiative profile, thus heralding a new era of in situ/operando measurements of catalytic solids. In this tutorial review we discuss the recent work in this exciting new research area and finally conclude with a future outlook on what will be possible/challenging to measure in the not-too-distant future.

  20. Catalytic activity of human carbonic anhydrase isoform IX is displayed both extra- and intracellularly.

    PubMed

    Klier, Michael; Jamali, Somayeh; Ames, Samantha; Schneider, Hans-Peter; Becker, Holger M; Deitmer, Joachim W

    2016-01-01

    Most carbonic anhydrases catalyse the reversible conversion of carbon dioxide to protons and bicarbonate, either as soluble cytosolic enzymes, in or at intracellular organelles, or at the extracellular face of the cell membrane as membrane-anchored proteins. Carbonic anhydrase isoform IX (CA IX), a membrane-bound enzyme with catalytic activity at the extracellular membrane surface, has come to prominence in recent years because of its association with hypoxic tissue, particularly tumours, often indicating poor prognosis. We have evaluated the catalytic activity of CA IX heterologously expressed in Xenopus laevis oocytes by measuring the amplitude and rate of cytosolic pH changes as well as pH changes at the outer membrane surface (pHs ) during addition and removal of 5% CO2 /25 mm HCO3-, and by mass spectrometry. Our results indicate both extracellular and intracellular catalytic activity of CA IX. Reduced rates of CO2 -dependent intracellular pH changes after knockdown of CA IX confirmed these findings in two breast cancer cell lines: MCF-7 and MDA-MB-231. Our results demonstrate a new function of CA IX that may be important in the search for therapeutic cancer drugs targeting CA IX.

  1. Voltage-dependent motion of the catalytic region of voltage-sensing phosphatase monitored by a fluorescent amino acid

    PubMed Central

    Sakata, Souhei; Jinno, Yuka; Kawanabe, Akira; Okamura, Yasushi

    2016-01-01

    The cytoplasmic region of voltage-sensing phosphatase (VSP) derives the voltage dependence of its catalytic activity from coupling to a voltage sensor homologous to that of voltage-gated ion channels. To assess the conformational changes in the cytoplasmic region upon activation of the voltage sensor, we genetically incorporated a fluorescent unnatural amino acid, 3-(6-acetylnaphthalen-2-ylamino)-2-aminopropanoic acid (Anap), into the catalytic region of Ciona intestinalis VSP (Ci-VSP). Measurements of Anap fluorescence under voltage clamp in Xenopus oocytes revealed that the catalytic region assumes distinct conformations dependent on the degree of voltage-sensor activation. FRET analysis showed that the catalytic region remains situated beneath the plasma membrane, irrespective of the voltage level. Moreover, Anap fluorescence from a membrane-facing loop in the C2 domain showed a pattern reflecting substrate turnover. These results indicate that the voltage sensor regulates Ci-VSP catalytic activity by causing conformational changes in the entire catalytic region, without changing their distance from the plasma membrane. PMID:27330112

  2. Voltage-dependent motion of the catalytic region of voltage-sensing phosphatase monitored by a fluorescent amino acid.

    PubMed

    Sakata, Souhei; Jinno, Yuka; Kawanabe, Akira; Okamura, Yasushi

    2016-07-05

    The cytoplasmic region of voltage-sensing phosphatase (VSP) derives the voltage dependence of its catalytic activity from coupling to a voltage sensor homologous to that of voltage-gated ion channels. To assess the conformational changes in the cytoplasmic region upon activation of the voltage sensor, we genetically incorporated a fluorescent unnatural amino acid, 3-(6-acetylnaphthalen-2-ylamino)-2-aminopropanoic acid (Anap), into the catalytic region of Ciona intestinalis VSP (Ci-VSP). Measurements of Anap fluorescence under voltage clamp in Xenopus oocytes revealed that the catalytic region assumes distinct conformations dependent on the degree of voltage-sensor activation. FRET analysis showed that the catalytic region remains situated beneath the plasma membrane, irrespective of the voltage level. Moreover, Anap fluorescence from a membrane-facing loop in the C2 domain showed a pattern reflecting substrate turnover. These results indicate that the voltage sensor regulates Ci-VSP catalytic activity by causing conformational changes in the entire catalytic region, without changing their distance from the plasma membrane.

  3. Catalytic combustion of residual fuels

    NASA Technical Reports Server (NTRS)

    Bulzan, D. L.; Tacina, R. R.

    1981-01-01

    A noble metal catalytic reactor was tested using two grades of petroleum derived residual fuels at specified inlet air temperatures, pressures, and reference velocities. Combustion efficiencies greater than 99.5 percent were obtained. Steady state operation of the catalytic reactor required inlet air temperatures of at least 800 K. At lower inlet air temperatures, upstream burning in the premixing zone occurred which was probably caused by fuel deposition and accumulation on the premixing zone walls. Increasing the inlet air temperature prevented this occurrence. Both residual fuels contained about 0.5 percent nitrogen by weight. NO sub x emissions ranged from 50 to 110 ppm by volume at 15 percent excess O2. Conversion of fuel-bound nitrogen to NO sub x ranged from 25 to 50 percent.

  4. Vapor Phase Catalytic Ammonia Reduction

    NASA Technical Reports Server (NTRS)

    Flynn, Michael T.; Harper, Lynn D. (Technical Monitor)

    1994-01-01

    This paper discusses the development of a Vapor Phase Catalytic Ammonia Reduction (VPCAR) teststand and the results of an experimental program designed to evaluate the potential of the technology as a water purification process. In the experimental program the technology is evaluated based upon product water purity, water recovery rate, and power consumption. The experimental work demonstrates that the technology produces high purity product water and attains high water recovery rates at a relatively high specific power consumption. The experimental program was conducted in 3 phases. In phase I an Igepon(TM) soap and water mixture was used to evaluate the performance of an innovative Wiped-Film Rotating-Disk evaporator and associated demister. In phase II a phenol-water solution was used to evaluate the performance of the high temperature catalytic oxidation reactor. In phase III a urine analog was used to evaluate the performance of the combined distillation/oxidation functions of the processor.

  5. Vapor Phase Catalytic Ammonia Reduction

    NASA Technical Reports Server (NTRS)

    Flynn, Michael T.; Harper, Lynn D. (Technical Monitor)

    1994-01-01

    This paper discusses the development of a Vapor Phase Catalytic Ammonia Reduction (VPCAR) teststand and the results of an experimental program designed to evaluate the potential of the technology as a water purification process. In the experimental program the technology is evaluated based upon product water purity, water recovery rate, and power consumption. The experimental work demonstrates that the technology produces high purity product water and attains high water recovery rates at a relatively high specific power consumption. The experimental program was conducted in 3 phases. In phase I an Igepon(TM) soap and water mixture was used to evaluate the performance of an innovative Wiped-Film Rotating-Disk evaporator and associated demister. In phase II a phenol-water solution was used to evaluate the performance of the high temperature catalytic oxidation reactor. In phase III a urine analog was used to evaluate the performance of the combined distillation/oxidation functions of the processor.

  6. Catalytic strategy used by the myosin motor to hydrolyze ATP.

    PubMed

    Kiani, Farooq Ahmad; Fischer, Stefan

    2014-07-22

    Myosin is a molecular motor responsible for biological motions such as muscle contraction and intracellular cargo transport, for which it hydrolyzes adenosine 5'-triphosphate (ATP). Early steps of the mechanism by which myosin catalyzes ATP hydrolysis have been investigated, but still missing are the structure of the final ADP·inorganic phosphate (Pi) product and the complete pathway leading to it. Here, a comprehensive description of the catalytic strategy of myosin is formulated, based on combined quantum-classical molecular mechanics calculations. A full exploration of catalytic pathways was performed and a final product structure was found that is consistent with all experiments. Molecular movies of the relevant pathways show the different reorganizations of the H-bond network that lead to the final product, whose γ-phosphate is not in the previously reported HPγO4(2-) state, but in the H2PγO4(-) state. The simulations reveal that the catalytic strategy of myosin employs a three-pronged tactic: (i) Stabilization of the γ-phosphate of ATP in a dissociated metaphosphate (PγO3(-)) state. (ii) Polarization of the attacking water molecule, to abstract a proton from that water. (iii) Formation of multiple proton wires in the active site, for efficient transfer of the abstracted proton to various product precursors. The specific role played in this strategy by each of the three loops enclosing ATP is identified unambiguously. It explains how the precise timing of the ATPase activation during the force generating cycle is achieved in myosin. The catalytic strategy described here for myosin is likely to be very similar in most nucleotide hydrolyzing enzymes.

  7. Hydrogen production from methane through catalytic partial oxidation reactions

    NASA Astrophysics Data System (ADS)

    Freni, S.; Calogero, G.; Cavallaro, S.

    This paper reviews recent developments in syn-gas production processes used for partial methane oxidation with and/or without steam. In particular, we examined different process charts (fixed bed, fluidised bed, membrane, etc.), kinds of catalysts (powders, foams, monoliths, etc.) and catalytically active phases (Ni, Pt, Rh, etc.). The explanation of the various suggested technical solutions accounted for the reaction mechanism that may selectively lead to calibrated mixtures of CO and H 2 or to the unwanted formation of products of total oxidation (CO 2 and H 2O) and pyrolysis (coke). Moreover, the new classes of catalysts allow the use of small reactors to treat large amounts of methane (monoliths) or separate hydrogen in situ from the other reaction products (membrane). This leads to higher conversions and selectivity than could have been expected thermodynamically. Although catalysts based on Rh are extremely expensive, they can be used to minimise H 2O formation by maximising H 2 yield.

  8. Catalytic σ-Bond Metathesis

    NASA Astrophysics Data System (ADS)

    Reznichenko, Alexander L.; Hultzsch, Kai C.

    This account summarizes information on recently reported applications of organo-rare-earth metal complexes in various catalytic transformations of small molecules. The σ-bond metathesis at d0rare-earth metal centers plays a pivotal role in carbon-carbon and carbon-heteroatom bond forming processes. Relevant mechanistic details are discussed and the focus of the review lies in practical applications of organo-rare-earth metal complexes.

  9. ADAM17 is regulated by a rapid and reversible mechanism that controls access to its catalytic site

    PubMed Central

    Le Gall, Sylvain M.; Maretzky, Thorsten; Issuree, Priya D. A.; Niu, Xiao-Da; Reiss, Karina; Saftig, Paul; Khokha, Rama; Lundell, Daniel; Blobel, Carl P.

    2010-01-01

    Protein ectodomain shedding is crucial for cell–cell interactions because it controls the bioavailability of soluble tumor necrosis factor-α (TNFα) and ligands of the epidermal growth factor (EGF) receptor, and the release of many other membrane proteins. Various stimuli can rapidly trigger ectodomain shedding, yet much remains to be learned about the identity of the enzymes that respond to these stimuli and the mechanisms underlying their activation. Here, we demonstrate that the membrane-anchored metalloproteinase ADAM17, but not ADAM10, is the sheddase that rapidly responds to the physiological signaling pathways stimulated by thrombin, EGF, lysophosphatidic acid and TNFα. Stimulation of ADAM17 is swift and quickly reversible, and does not depend on removal of its inhibitory pro-domain by pro-protein convertases, or on dissociation of an endogenous inhibitor, TIMP3. Moreover, activation of ADAM17 by physiological stimuli requires its transmembrane domain, but not its cytoplasmic domain, arguing against inside–out signaling via cytoplasmic phosphorylation as the underlying mechanism. Finally, experiments with the tight binding hydroxamate inhibitor DPC333, used here to probe the accessibility of the active site of ADAM17, demonstrate that this inhibitor can quickly bind to ADAM17 in stimulated, but not quiescent cells. These findings support the concept that activation of ADAM17 involves a rapid and reversible exposure of its catalytic site. PMID:20980382

  10. Biological membranes

    PubMed Central

    Watson, Helen

    2015-01-01

    Biological membranes allow life as we know it to exist. They form cells and enable separation between the inside and outside of an organism, controlling by means of their selective permeability which substances enter and leave. By allowing gradients of ions to be created across them, membranes also enable living organisms to generate energy. In addition, they control the flow of messages between cells by sending, receiving and processing information in the form of chemical and electrical signals. This essay summarizes the structure and function of membranes and the proteins within them, and describes their role in trafficking and transport, and their involvement in health and disease. Techniques for studying membranes are also discussed. PMID:26504250

  11. Intracellular Targeting Signals and Lipid Specificity Determinants of the ALA/ALIS P4-ATPase Complex Reside in the Catalytic ALA α-Subunit

    PubMed Central

    Poulsen, Lisbeth R.; Hanisch, Susanne; Meffert, Katharina; Buch-Pedersen, Morten J.; Jakobsen, Mia K.; Pomorski, Thomas Günther; Palmgren, Michael G.

    2010-01-01

    Members of the P4 subfamily of P-type ATPases are believed to catalyze flipping of phospholipids across cellular membranes, in this way contributing to vesicle biogenesis in the secretory and endocytic pathways. P4-ATPases form heteromeric complexes with Cdc50-like proteins, and it has been suggested that these act as β-subunits in the P4-ATPase transport machinery. In this work, we investigated the role of Cdc50-like β-subunits of P4-ATPases for targeting and function of P4-ATPase catalytic α-subunits. We show that the Arabidopsis P4-ATPases ALA2 and ALA3 gain functionality when coexpressed with any of three different ALIS Cdc50-like β-subunits. However, the final cellular destination of P4-ATPases as well as their lipid substrate specificity are independent of the nature of the ALIS β-subunit they were allowed to interact with. PMID:20053675

  12. Thermodynamics of catalytic nanoparticle morphology

    NASA Astrophysics Data System (ADS)

    Zwolak, Michael; Sharma, Renu; Lin, Pin Ann

    Metallic nanoparticles are an important class of industrial catalysts. The variability of their properties and the environment in which they act, from their chemical nature & surface modification to their dispersion and support, allows their performance to be optimized for many chemical processes useful in, e.g., energy applications and other areas. Their large surface area to volume ratio, as well as varying sizes and faceting, in particular, makes them an efficient source for catalytically active sites. These characteristics of nanoparticles - i.e., their morphology - can often display intriguing behavior as a catalytic process progresses. We develop a thermodynamic model of nanoparticle morphology, one that captures the competition of surface energy with other interactions, to predict structural changes during catalytic processes. Comparing the model to environmental transmission electron microscope images of nickel nanoparticles during carbon nanotube (and other product) growth demonstrates that nickel deformation in response to the nanotube growth is due to a favorable interaction with carbon. Moreover, this deformation is halted due to insufficient volume of the particles. We will discuss the factors that influence morphology and also how the model can be used to extract interaction strengths from experimental observations.

  13. Final Report of a CRADA Between Pacific Northwest National Laboratory and the Ford Motor Company (CRADA No. PNNL/265): “Deactivation Mechanisms of Base Metal/Zeolite Urea Selective Catalytic Reduction Materials, and Development of Zeolite-Based Hydrocarbon Adsorber Materials”

    SciTech Connect

    Gao, Feng; Kwak, Ja Hun; Lee, Jong H.; Tran, Diana N.; Peden, Charles HF; Howden, Ken; Cheng, Yisun; Lupescu, Jason; Cavattaio, Giovanni; Lambert, Christine; McCabe, Robert W.

    2013-02-14

    the engine exhaust. For these reasons, automakers and engine manufacturers have difficulty improving their catalytic converters for meeting the stringent HC emission standards. In this collaborative program, scientists and engineers in the Institute for Integrated Catalysis at Pacific Northwest National Laboratory and at Ford Motor Company have investigated laboratory- and engine-aged SCR catalysts, containing mainly base metal zeolites. These studies are leading to a better understanding of various aging factors that impact the long-term performance of SCR catalysts and improve the correlation between laboratory and engine aging, saving experimental time and cost. We have also studied materials effective for the temporary storage of HC species during the cold-start period. In particular, we have examined the adsorption and desorption of various HC species produced during the combustion with different fuels (e.g., gasoline, E85, diesel) over potential HC adsorber materials, and measured the kinetic parameters to update Ford’s HC adsorption model. Since this CRADA has now been completed, in this final report we will provide brief summaries of most of the work carried out on this CRADA over the last several years.

  14. Postextraction Separation, On-Board Storage, and Catalytic Conversion of Methane in Natural Gas: A Review.

    PubMed

    Saha, Dipendu; Grappe, Hippolyte A; Chakraborty, Amlan; Orkoulas, Gerassimos

    2016-10-12

    In today's perspective, natural gas has gained considerable attention, due to its low emission, indigenous availability, and improvement in the extraction technology. Upon extraction, it undergoes several purification protocols including dehydration, sweetening, and inert rejection. Although purification is a commercially established technology, several drawbacks of the current process provide an essential impetus for developing newer separation protocols, most importantly, adsorption and membrane separation. This Review summarizes the needs of natural gas separation, gives an overview of the current technology, and provides a detailed discussion of the progress in research on separation and purification of natural gas including the benefits and drawbacks of each of the processes. The transportation sector is another growing sector of natural gas utilization, and it requires an efficient and safe on-board storage system. Compressed natural gas (CNG) and liquefied natural gas (LNG) are the most common forms in which natural gas can be stored. Adsorbed natural gas (ANG) is an alternate storage system of natural gas, which is advantageous as compared to CNG and LNG in terms of safety and also in terms of temperature and pressure requirements. This Review provides a detailed discussion on ANG along with computation predictions. The catalytic conversion of methane to different useful chemicals including syngas, methanol, formaldehyde, dimethyl ether, heavier hydrocarbons, aromatics, and hydrogen is also reviewed. Finally, direct utilization of methane onto fuel cells is also discussed.

  15. Final Report

    SciTech Connect

    Gurney, Kevin R.

    2015-01-12

    This document constitutes the final report under DOE grant DE-FG-08ER64649. The organization of this document is as follows: first, I will review the original scope of the proposed research. Second, I will present the current draft of a paper nearing submission to Nature Climate Change on the initial results of this funded effort. Finally, I will present the last phase of the research under this grant which has supported a Ph.D. student. To that end, I will present the graduate student’s proposed research, a portion of which is completed and reflected in the paper nearing submission. This final work phase will be completed in the next 12 months. This final workphase will likely result in 1-2 additional publications and we consider the results (as exemplified by the current paper) high quality. The continuing results will acknowledge the funding provided by DOE grant DE-FG-08ER64649.

  16. Final Report

    SciTech Connect

    DeTar, Carleton

    2012-12-10

    This document constitutes the Final Report for award DE-FC02-06ER41446 as required by the Office of Science. It summarizes accomplishments and provides copies of scientific publications with significant contribution from this award.

  17. High temperature ceramic membrane reactors for coal liquid upgrading. Quarterly report No. 1, September 21, 1989--December 20, 1989

    SciTech Connect

    Tsotsis, T.T.

    1992-06-19

    In this project we well evaluate the performance of Sel-Gel alumina membranes in coal liquid upgrading processes under realistic temperature and pressure conditions and investigate the feasibility of using such membranes in a membrane reactor based coal liquid upgrading process. In addition, the development of novel ceramic membranes with enhanced catalytic activity for coal-liquid upgrading applications, such as carbon-coated alumina membranes, will be also investigated. (VC)

  18. Catalytic Core of Human Topoisomerase IIα: Insights into Enzyme–DNA Interactions and Drug Mechanism

    PubMed Central

    2015-01-01

    Coordination between the N-terminal gate and the catalytic core of topoisomerase II allows the proper capture, cleavage, and transport of DNA during the catalytic cycle. Because the activities of these domains are tightly linked, it has been difficult to discern their individual contributions to enzyme–DNA interactions and drug mechanism. To further address the roles of these domains, we analyzed the activity of the catalytic core of human topoisomerase IIα. The catalytic core and the wild-type enzyme both maintained higher levels of cleavage with negatively (as compared to positively) supercoiled plasmid, indicating that the ability to distinguish supercoil handedness is embedded within the catalytic core. However, the catalytic core alone displayed little ability to cleave DNA substrates that did not intrinsically provide the enzyme with a transport segment (i.e., substrates that did not contain crossovers). Finally, in contrast to interfacial topoisomerase II poisons, covalent poisons did not enhance DNA cleavage mediated by the catalytic core. This distinction allowed us to further characterize the mechanism of etoposide quinone, a drug metabolite that functions primarily as a covalent poison. Etoposide quinone retained some ability to enhance DNA cleavage mediated by the catalytic core, indicating that it still can function as an interfacial poison. These results further define the distinct contributions of the N-terminal gate and the catalytic core to topoisomerase II function. The catalytic core senses the handedness of DNA supercoils during cleavage, while the N-terminal gate is critical for capturing the transport segment and for the activity of covalent poisons. PMID:25280269

  19. A phospholipid substrate molecule residing in the membrane surface mediates opening of the lid region in group IVA cytosolic phospholipase A2.

    PubMed

    Burke, John E; Hsu, Yuan-Hao; Deems, Raymond A; Li, Sheng; Woods, Virgil L; Dennis, Edward A

    2008-11-07

    The Group IVA (GIVA) phospholipase A(2) associates with natural membranes in response to an increase in intracellular Ca(2+) along with increases in certain lipid mediators. This enzyme associates with the membrane surface as well as binding a single phospholipid molecule in the active site for catalysis. Employing deuterium exchange mass spectrometry, we have identified the regions of the protein binding the lipid surface and conformational changes upon a single phospholipid binding in the absence of a lipid surface. Experiments were carried out using natural palmitoyl arachidonyl phosphatidylcholine vesicles with the intact GIVA enzyme as well as the isolated C2 and catalytic domains. Lipid binding produced changes in deuterium exchange in eight different regions of the protein. The regions with decreased exchange included Ca(2+) binding loop one, which has been proposed to penetrate the membrane surface, and a charged patch of residues, which may be important in interacting with the polar head groups of phospholipids. The regions with an increase in exchange are all located either in the hydrophobic core underneath the lid region or near the lid and hinge regions from 403 to 457. Using the GIVA phospholipase A(2) irreversible inhibitor methyl-arachidonyl fluorophosphonate, we were able to isolate structural changes caused only by pseudo-substrate binding. This produced results that were very similar to natural lipid binding in the presence of a lipid interface with the exception of the C2 domain and region 466-470. This implies that most of the changes seen in the catalytic domain are due to a substrate-mediated, not interface-mediated, lid opening, which exposes the active site to water. Finally experiments carried out with inhibitor plus phospholipid vesicles showed decreases at the C2 domain as well as charged residues on the putative membrane binding surface of the catalytic domain revealing the binding sites of the enzyme to the lipid surface.

  20. Translocation of the Catalytic Domain of Diphtheria Toxin across Planar Phospholipid Bilayers by Its Own T Domain

    NASA Astrophysics Data System (ADS)

    Oh, Kyoung Joon; Senzel, Lisa; Collier, R. John; Finkelstein, Alan

    1999-07-01

    The T domain of diphtheria toxin is known to participate in the pH-dependent translocation of the catalytic C domain of the toxin across the endosomal membrane, but how it does so, and whether cellular proteins are also required for this process, remain unknown. Here, we report results showing that the T domain alone is capable of translocating the entire C domain across model, planar phospholipid bilayers in the absence of other proteins. The T domain therefore contains the entire molecular machinery for mediating transfer of the catalytic domain of diphtheria toxin across membranes.

  1. Bio-catalytic nanocompartments for in situ production of glucose-6-phosphate.

    PubMed

    Lomora, M; Gunkel-Grabole, G; Mantri, S; Palivan, C G

    2017-08-29

    Cells are sophisticated biocatalytic systems driving a complex network of biochemical reactions. A bioinspired strategy to create advanced functional systems is to design confined spaces for complex enzymatic reactions by using a combination of synthetic polymer assemblies and natural cell components. Here, we developed bio-catalytic nanocompartments that contain phosphoglucomutase protected by a biomimetic polymer membrane, which was permeabilized for reactants through insertion of an engineered α-hemolysin pore protein. These bio-catalytic nanocompartments serve for production of glucose-6-phosphate, and thus possess great potential for applications in an incomplete glycolysis, pentose phosphate pathway, or in plant biological reactions.

  2. Electrostatic interactions in catalytic centers of F1-ATPase

    NASA Astrophysics Data System (ADS)

    Pogrebnaya, Alexandra F.; Romanovsky, Yury M.; Tikhonov, Alexander N.

    2003-10-01

    F1-ATPase is one of the most important enzymes of membrane bioenergetics. F1-ATPase is the constituent complex that provides the ATP formation from ADP and inorganic phosphate (Pi) at the expense of energy of electrochemical gradient of hydrogen ions generated across the energy transducing mitochondrial, chloroplast or bacterial membrane. F1-ATPase is a reversible molecular machine that can work as a proton pump due to energy released in the course of ATP hydrolysis (ATPase reaction). The unusual feature of this enzyme is that it operates as a rotary molecular motor. Recently, using the fluorescence microscopy method for the real time visualization of molecular mobility of individual molecules, it was demonstrated directly that the ATP hydrolysis by F1-ATPase is accompanied by unidirectional rotations of mobile subunits (rotor) of F1F0-ATP synthase. In this work, we calculated the contribution of electrostatic interactions between charged groups of a substrate (MgATP), products molecules (MgADP and Pi), and charged amino acid residuals of ATPase molecule to the energy changes associated with the substrate binding and their chemical transformations in the catalytic centers located at the interface of α and β subunits of the enzyme (oligomer complex α3β3γ of bovine mitochondria ATPase). A catalytic cycle of ATP hydrolysis considered in our work includes conformational changes of α and β subunits caused by unidirectional rotations of an eccentric γ subunit. The knowledge of energy characteristics and force field in catalytic center of an enzyme in different conformational states may be important for further simulation dynamic properties of ATP synthase complex.

  3. The nature of hot electrons generated by exothermic catalytic reactions

    NASA Astrophysics Data System (ADS)

    Nedrygailov, Ievgen I.; Park, Jeong Young

    2016-02-01

    We review recent progress in studies of the nature of hot electrons generated in metal nanoparticles and thin films on oxide supports and their role in heterogeneous catalysis. We show that the creation of hot electrons and their transport across the metal-oxide interface is an inherent component of energy dissipation accompanying catalytic and photocatalytic surface reactions. The intensity of hot electron flow is well correlated with turnover rates of corresponding reactions. We also show that controlling the flow of hot electrons crossing the interface can lead to the control of chemical reaction rates. Finally, we discuss perspectives of hot-electron-mediated surface chemistry that promise the capability to drive catalytic reactions with enhanced efficiency and selectivity through electron-mediated, non-thermal processes.

  4. Shape control of multi-material heterostructures for catalytic applications

    NASA Astrophysics Data System (ADS)

    Habas, Susan Ellen

    epitaxial overgrowth of palladium to give shape-controlled core-shell type nanocrystals with structure-sensitive catalytic properties. Incorporation of a lattice-mismatched metal such as gold, on the other hand, introduces an element of selectivity leading to the growth of anisotropic binary nanocrystals where both metals are exposed. The development of multi-component nanoparticles represents a new approach for creating smart materials, requiring controlled and selective growth of different materials on a single particle. In the final section, the concept of seeded overgrowth has been extended to include semiconductor nanostructures as seeds, introducing even greater potential for selective overgrowth of metals due to the unique chemical composition of the different crystallographic facets. Platinum and related binary metals were grown with high selectivity on the tips of cadmium sulfide nanorods for catalytic and energy applications.

  5. Microscopic Simulation of Membrane Molecule Diffusion on Corralled Membrane Surfaces☆

    PubMed Central

    Niehaus, Anne Marie S.; Vlachos, Dionisios G.; Edwards, Jeremy S.; Plechac, Petr; Tribe, Roger

    2008-01-01

    The current understanding of how receptors diffuse and cluster in the plasma membrane is limited. Data from single-particle tracking and laser tweezer experiments have suggested that membrane molecule diffusion is affected by the presence of barriers dividing the membrane into corrals. Here, we have developed a stochastic spatial model to simulate the effect of corrals on the diffusion of molecules in the plasma membrane. The results of this simulation confirm that a fence barrier (the ratio of the transition probability for diffusion across a boundary to that within a corral) on the order of 103–104 recreates the experimentally measured difference in diffusivity between artificial and natural plasma membranes. An expression for the macroscopic diffusivity of receptors on corralled membranes is derived to analyze the effects of the corral parameters on diffusion rate. We also examine whether the lattice model is an appropriate description of the plasma membrane and look at three different sets of boundary conditions that describe diffusion over the barriers and whether diffusion events on the plasma membrane may occur with a physically relevant length scale. Finally, we show that to observe anomalous (two-timescale) diffusion, one needs high temporal (microsecond) resolution along with sufficiently long (more than milliseconds) trajectories. PMID:17993499

  6. Favorable effect of in-situ generated platinum in the membrane on fuel cell membrane durability

    NASA Astrophysics Data System (ADS)

    Macauley, Natalia; Wong, Ka Hung; Watson, Mark; Kjeang, Erik

    2015-12-01

    The overall lifetime of polymer electrolyte fuel cells is often determined by the membrane durability. Platinum, which may dissolve from the catalyst layers during fuel cell operation and deposit in the membrane, has been shown to have both positive and negative effects on membrane stability. In the present work, we analyze what specific conditions are required in order to reach a favorable, membrane stabilizing effect with the controlled use of platinum in the membrane. Using accelerated membrane durability testing, field operated membrane samples, and electron microscopy, we demonstrate that a high platinum concentration with specific particle shapes and sizes is essential for enhanced membrane stability. Specifically, star shaped and dendritic particles with high particle density and high surface area are shown to be preferable. These particles contain high levels of Pt(111) and are expected to have high catalytic activity toward peroxide quenching and crossover gas consumption, thereby mitigating chemical membrane degradation. On the other hand, small, dispersed cubic particles are found to have no effect or the opposite, negative effect on membrane stability.

  7. Parameters influencing zeolite incorporation in PDMS membranes

    SciTech Connect

    Vankelecom, I.F.J.; Scheppers, E.; Heus, R.; Uytterhoeven, J.B. )

    1994-11-24

    The incorporation of several types of zeolite in PDMS membranes is studied, by measuring the tensile strength, xylene sorption, and density of the membranes. The zeolite is shown to be involved in the cross-linking of the membrane. The interaction between the PDMS matrix and the zeolites results in reinforced membranes in the case of zeolite Y. The parameters influencing the dispersion of the zeolite in the membrane are investigated, as well as several aspects of the preparation method. Finally, the idea of cross-linking is applied to explain the results of water/ethanol pervaporation. 25 refs., 9 figs., 4 tabs.

  8. Dynamic Responsive Systems for Catalytic Function.

    PubMed

    Vlatković, Matea; Collins, Beatrice S L; Feringa, Ben L

    2016-11-21

    Responsive systems have recently gained much interest in the scientific community in attempts to mimic dynamic functions in biological systems. One of the fascinating potential applications of responsive systems lies in catalysis. Inspired by nature, novel responsive catalytic systems have been built that show analogy with allosteric regulation of enzymes. The design of responsive catalytic systems allows control of catalytic activity and selectivity. In this Review, advances in the field over the last four decades are discussed and a comparison is made amongst the dynamic responsive systems based on the principles underlying their catalytic mechanisms. The catalyst systems are sorted according to the triggers used to achieve control of the catalytic activity and the distinct catalytic reactions illustrated. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Tubular hydrogen permeable metal foil membrane and method of fabrication

    DOEpatents

    Paglieri, Stephen N.; Birdsell, Stephen A.; Barbero, Robert S.; Snow, Ronny C.; Smith, Frank M.

    2006-04-04

    A tubular hydrogen permeable metal membrane and fabrication process comprises obtaining a metal alloy foil having two surfaces, coating the surfaces with a metal or metal alloy catalytic layer to produce a hydrogen permeable metal membrane, sizing the membrane into a sheet with two long edges, wrapping the membrane around an elongated expandable rod with the two long edges aligned and overlapping to facilitate welding of the two together, placing the foil wrapped rod into a surrounding fixture housing with the two aligned and overlapping foil edges accessible through an elongated aperture in the surrounding fixture housing, expanding the elongated expandable rod within the surrounding fixture housing to tighten the foil about the expanded rod, welding the two long overlapping foil edges to one another generating a tubular membrane, and removing the tubular membrane from within the surrounding fixture housing and the expandable rod from with the tubular membrane.

  10. Interaction of peptides with cell membranes: insights from molecular modeling

    NASA Astrophysics Data System (ADS)

    Li, Zhen-lu; Ding, Hong-ming; Ma, Yu-qiang

    2016-03-01

    The investigation of the interaction of peptides with cell membranes is the focus of active research. It can enhance the understanding of basic membrane functions such as membrane transport, fusion, and signaling processes, and it may shed light on potential applications of peptides in biomedicine. In this review, we will present current advances in computational studies on the interaction of different types of peptides with the cell membrane. Depending on the properties of the peptide, membrane, and external environment, the peptide-membrane interaction shows a variety of different forms. Here, on the basis of recent computational progress, we will discuss how different peptides could initiate membrane pores, translocate across the membrane, induce membrane endocytosis, produce membrane curvature, form fibrils on the membrane surface, as well as interact with functional membrane proteins. Finally, we will present a conclusion summarizing recent progress and providing some specific insights into future developments in this field.

  11. An update on catalytic reforming

    SciTech Connect

    Wei, D.H.; Moser, M.D.; Haizmann, R.S.

    1996-10-01

    The UOP Platforming process is a catalytic reforming process in widespread use throughout the petroleum and petrochemical industries. Since the first unit went onstream in 1949, the process has become a standard feature in refineries worldwide. Over the years, significant improvements have been made in process catalysts and process design. The most recent improvement is the combination of a catalyst called R-72 with a new patented flow scheme, R-72 staged loading, which gives significantly higher yields and provides increased catalyst stability. In this article, the authors describe two types of Platforming processes and the new R-72 staged loading scheme.

  12. Catalytic Decoupling of Quantum Information.

    PubMed

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric; Renner, Renato; Christandl, Matthias

    2017-02-24

    The decoupling technique is a fundamental tool in quantum information theory with applications ranging from thermodynamics to many-body physics and black hole radiation whereby a quantum system is decoupled from another one by discarding an appropriately chosen part of it. Here, we introduce catalytic decoupling, i.e., decoupling with the help of an independent system. Thereby, we remove a restriction on the standard decoupling notion and present a tight characterization in terms of the max-mutual information. The novel notion unifies various tasks and leads to a resource theory of decoupling.

  13. Molecular catalytic coal liquid conversion

    SciTech Connect

    Stock, L.M.; Yang, Shiyong

    1995-12-31

    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  14. Catalytic cracking of heavy oils

    SciTech Connect

    Otterstedt, J.E.; Gevert, B.; Sterte, J. )

    1987-08-01

    Of the many factors which influence product yields in a fluid catalytic cracker, the feed stock quality and the catalyst composition are of particular interest as they can be controlled only to a limited extent by the refiner. In the past decade there has been a trend towards using heavier feedstocks in the FCC-unit, which is expected to continue in the foreseeable future. It is therefore important to study how molecular types, characteristic not only of heavy petroleum oil but also of e.g. coal liquid, shale oil and biomass oil, respond to cracking over catalysts of different compositions.

  15. Catalytic Organometallic Reactions of Ammonia

    PubMed Central

    Klinkenberg, Jessica L.

    2012-01-01

    Until recently, ammonia had rarely succumbed to catalytic transformations with homogeneous catalysts, and the development of such reactions that are selective for the formation of single products under mild conditions has encountered numerous challenges. However, recently developed catalysts have allowed several classes of reactions to create products with nitrogen-containing functional groups from ammonia. These reactions include hydroaminomethylation, reductive amination, alkylation, allylic substitution, hydroamination, and cross-coupling. This Minireview describes examples of these processes and the factors that control catalyst activity and selectivity. PMID:20857466

  16. A sustainable catalytic pyrrole synthesis

    NASA Astrophysics Data System (ADS)

    Michlik, Stefan; Kempe, Rhett

    2013-02-01

    The pyrrole heterocycle is a prominent chemical motif and is found widely in natural products, drugs, catalysts and advanced materials. Here we introduce a sustainable iridium-catalysed pyrrole synthesis in which secondary alcohols and amino alcohols are deoxygenated and linked selectively via the formation of C-N and C-C bonds. Two equivalents of hydrogen gas are eliminated in the course of the reaction, and alcohols based entirely on renewable resources can be used as starting materials. The catalytic synthesis protocol tolerates a large variety of functional groups, which includes olefins, chlorides, bromides, organometallic moieties, amines and hydroxyl groups. We have developed a catalyst that operates efficiently under mild conditions.

  17. Metamaterial membranes

    NASA Astrophysics Data System (ADS)

    Restrepo-Flórez, Juan Manuel; Maldovan, Martin

    2017-01-01

    We introduce a new class of metamaterial device to achieve separation of compounds by using coordinate transformations and metamaterial theory. By rationally designing the spatial anisotropy for mass diffusion, we simultaneously concentrate different compounds in different spatial locations, leading to separation of mixtures across a metamaterial membrane. The separation of mixtures into their constituent compounds is critically important in biophysics, biomedical, and chemical applications. We present a practical case where a mixture of oxygen and nitrogen diffusing through a polymeric planar matrix is separated. This work opens doors to new paradigms in membrane separations via coordinate transformations and metamaterials by introducing novel properties and unconventional mass diffusion phenomena.

  18. Mechanisms and Kinetics of Catalytic Reactions

    DTIC Science & Technology

    1990-08-01

    CHEMICAL RESEARCH, r- DEVELOPMENT 5 N ENGINEERING CRDE-R-084 "" CENTER CENER(GC-TR-1728-008) ’ 04 N MECHANISMS AND KINETICS OF CATALYTIC REACTIONS Q...and Kinetics of Catalytic Reactions &AUTHOR(S) Garlick, Stephanie M. 7. PERFORMING ORGANIZATION NAME(S) AND ADORESS(ES) . PERFORMING ORGANIZATION...Tables........................87 vi MECHANISMS AND KINETICS OF CATALYTIC REACTIONS 1. INTRODUCTION The hydrolysis of phosphate esters in microemulsion

  19. Metal-organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations.

    PubMed

    Chughtai, Adeel H; Ahmad, Nazir; Younus, Hussein A; Laypkov, A; Verpoort, Francis

    2015-10-07

    Novel catalytic materials are highly demanded to perform a variety of catalytic organic reactions. MOFs combine the benefits of heterogeneous catalysis like easy post reaction separation, catalyst reusability, high stability and homogeneous catalysis such as high efficiency, selectivity, controllability and mild reaction conditions. The possible organization of active centers like metallic nodes, organic linkers, and their chemical synthetic functionalization on the nanoscale shows potential to build up MOFs particularly modified for catalytic challenges. In this review, we have summarized the recent research progress in heterogeneous catalysis by MOFs and their catalytic behavior in various organic reactions, highlighting the key features of MOFs as catalysts based on the active sites in the framework. Examples of their post functionalization, inclusion of active guest species and metal nanoparticles have been discussed. Finally, the use of MOFs as catalysts for asymmetric heterogeneous catalysis and stability of MOFs has been presented as separate sections.

  20. Installation Restoration of Rocky Mountain Arsenal, Pilot Containment Operations, Final Environmental Impact Statement, Part 1.

    DTIC Science & Technology

    1977-02-01

    causing crop damage. b. As a result of these actions, Reservoir F was constructed. The reservoir was- lined and sealed by laying a catalytic air- blown ... asphalt membrane over the su2rface and then protecting the membrane by covering it with a foot of soil. When Reservoir F was completed in early 1957

  1. Ternary structure reveals mechanism of a membrane diacylglycerol kinase

    SciTech Connect

    Li, Dianfan; Stansfeld, Phillip J.; Sansom, Mark S. P.; Keogh, Aaron; Vogeley, Lutz; Howe, Nicole; Lyons, Joseph A.; Aragao, David; Fromme, Petra; Fromme, Raimund; Basu, Shibom; Grotjohann, Ingo; Kupitz, Christopher; Rendek, Kimberley; Weierstall, Uwe; Zatsepin, Nadia A.; Cherezov, Vadim; Liu, Wei; Bandaru, Sateesh; English, Niall J.; Gati, Cornelius; Barty, Anton; Yefanov, Oleksandr; Chapman, Henry N.; Diederichs, Kay; Messerschmidt, Marc; Boutet, Sébastien; Williams, Garth J.; Marvin Seibert, M.; Caffrey, Martin

    2015-12-17

    Diacylglycerol kinase catalyses the ATP-dependent conversion of diacylglycerol to phosphatidic acid in the plasma membrane of Escherichia coli. The small size of this integral membrane trimer, which has 121 residues per subunit, means that available protein must be used economically to craft three catalytic and substrate-binding sites centred about the membrane/cytosol interface. How nature has accomplished this extraordinary feat is revealed here in a crystal structure of the kinase captured as a ternary complex with bound lipid substrate and an ATP analogue. Residues, identified as essential for activity by mutagenesis, decorate the active site and are rationalized by the ternary structure. The γ-phosphate of the ATP analogue is positioned for direct transfer to the primary hydroxyl of the lipid whose acyl chain is in the membrane. A catalytic mechanism for this unique enzyme is proposed. As a result, the active site architecture shows clear evidence of having arisen by convergent evolution.

  2. Ternary structure reveals mechanism of a membrane diacylglycerol kinase

    NASA Astrophysics Data System (ADS)

    Li, Dianfan; Stansfeld, Phillip J.; Sansom, Mark S. P.; Keogh, Aaron; Vogeley, Lutz; Howe, Nicole; Lyons, Joseph A.; Aragao, David; Fromme, Petra; Fromme, Raimund; Basu, Shibom; Grotjohann, Ingo; Kupitz, Christopher; Rendek, Kimberley; Weierstall, Uwe; Zatsepin, Nadia A.; Cherezov, Vadim; Liu, Wei; Bandaru, Sateesh; English, Niall J.; Gati, Cornelius; Barty, Anton; Yefanov, Oleksandr; Chapman, Henry N.; Diederichs, Kay; Messerschmidt, Marc; Boutet, Sébastien; Williams, Garth J.; Marvin Seibert, M.; Caffrey, Martin

    2015-12-01

    Diacylglycerol kinase catalyses the ATP-dependent conversion of diacylglycerol to phosphatidic acid in the plasma membrane of Escherichia coli. The small size of this integral membrane trimer, which has 121 residues per subunit, means that available protein must be used economically to craft three catalytic and substrate-binding sites centred about the membrane/cytosol interface. How nature has accomplished this extraordinary feat is revealed here in a crystal structure of the kinase captured as a ternary complex with bound lipid substrate and an ATP analogue. Residues, identified as essential for activity by mutagenesis, decorate the active site and are rationalized by the ternary structure. The γ-phosphate of the ATP analogue is positioned for direct transfer to the primary hydroxyl of the lipid whose acyl chain is in the membrane. A catalytic mechanism for this unique enzyme is proposed. The active site architecture shows clear evidence of having arisen by convergent evolution.

  3. Ternary structure reveals mechanism of a membrane diacylglycerol kinase

    PubMed Central

    Li, Dianfan; Stansfeld, Phillip J.; Sansom, Mark S. P.; Keogh, Aaron; Vogeley, Lutz; Howe, Nicole; Lyons, Joseph A.; Aragao, David; Fromme, Petra; Fromme, Raimund; Basu, Shibom; Grotjohann, Ingo; Kupitz, Christopher; Rendek, Kimberley; Weierstall, Uwe; Zatsepin, Nadia A.; Cherezov, Vadim; Liu, Wei; Bandaru, Sateesh; English, Niall J.; Gati, Cornelius; Barty, Anton; Yefanov, Oleksandr; Chapman, Henry N.; Diederichs, Kay; Messerschmidt, Marc; Boutet, Sébastien; Williams, Garth J.; Marvin Seibert, M.; Caffrey, Martin

    2015-01-01

    Diacylglycerol kinase catalyses the ATP-dependent conversion of diacylglycerol to phosphatidic acid in the plasma membrane of Escherichia coli. The small size of this integral membrane trimer, which has 121 residues per subunit, means that available protein must be used economically to craft three catalytic and substrate-binding sites centred about the membrane/cytosol interface. How nature has accomplished this extraordinary feat is revealed here in a crystal structure of the kinase captured as a ternary complex with bound lipid substrate and an ATP analogue. Residues, identified as essential for activity by mutagenesis, decorate the active site and are rationalized by the ternary structure. The γ-phosphate of the ATP analogue is positioned for direct transfer to the primary hydroxyl of the lipid whose acyl chain is in the membrane. A catalytic mechanism for this unique enzyme is proposed. The active site architecture shows clear evidence of having arisen by convergent evolution. PMID:26673816

  4. Multidimensional Classification of Dialysis Membranes.

    PubMed

    Ronco, Claudio; Neri, Mauro; Lorenzin, Anna; Garzotto, Francesco; Clark, William R

    2017-01-01

    Hemodialysis is a process of mass separation by a semipermeable membrane, utilized to cleanse blood from waste products retained in case of kidney failure. Traditionally, dialysis membranes have been classified based on composition and hydraulic conductance, creating the net differentiation between cellulosic versus non-cellulosic on one hand and low-flux versus high-flux on the other. With the evolution of biomaterials and improved spinning technology, new membranes have been introduced in the market with specific characteristics and refined individual properties. Therefore, we should consider new parameters to classify dialysis membranes including polymer blending, surface functionalization, molecular weight cut-off (MWCO), hydrophilic/hydrophobic properties, thickness and architecture, adsorption capacity, and electric potential. All these parameters may be utilized to characterize a membrane alone or in combination. Recently, a new parameter has been identified as an important element to characterize a new class of membranes. Beyond the classic MWCO describing the molecular weight at which the sieving value in pure convection = 0.1, the molecular weight retention onset (MWRO) is a new parameter that defines membrane sieving properties. The retention onset value is the molecular weight at which the sieving value = 0.9. The relationship between MWCO and MWRO describes the steepness of the sieving curve and the membrane pore size distribution with important consequences on the final mass separation process and solute removal. © 2017 S. Karger AG, Basel.

  5. Membrane curvature at a glance

    PubMed Central

    McMahon, Harvey T.; Boucrot, Emmanuel

    2015-01-01

    ABSTRACT Membrane curvature is an important parameter in defining the morphology of cells, organelles and local membrane subdomains. Transport intermediates have simpler shapes, being either spheres or tubules. The generation and maintenance of curvature is of central importance for maintaining trafficking and cellular functions. It is possible that local shapes in complex membranes could help to define local subregions. In this Cell Science at a Glance article and accompanying poster, we summarize how generating, sensing and maintaining high local membrane curvature is an active process that is mediated and controlled by specialized proteins using general mechanisms: (i) changes in lipid composition and asymmetry, (ii) partitioning of shaped transmembrane domains of integral membrane proteins or protein or domain crowding, (iii) reversible insertion of hydrophobic protein motifs, (iv) nanoscopic scaffolding by oligomerized hydrophilic protein domains and, finally, (v) macroscopic scaffolding by the cytoskeleton with forces generated by polymerization and by molecular motors. We also summarize some of the discoveries about the functions of membrane curvature, where in addition to providing cell or organelle shape, local curvature can affect processes like membrane scission and fusion as well as protein concentration and enzyme activation on membranes. PMID:25774051

  6. Pore dynamics in lipid membranes

    NASA Astrophysics Data System (ADS)

    Gozen, I.; Dommersnes, P.

    2014-09-01

    Transient circular pores can open in plasma membrane of cells due to mechanical stress, and failure to repair such pores lead to cell death. Similar pores in the form of defects also exist among smectic membranes, such as in myelin sheaths or mitochondrial membranes. The formation and growth of membrane defects are associated with diseases, for example multiple sclerosis. A deeper understanding of membrane pore dynamics can provide a more refined picture of membrane integrity-related disease development, and possibly also treatment options and strategies. Pore dynamics is also of great importance regarding healthcare applications such as drug delivery, gene or as recently been implied, cancer therapy. The dynamics of pores significantly differ in stacks which are confined in 2D compared to those in cells or vesicles. In this short review, we will summarize the dynamics of different types of pores that can be observed in biological membranes, which include circular transient, fusion and hemi-fusion pores. We will dedicate a section to floral and fractal pores which were discovered a few years ago and have highly peculiar characteristics. Finally, we will discuss the repair mechanisms of large area pores in conjunction with the current cell membrane repair hypotheses.

  7. Catalytic microrotor driven by geometrical asymmetry.

    PubMed

    Yang, Mingcheng; Ripoll, Marisol; Chen, Ke

    2015-02-07

    An asymmetric gear with homogeneous surface properties is, here, presented as a prototype to fabricate catalytic microrotors. The driving torque arises from the diffusiophoretic effect induced by the concentration gradients generated by catalytic chemical reactions at the gear surface. This torque produces a spontaneous and unidirectional rotation of the asymmetric gear. By means of mesoscopic simulations, we prove and characterize this scenario. The gear rotational velocity is determined by the gear-solvent interactions, the gear geometry, the solvent viscosity, and the catalytic reaction ratio. Our work presents a simple way to design self-propelled microrotors, alternative to existing catalytic bi-component, or thermophoretic ones.

  8. Catalytic microrotor driven by geometrical asymmetry

    NASA Astrophysics Data System (ADS)

    Yang, Mingcheng; Ripoll, Marisol; Chen, Ke

    2015-02-01

    An asymmetric gear with homogeneous surface properties is, here, presented as a prototype to fabricate catalytic microrotors. The driving torque arises from the diffusiophoretic effect induced by the concentration gradients generated by catalytic chemical reactions at the gear surface. This torque produces a spontaneous and unidirectional rotation of the asymmetric gear. By means of mesoscopic simulations, we prove and characterize this scenario. The gear rotational velocity is determined by the gear-solvent interactions, the gear geometry, the solvent viscosity, and the catalytic reaction ratio. Our work presents a simple way to design self-propelled microrotors, alternative to existing catalytic bi-component, or thermophoretic ones.

  9. Catalytic oxidizers and Title V requirements

    SciTech Connect

    Uberoi, M.; Rach, S.E.

    1999-07-01

    Catalytic oxidizers have been used to reduce VOC emissions from various industries including printing, chemical, paint, coatings, etc. A catalytic oxidizer uses a catalyst to reduce the operating temperature for combustion to approximately 600 F, which is substantially lower than thermal oxidation unit. Title V requirements have renewed the debate on the best methods to assure compliance of catalytic oxidizers, with some suggesting the need for continuous emission monitoring equipment. This paper will discuss the various aspects of catalytic oxidation and consider options such as monitoring inlet/outlet temperatures, delta T across the catalyst, periodic laboratory testing of catalyst samples, and preventive maintenance procedures as means of assuring continuous compliance.

  10. Membrane Packing Problems: A short Review on computational Membrane Modeling Methods and Tools

    PubMed Central

    Sommer, Björn

    2013-01-01

    The use of model membranes is currently part of the daily workflow for many biochemical and biophysical disciplines. These membranes are used to analyze the behavior of small substances, to simulate transport processes, to study the structure of macromolecules or for illustrative purposes. But, how can these membrane structures be generated? This mini review discusses a number of ways to obtain these structures. First, the problem will be formulated as the Membrane Packing Problem. It will be shown that the theoretical problem of placing proteins and lipids onto a membrane area differ significantly. Thus, two sub-problems will be defined and discussed. Then, different – partly historical – membrane modeling methods will be introduced. And finally, membrane modeling tools will be evaluated which are able to semi-automatically generate these model membranes and thus, drastically accelerate and simplify the membrane generation process. The mini review concludes with advice about which tool is appropriate for which application case. PMID:24688707

  11. Catalytic conversion of light alkanes

    SciTech Connect

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  12. Evolution of a Catalytic Mechanism

    PubMed Central

    Rauwerdink, Alissa; Lunzer, Mark; Devamani, Titu; Jones, Bryan; Mooney, Joanna; Zhang, Zhi-Jun; Xu, Jian-He; Kazlauskas, Romas J.; Dean, Antony M.

    2016-01-01

    The means by which superfamilies of specialized enzymes arise by gene duplication and functional divergence are poorly understood. The escape from adaptive conflict hypothesis, which posits multiple copies of a gene encoding a primitive inefficient and highly promiscuous generalist ancestor, receives support from experiments showing that resurrected ancestral enzymes are indeed more substrate-promiscuous than their modern descendants. Here, we provide evidence in support of an alternative model, the innovation–amplification–divergence hypothesis, which posits a single-copied ancestor as efficient and specific as any modern enzyme. We argue that the catalytic mechanisms of plant esterases and descendent acetone cyanohydrin lyases are incompatible with each other (e.g., the reactive substrate carbonyl must bind in opposite orientations in the active site). We then show that resurrected ancestral plant esterases are as catalytically specific as modern esterases, that the ancestor of modern acetone cyanohydrin lyases was itself only very weakly promiscuous, and that improvements in lyase activity came at the expense of esterase activity. These observations support the innovation–amplification–divergence hypothesis, in which an ancestor gains a weak promiscuous activity that is improved by selection at the expense of the ancestral activity, and not the escape from adaptive conflict in which an inefficient generalist ancestral enzyme steadily loses promiscuity throughout the transition to a highly active specialized modern enzyme. PMID:26681154

  13. Membrane magic

    SciTech Connect

    Buecker, B.

    2005-09-01

    The Kansas Power and Light Co.'s La Cyne generating station has found success with membrane filtration water pretreatment technology. The article recounts the process followed in late 2004 to install a Pall Aria 4 microfilter in Unit 1 makeup water system at the plant to produce cleaner water for reverse osmosis feed. 2 figs., 2 photos.

  14. Glycerol Production and Transformation: A Critical Review with Particular Emphasis on Glycerol Reforming Reaction for Producing Hydrogen in Conventional and Membrane Reactors.

    PubMed

    Bagnato, Giuseppe; Iulianelli, Adolfo; Sanna, Aimaro; Basile, Angelo

    2017-03-23

    Glycerol represents an emerging renewable bio-derived feedstock, which could be used as a source for producing hydrogen through steam reforming reaction. In this review, the state-of-the-art about glycerol production processes is reviewed, with particular focus on glycerol reforming reactions and on the main catalysts under development. Furthermore, the use of membrane catalytic reactors instead of conventional reactors for steam reforming is discussed. Finally, the review describes the utilization of the Pd-based membrane reactor technology, pointing out the ability of these alternative fuel processors to simultaneously extract high purity hydrogen and enhance the whole performances of the reaction system in terms of glycerol conversion and hydrogen yield.

  15. Glycerol Production and Transformation: A Critical Review with Particular Emphasis on Glycerol Reforming Reaction for Producing Hydrogen in Conventional and Membrane Reactors

    PubMed Central

    Bagnato, Giuseppe; Iulianelli, Adolfo; Sanna, Aimaro; Basile, Angelo

    2017-01-01

    Glycerol represents an emerging renewable bio-derived feedstock, which could be used as a source for producing hydrogen through steam reforming reaction. In this review, the state-of-the-art about glycerol production processes is reviewed, with particular focus on glycerol reforming reactions and on the main catalysts under development. Furthermore, the use of membrane catalytic reactors instead of conventional reactors for steam reforming is discussed. Finally, the review describes the utilization of the Pd-based membrane reactor technology, pointing out the ability of these alternative fuel processors to simultaneously extract high purity hydrogen and enhance the whole performances of the reaction system in terms of glycerol conversion and hydrogen yield. PMID:28333121

  16. Oxygen Transport Ceramic Membranes

    SciTech Connect

    S. Bandopadhyay; N. Nagabhushana; Thomas W. Eagar; Harold R. Larson; Raymundo Arroyave; X.-D Zhou; Y.-W. Shin; H.U. Anderson; Nigel Browning; Alan Jacobson; C.A. Mims

    2003-11-01

    The present quarterly report describes some of the initial studies on newer compositions and also includes newer approaches to address various materials issues such as in metal-ceramic sealing. The current quarter's research has also focused on developing a comprehensive reliability model for predicting the structural behavior of the membranes in realistic conditions. In parallel to industry provided compositions, models membranes have been evaluated in varying environment. Of importance is the behavior of flaws and generation of new flaws aiding in fracture. Fracture mechanics parameters such as crack tip stresses are generated to characterize the influence of environment. Room temperature slow crack growth studies have also been initiated in industry provided compositions. The electrical conductivity and defect chemistry of an A site deficient compound (La{sub 0.55}Sr{sub 0.35}FeO{sub 3}) was studied. A higher conductivity was observed for La{sub 0.55}Sr{sub 0.35}FeO{sub 3} than that of La{sub 0.60}Sr{sub 0.40}FeO{sub 3} and La{sub 0.80}Sr{sub 0.20}FeO{sub 3}. Defect chemistry analysis showed that it was primarily contributed by a higher carrier concentration in La{sub 0.55}Sr{sub 0.35}FeO{sub 3}. Moreover, the ability for oxygen vacancy generation is much higher in La{sub 0.55}Sr{sub 0.35}FeO{sub 3} as well, which indicates a lower bonding strength between Fe-O and a possible higher catalytic activity for La{sub 0.55}Sr{sub 0.35}FeO{sub 3}. The program continued to investigate the thermodynamic properties (stability and phase separation behavior) and total conductivity of prototype membrane materials. The data are needed together with the kinetic information to develop a complete model for the membrane transport. Previous report listed initial measurements on a sample of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-x} prepared in-house by Praxair. Subsequently, a second sample of powder from a larger batch of sample were characterized and compared with

  17. Final Report

    SciTech Connect

    Stinis, Panos

    2016-08-07

    This is the final report for the work conducted at the University of Minnesota (during the period 12/01/12-09/18/14) by PI Panos Stinis as part of the "Collaboratory on Mathematics for Mesoscopic Modeling of Materials" (CM4). CM4 is a multi-institution DOE-funded project whose aim is to conduct basic and applied research in the emerging field of mesoscopic modeling of materials.

  18. Final Report

    SciTech Connect

    Marchant, Gary E.

    2013-04-23

    This is the final report of a two year project entitled "Governing Nanotechnology Risks and Benefits in the Transition to Regulation: Innovative Public and Private Approaches." This project examined the role of new governance or "soft law" mechanisms such as codes of conduct, voluntary programs and partnership agreements to manage the risks of emerging technologies such as nanotechnology. A series of published or in publication papers and book chapters are attached.

  19. Final Report

    SciTech Connect

    R. Paul Drake

    2001-11-30

    This final report describes work involving 22 investigators from 11 institutions to explore the dynamics present in supernova explosions by means of experiments on the Omega laser. The specific experiments emphasized involved the unstable expansion of a spherical capsule and the coupling of perturbations at a first interface to a second interface by means of a strong shock. Both effects are present in supernovae. The experiments were performed at Omega and the computer simulations were undertaken at several institutions. B139

  20. Preparing two-dimensional nano-catalytic combustion patterns using direct inkjet printing

    NASA Astrophysics Data System (ADS)

    Luo, Xi; Zeng, Zhigang; Wang, Xiaohong; Xiao, Jinhua; Gan, Zhongxue; Wu, Hao; Hu, Zhiyu

    2014-12-01

    Two-dimensional catalytic combustion patterns, which can be used as heat source in micro-nano scale MEMS devices such as gas sensor and micro-generator, are fabricated by inkjet printing (IJP). The performances of the catalytic patterns are evaluated by both traditional catalytic activity measurement and infrared thermography (IR) camera. Results show that ultra-low (0.014 mg cm-2) loading and high utilizing (34,710 mW mg-1) of Pt catalysts can be achieved by inkjet printing method. Spontaneous combustion is also observed for the printed Pt/Al2O3 powder membrane at rather low initiation temperature and small scale. The IR camera analysis indicates the uniform temperature distribution and rapid temperature response of the micro-patterned catalyst surface. With the advantages of the inkjet printing, this new direct-write method would, in principle, open up possibilities of these special catalyst patterns serving as micro energy sources for MEMS applications.

  1. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    SciTech Connect

    Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

    1998-04-01

    The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

  2. Studies on the Orientation of Cyclic AMP-Dependent Protein Kinase in Human Erythrocyte Membranes

    PubMed Central

    Rubin, Charles S.; Rosenfeld, Robert D.; Rosen, Ora M.

    1973-01-01

    The topographic location of cyclic AMP-dependent protein kinase has been studied in preparations of permeable and sealed membranes derived from human erythrocytes. Both the catalytic and cyclic AMP-binding components of protein kinase are localized on the inner, cytoplasmic, surface of the plasma membrane. PMID:4359486

  3. Catalytic Leadership: Strategies for an Interconnected World.

    ERIC Educational Resources Information Center

    Luke, Jeffrey S.

    A catalytic leader brings together diverse individuals from multiple agencies to address intractable public problems. Strategies for promoting catalytic leadership are explored. The book opens with a review of the problems facing public leaders, emphasizing the complexity and interconnectedness of problems in the public sphere. The book highlights…

  4. Catalytic Leadership: Strategies for an Interconnected World.

    ERIC Educational Resources Information Center

    Luke, Jeffrey S.

    A catalytic leader brings together diverse individuals from multiple agencies to address intractable public problems. Strategies for promoting catalytic leadership are explored. The book opens with a review of the problems facing public leaders, emphasizing the complexity and interconnectedness of problems in the public sphere. The book highlights…

  5. Catalytic Radical Domino Reactions in Organic Synthesis.

    PubMed

    Sebren, Leanne J; Devery, James J; Stephenson, Corey R J

    2014-02-07

    Catalytic radical-based domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing atom- and step-economical methods to complex molecules. Intricate combinations of radical, cationic, anionic, oxidative/reductive, and transition metal mechanistic steps result in cyclizations, additions, fragmentations, ring-expansions, and rearrangements. This Perspective summarizes recent developments in the field of catalytic domino processes.

  6. Effect of hierarchical porosity and phosphorus modification on the catalytic properties of zeolite Y

    NASA Astrophysics Data System (ADS)

    Li, Wenlin; Zheng, Jinyu; Luo, Yibin; Da, Zhijian

    2016-09-01

    The zeolite Y is considered as a leading catalyst for FCC industry. The acidity and porosity modification play important roles in determining the final catalytic properties of zeolite Y. The alkaline treatment of zeolite Y by dealumination and alkaline treatment with NaOH and NaOH&TBPH was investigated. The zeolites were characterized by X-ray diffraction, low-temperature adsorption of nitrogen, transmission electron microscope, NMR, NH3-TPD and IR study of acidity. Accordingly, the hierarchical porosity and acidity property were discussed systematically. Finally, the catalytic performance of the zeolites Y was evaluated in the cracking of 1,3,5-TIPB. It was found that desilication with NaOH&TBPH ensured the more uniform intracrystalline mesoporosity with higher microporosity, while preserving higher B/L ratio and moderate Brønsted acidities resulting in catalysts with the most appropriated acidity and then with better catalytic performance.

  7. Catalytic reactor with improved burner

    DOEpatents

    Faitani, Joseph J.; Austin, George W.; Chase, Terry J.; Suljak, George T.; Misage, Robert J.

    1981-01-01

    To more uniformly distribute heat to the plurality of catalyst tubes in a catalytic reaction furnace, the burner disposed in the furnace above the tops of the tubes includes concentric primary and secondary annular fuel and air outlets. The fuel-air mixture from the primary outlet is directed towards the tubes adjacent the furnace wall, and the burning secondary fuel-air mixture is directed horizontally from the secondary outlet and a portion thereof is deflected downwardly by a slotted baffle toward the tubes in the center of the furnace while the remaining portion passes through the slotted baffle to another baffle disposed radially outwardly therefrom which deflects it downwardly in the vicinity of the tubes between those in the center and those near the wall of the furnace.

  8. APPARATUS FOR CATALYTICALLY COMBINING GASES

    DOEpatents

    Busey, H.M.

    1958-08-12

    A convection type recombiner is described for catalytically recombining hydrogen and oxygen which have been radiolytically decomposed in an aqueous homogeneous nuclear reactor. The device is so designed that the energy of recombination is used to circulate the gas mixture over the catalyst. The device consists of a vertical cylinder having baffles at its lower enda above these coarse screens having platinum and alumina pellets cemented thereon, and an annular passage for the return of recombined, condensed water to the reactor moderator system. This devicea having no moving parts, provides a simple and efficient means of removing the danger of accumulated hot radioactive, explosive gases, and restoring them to the moderator system for reuse.

  9. Catalytic cartridge SO3 decomposer

    SciTech Connect

    Galloway, T.R.

    1982-05-25

    A catalytic cartridge surrounding a heat pipe driven by a heat source is utilized as a SO3 decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a crossflow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO3 gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube surrounding the heat pipe. In the axialflow cartridge, so3 gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and surrounding the heat pipe. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety.

  10. Non-catalytic recuperative reformer

    SciTech Connect

    Khinkis, Mark J.; Kozlov, Aleksandr P.; Kurek, Harry

    2015-12-22

    A non-catalytic recuperative reformer has a flue gas flow path for conducting hot flue gas from a thermal process and a reforming mixture flow path for conducting a reforming mixture. At least a portion of the reforming mixture flow path is embedded in the flue gas flow path to permit heat transfer from the hot flue gas to the reforming mixture. The reforming mixture flow path contains substantially no material commonly used as a catalyst for reforming hydrocarbon fuel (e.g., nickel oxide, platinum group elements or rhenium), but instead the reforming mixture is reformed into a higher calorific fuel via reactions due to the heat transfer and residence time. In a preferred embodiment, extended surfaces of metal material such as stainless steel or metal alloy that are high in nickel content are included within at least a portion of the reforming mixture flow path.

  11. Electrochemical promotion of catalytic reactions

    NASA Astrophysics Data System (ADS)

    Imbihl, R.

    2010-05-01

    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  12. Catalytic hydrocracking of heavy oils

    SciTech Connect

    Khulbe, C.P.; Patmore, D.J.; Pruden, B.B.; Ranganathan, R.

    1983-01-25

    An improved process is described for the hydrocracking of heavy hydrocarbon oil, such as oils extracted from tar sands. The charge oil in the presence of an excess of hydrogen is passed through a tubular hydrocracking zone, and the effluent emerging from the top of the zone is separated into a gaseous stream containing a wide boiling range material and a liquid stream containing heavy hydrocarbons. According to the novel feature, the hydrocracking process is carried out in the presence of a catalyst consisting of finely divided coal or other carbonaceous material carrying catalytically active metals from group via and group viii of the periodic table of elements, E.G. Cobalt and molybdenum. The catalyst is slurried with the charge stock and has been found to greatly reduce coke precursors and thereby prevent the formation of carbonaceous deposits in the reaction zone while also being effective in reducing the sulfur concentration of the product.

  13. Trafficking to the Ciliary Membrane

    PubMed Central

    Nachury, Maxence V.; Seeley, E. Scott; Jin, Hua

    2010-01-01

    The primary cilium organizes numerous signal transduction cascades and an understanding of signaling receptors trafficking to cilia is now emerging. A defining feature of cilia is the periciliary diffusion barrier that separates the ciliary and plasma membranes despite the topological continuity between these two membranes. Although lateral transport through this barrier may take place, polarized exocytosis to the base of the cilium has been the prevailing model for delivering membrane proteins to cilia. Key players for this polarized exocytosis model include the GTPases Rab8 and Rab11, the exocyst and possibly the intraflagellar tranport machinery. Sorting membrane proteins to cilia critically relies on the recognition of ciliary targeting signals by sorting machines such as the BBSome coat complex or the GTPase Arf4. Finally, signaling at the cilium entails the bidirectional movement of proteins between cytoplasm and cilia and ubiquitination may promote exit from cilia. PMID:19575670

  14. Modulated mechanism of phosphatidylserine on the catalytic activity of Naja naja atra phospholipase A2 and Notechis scutatus scutatus notexin.

    PubMed

    Chiou, Yi-Ling; Lin, Shinne-Ren; Hu, Wan-Ping; Chang, Long-Sen

    2014-12-15

    Phosphatidylserine (PS) externalization is a hallmark for apoptotic death of cells. Previous studies showed that Naja naja atra phospholipase A2 (NnaPLA2) and Notechis scutatus scutatus notexin induced apoptosis of human cancer cells. However, NnaPLA2 and notexin did not markedly disrupt the integrity of cellular membrane as evidenced by membrane permeability of propidium iodide. These findings reflected that the ability of NnaPLA2 and notexin to hydrolyze membrane phospholipids may be affected by PS externalization. To address that question, this study investigated the membrane-interacted mode and catalytic activity of NnaPLA2 and notexin toward outer leaflet (phosphatidylcholine/sphingomyelin/cholesterol, PC/SM/Chol) and inner leaflet (phosphatidylserine/phosphatidylethanolamine/cholesterol, PS/PE/Chol) of plasma membrane-mimicking vesicles. PS incorporation promoted enzymatic activity of NnaPLA2 and notexin on PC and PC/SM vesicles, but suppressed NnaPLA2 and notexin activity on PC/SM/Chol and PE/Chol vesicles. PS incorporation increased the membrane fluidity of PC vesicles but reduced membrane fluidity of PC/SM, PC/SM/Chol and PE/Chol vesicles. PS increased the phospholipid order of all the tested vesicles. Moreover, PS incorporation did not greatly alter the binding affinity of notexin and NnaPLA2 with phospholipid vesicles. Acrylamide quenching studies and trinitrophenylation of Lys residues revealed that membrane-bound mode of notexin and NnaPLA2 varied with the targeted membrane compositions. The fine structure of catalytic site in NnaPLA2 and notexin in all the tested vesicles showed different changes. Collectively, the present data suggest that membrane-inserted PS modulates PLA2 interfacial activity via its effects on membrane structure and membrane-bound mode of NnaPLA2 and notexin, and membrane compositions determine the effect of PS on PLA2 activity. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Characterization of a Membrane-active Peptide from the Bordetella pertussis CyaA Toxin*

    PubMed Central

    Subrini, Orso; Sotomayor-Pérez, Ana-Cristina; Hessel, Audrey; Spiaczka-Karst, Johanna; Selwa, Edithe; Sapay, Nicolas; Veneziano, Rémi; Pansieri, Jonathan; Chopineau, Joel; Ladant, Daniel; Chenal, Alexandre

    2013-01-01

    Bordetella pertussis, the pathogenic bacteria responsible for whooping cough, secretes several virulence factors, among which is the adenylate cyclase toxin (CyaA) that plays a crucial role in the early stages of human respiratory tract colonization. CyaA invades target cells by translocating its catalytic domain directly across the plasma membrane and overproduces cAMP, leading to cell death. The molecular process leading to the translocation of the catalytic domain remains largely unknown. We have previously shown that the catalytic domain per se, AC384, encompassing residues 1–384 of CyaA, did not interact with lipid bilayer, whereas a longer polypeptide, AC489, spanning residues 1–489, binds to membranes and permeabilizes vesicles. Moreover, deletion of residues 375–485 within CyaA abrogated the translocation of the catalytic domain into target cells. Here, we further identified within this region a peptidic segment that exhibits membrane interaction properties. A synthetic peptide, P454, corresponding to this sequence (residues 454–485 of CyaA) was characterized by various biophysical approaches. We found that P454 (i) binds to membranes containing anionic lipids, (ii) adopts an α-helical structure oriented in plane with respect to the lipid bilayer, and (iii) permeabilizes vesicles. We propose that the region encompassing the helix 454–485 of CyaA may insert into target cell membrane and induce a local destabilization of the lipid bilayer, thus favoring the translocation of the catalytic domain across the plasma membrane. PMID:24064217

  16. Method of fabricating a catalytic structure

    DOEpatents

    Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

    2009-09-22

    A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

  17. Catalytic ignition of hydrogen/oxygen

    NASA Technical Reports Server (NTRS)

    Green, James M.; Zurawski, Robert L.

    1988-01-01

    An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen. Shell 405 granular catalyst and a unique monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant inlet temperature, and back pressure were varied parametrically in testing to determine the operational limits of a catalytic igniter. The test results showed that the gaseous hydrogen/oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. The results of the experimental program and the established operational limits for a catalytic igniter using both the granular and monolithic catalysts are presented. The capabilities of a facility constructed to conduct the igniter testing and the advantages of a catalytic igniter over other ignition systems for gaseous hydrogen and oxygen are also discussed.

  18. Catalytic ignition of hydrogen and oxygen propellants

    NASA Technical Reports Server (NTRS)

    Zurawski, Robert L.; Green, James M.

    1988-01-01

    An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen propellants. Shell 405 granular catalyst and a monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant temperature, and back pressure were varied parametrically in testing to determine the operational limits of the catalytic igniter. The test results show that the gaseous hydrogen and oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. A cyclic life of nearly 2000, 2 sec pulses at nominal operating conditions was demonstrated with the catalytic igniter. The results of the experimental program and the established operational limits for a catalytic igniter using the Shell 405 catalyst are presented.

  19. Diesel engine catalytic combustor system. [aircraft engines

    NASA Technical Reports Server (NTRS)

    Ream, L. W. (Inventor)

    1984-01-01

    A low compression turbocharged diesel engine is provided in which the turbocharger can be operated independently of the engine to power auxiliary equipment. Fuel and air are burned in a catalytic combustor to drive the turbine wheel of turbine section which is initially caused to rotate by starter motor. By opening a flapper value, compressed air from the blower section is directed to catalytic combustor when it is heated and expanded, serving to drive the turbine wheel and also to heat the catalytic element. To start, engine valve is closed, combustion is terminated in catalytic combustor, and the valve is then opened to utilize air from the blower for the air driven motor. When the engine starts, the constituents in its exhaust gas react in the catalytic element and the heat generated provides additional energy for the turbine section.

  20. Silver nanocluster catalytic microreactors for water purification

    NASA Astrophysics Data System (ADS)

    Da Silva, B.; Habibi, M.; Ognier, S.; Schelcher, G.; Mostafavi-Amjad, J.; Khalesifard, H. R. M.; Tatoulian, M.; Bonn, D.

    2016-07-01

    A new method for the elaboration of a novel type of catalytic microsystem with a high specific area catalyst is developed. A silver nanocluster catalytic microreactor was elaborated by doping a soda-lime glass with a silver salt. By applying a high power laser beam to the glass, silver nanoclusters are obtained at one of the surfaces which were characterized by BET measurements and AFM. A microfluidic chip was obtained by sealing the silver coated glass with a NOA 81 microchannel. The catalytic activity of the silver nanoclusters was then tested for the efficiency of water purification by using catalytic ozonation to oxidize an organic pollutant. The silver nanoclusters were found to be very stable in the microreactor and efficiently oxidized the pollutant, in spite of the very short residence times in the microchannel. This opens the way to study catalytic reactions in microchannels without the need of introducing the catalyst as a powder or manufacturing complex packed bed microreactors.

  1. Catalytic ignition of hydrogen and oxygen propellants

    NASA Technical Reports Server (NTRS)

    Zurawski, Robert L.; Green, James M.

    1988-01-01

    An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen propellants. Shell 405 granular catalyst and a monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant temperature, and back pressure were varied parametrically in testing to determine the operational limits of the catalytic igniter. The test results show that the gaseous hydrogen and oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. A cyclic life of nearly 2000, 2 sec pulses at nominal operating conditions was demonstrated with the catalytic igniter. The results of the experimental program and the established operational limits for a catalytic igniter using the Shell 405 catalysts are presented.

  2. Catalytic ignition of hydrogen and oxygen propellants

    NASA Technical Reports Server (NTRS)

    Zurawski, Robert L.; Green, James M.

    1988-01-01

    An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen propellants. Shell 405 granular catalyst and a monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant temperature, and back pressure were varied parametrically in testing to determine the operational limits of the catalytic igniter. The test results show that the gaseous hydrogen and oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. A cyclic life of nearly 2000, 2 sec pulses at nominal operating conditions was demonstrated with the catalytic igniter. The results of the experimental program and the established operational limits for a catalytic igniter using the Shell 405 catalysts are presented.

  3. Catalytic converter with thermoelectric generator

    SciTech Connect

    Parise, R.J.

    1998-07-01

    The unique design of an electrically heated catalyst (EHC) and the inclusion of an ECO valve in the exhaust of an internal combustion engine will meet the strict new emission requirements, especially at vehicle cold start, adopted by several states in this country as well as in Europe and Japan. The catalytic converter (CC) has been a most useful tool in pollution abatement for the automobile. But the emission requirements are becoming more stringent and, along with other improvements, the CC must be improved to meet these new standards. Coupled with the ECO valve, the EHC can meet these new emission limits. In an internal combustion engine vehicle (ICEV), approximately 80% of the energy consumed leaves the vehicle as waste heat: out the tail pipe, through the radiator, or convected/radiated off the engine. Included with the waste heat out the tail pipe are the products of combustion which must meet strict emission requirements. The design of a new CC is presented here. This is an automobile CC that has the capability of producing electrical power and reducing the quantity of emissions at vehicle cold start, the Thermoelectric Catalytic Power Generator. The CC utilizes the energy of the exothermic reactions that take place in the catalysis substrate to produce electrical energy with a thermoelectric generator. On vehicle cold start, the thermoelectric generator is used as a heat pump to heat the catalyst substrate to reduce the time to catalyst light-off. Thus an electrically heated catalyst (EHC) will be used to augment the abatement of tail pipe emissions. Included with the EHC in the exhaust stream of the automobile is the ECO valve. This valve restricts the flow of pollutants out the tail pipe of the vehicle for a specified amount of time until the EHC comes up to operating temperature. Then the ECO valve opens and allows the full exhaust, now treated by the EHC, to leave the vehicle.

  4. Regulation of catalytic activity of acid phosphatase by lipids in a reverse micellar system.

    PubMed

    Kudryashova, E V; Bronza, V L; Levashov, A V

    2009-03-01

    The influence of biomembrane lipids on the catalytic activity of a peripheral membrane enzyme, acid phosphatase (AP), was studied in a reverse micellar system. It was found that the interaction of AP with lipids led to a number of kinetic effects depending on lipid nature on enzyme function. The observed effects might be caused by the formation of lipoprotein complexes as well as by the influence of lipids on structure and properties of the micellar matrix. The results are important for clear understanding of molecular mechanisms of regulation of the catalytic activity of the membrane-associated enzyme in vivo. These data can also be used as a physicochemical basis for application of AP in medical fields as a diagnostic tool for diseases caused by changes in lipid metabolism, e.g. urinary, orthopedic, and allergic diseases.

  5. Surface Modification of Water Purification Membranes.

    PubMed

    Miller, Daniel J; Dreyer, Daniel R; Bielawski, Christopher W; Paul, Donald R; Freeman, Benny D

    2017-04-18

    Polymeric membranes are an energy-efficient means of purifying water, but they suffer from fouling during filtration. Modification of the membrane surface is one route to mitigating membrane fouling, as it helps to maintain high levels of water productivity. Here, a series of common techniques for modification of the membrane surface are reviewed, including surface coating, grafting, and various treatment techniques such as chemical treatment, UV irradiation, and plasma treatment. Historical background on membrane development and surface modification is also provided. Finally, polydopamine, an emerging material that can be easily deposited onto a wide variety of substrates, is discussed within the context of membrane modification. A brief summary of the chemistry of polydopamine, particularly as it may pertain to membrane development, is also described.

  6. Final Report

    SciTech Connect

    R Paul Drake

    2004-01-12

    OAK-B135 This is the final report from the project Hydrodynamics by High-Energy-Density Plasma Flow and Hydrodynamics and Radiation Hydrodynamics with Astrophysical Applications. This project supported a group at the University of Michigan in the invention, design, performance, and analysis of experiments using high-energy-density research facilities. The experiments explored compressible nonlinear hydrodynamics, in particular at decelerating interfaces, and the radiation hydrodynamics of strong shock waves. It has application to supernovae, astrophysical jets, shock-cloud interactions, and radiative shock waves.

  7. A Structural Study of CESA1 Catalytic Domain of Arabidopsis Cellulose Synthesis Complex: Evidence for CESA Trimers

    DOE PAGES

    Vandavasi, Venu Gopal; Putnam, Daniel K.; Zhang, Qiu; ...

    2015-11-10

    In a cellulose synthesis complex a "rosette" shape is responsible for the synthesis of cellulose chains and their assembly into microfibrils within the cell walls of land plants and their charophyte algal progenitors. The number of cellulose synthase proteins in this large multisubunit transmembrane protein complex and the number of cellulose chains in a microfibril have been debated for many years. Our work reports a low resolution structure of the catalytic domain of CESA1 from Arabidopsis (Arabidopsis thaliana; AtCESA1CatD) determined by small-angle scattering techniques and provides the first experimental evidence for the self-assembly of CESA into a stable trimer inmore » solution. The catalytic domain was overexpressed in Escherichia coli, and using a two-step procedure, it was possible to isolate monomeric and trimeric forms of AtCESA1CatD. Moreover, the conformation of monomeric and trimeric AtCESA1CatD proteins were studied using small-angle neutron scattering and small-angle x-ray scattering. A series of AtCESA1CatD trimer computational models were compared with the small-angle x-ray scattering trimer profile to explore the possible arrangement of the monomers in the trimers. Several candidate trimers were identified with monomers oriented such that the newly synthesized cellulose chains project toward the cell membrane. In these models, the class-specific region is found at the periphery of the complex, and the plant-conserved region forms the base of the trimer. Finally, this study strongly supports the "hexamer of trimers" model for the rosette cellulose synthesis complex that synthesizes an 18-chain cellulose microfibril as its fundamental product.« less

  8. A Structural Study of CESA1 Catalytic Domain of Arabidopsis Cellulose Synthesis Complex: Evidence for CESA Trimers

    SciTech Connect

    Vandavasi, Venu Gopal; Putnam, Daniel K.; Zhang, Qiu; Petridis, Loukas; Heller, William T.; Nixon, B. Tracy; Haigler, Candace H.; Kalluri, Udaya; Coates, Leighton; Langan, Paul; Smith, Jeremy C.; Meiler, Jens; O’Neill, Hugh

    2015-11-10

    In a cellulose synthesis complex a "rosette" shape is responsible for the synthesis of cellulose chains and their assembly into microfibrils within the cell walls of land plants and their charophyte algal progenitors. The number of cellulose synthase proteins in this large multisubunit transmembrane protein complex and the number of cellulose chains in a microfibril have been debated for many years. Our work reports a low resolution structure of the catalytic domain of CESA1 from Arabidopsis (Arabidopsis thaliana; AtCESA1CatD) determined by small-angle scattering techniques and provides the first experimental evidence for the self-assembly of CESA into a stable trimer in solution. The catalytic domain was overexpressed in Escherichia coli, and using a two-step procedure, it was possible to isolate monomeric and trimeric forms of AtCESA1CatD. Moreover, the conformation of monomeric and trimeric AtCESA1CatD proteins were studied using small-angle neutron scattering and small-angle x-ray scattering. A series of AtCESA1CatD trimer computational models were compared with the small-angle x-ray scattering trimer profile to explore the possible arrangement of the monomers in the trimers. Several candidate trimers were identified with monomers oriented such that the newly synthesized cellulose chains project toward the cell membrane. In these models, the class-specific region is found at the periphery of the complex, and the plant-conserved region forms the base of the trimer. Finally, this study strongly supports the "hexamer of trimers" model for the rosette cellulose synthesis complex that synthesizes an 18-chain cellulose microfibril as its fundamental product.

  9. High temperature ceramic membrane reactors for coal liquid upgrading

    SciTech Connect

    Tsotsis, T.T.

    1992-01-01

    In this project we intend to study a novel process concept, i.e, the use of ceramic membranes reactors in upgrading of coal derived liquids. Membrane reactors have been used in a number of catalytic reaction processes in order to overcome the limitations on conversion imposed by thermodynamic equilibrium. They have, furthermore, the inherent capability for combining reaction and separation in a single step. Thus they offer promise for improving and optimizing yield, selectivity and performance of processes involving complex liquids, as those typically found in coal liquid upgrading. Ceramic membranes are a new class of materials, which have shown promise in a variety of industrial applications. Their mechanical and chemical stability coupled with a wide range of operating temperatures and pressures make them suitable for environments found in coal liquid upgrading. In this project we will evaluate the performance of Sol-Gel alumina membranes in coal liquid upgrading processes under realistic temperature and pressure conditions and investigate the feasibility of using such membranes in a membrane reactor based coal liquid upgrading process. In addition, the development of novel ceramic membranes with enhanced catalytic activity for coal-liquid upgrading applications, such as carbon-coated alumina membranes, will be also investigated.

  10. High temperature ceramic membrane reactors for coal liquid upgrading

    SciTech Connect

    Tsotsis, T.T.

    1992-01-01

    In this project we intend to study a novel process concept, i.e.,the use of ceramic membranes reactors in upgrading of coal derived liquids. Membrane reactors have been used in a number of catalytic reaction processes in order to overcome the limitations on conversion imposed by thermodynamic equilibrium. They have, furthermore, the inherent capability for combining reaction and separation in a single step. Thus they offer promise for improving and optimizing yield, selectivity and performance of processes involving complex liquids, as those typically found in coal liquid upgrading. Ceramic membranes are a new class of materials, which have shown promise in a variety of industrial applications. Their mechanical and chemical stability coupled with a wide range of operating temperatures and pressures make them suitable for environments found in coal liquid upgrading. In this project we wig evaluate the performance of Sel-Gel alumina membranes in coal liquid upgrading processes under realistic temperature and pressure conditions and investigate the feasibility of using such membranes in a membrane reactor based coal liquid upgrading process. In addition, the development of novel ceramic membranes with enhanced catalytic activity for coal-liquid upgrading applications, such as carbon-coated alumina membranes, will be also investigated.

  11. High temperature ceramic membrane reactors for coal liquid upgrading

    SciTech Connect

    Tsotsis, T.T.

    1992-06-19

    Ceramic membranes are a new class of materials, which have shown promise in a variety of industrial applications. Their mechanical and chemical stability coupled with a wide range of operating temperatures and pressures make them suitable for environments found in coal liquid upgrading. In this project we will evaluate the performance of Sel-Gel alumina membranes in coal liquid upgrading processes under realistic temperature and pressure conditions and investigate the feasibility of using such membranes in a membrane reactor based coal liquid upgrading process. In addition, the development of novel ceramic membranes with enhanced catalytic activity for coal-liquid upgrading applications, such as carbon-coated alumina membranes, will be also investigated.

  12. High temperature ceramic membrane reactors for coal liquid upgrading

    SciTech Connect

    Tsotsis, T.T.

    1992-06-19

    Ceramic membranes are a new class of materials, which have shown promise in a variety of industrial applications. Their mechanical and chemical stability coupled with a wide range of operating temperatures and pressures make them suitable for environments found in coal liquid upgrading. In this project we will evaluate the performance of Sel-Gel alumina membranes in coal liquid upgrading processes under realistic temperature and pressure conditions and investigate the feasibility of using such membranes in a membrane reactor based coal liquid upgrading process. In addition, the development of novel ceramic membranes with enhanced catalytic activity for coal-liquid upgrading applications, such as carbon-coated alumina membranes, will be also investigated.

  13. High temperature ceramic membrane reactors for coal liquid upgrading

    SciTech Connect

    Tsotsis, T.T.

    1992-06-19

    Ceramic membranes are a new class of materials, which have shown promise in a variety of industrial applications. Their mechanical and chemical stability coupled with a wide range of operating temperatures and pressures make them suitable for environments found in coal liquid upgrading. In this project we will evaluate the performance of Sel-Gel alumina membranes in coal liquid upgrading processes under realistic temperature and pressure conditions and investigate the feasibility of using such membranes in a membrane reactor based coal liquid upgrading process. In addition, the development of novel ceramic membranes with enhanced catalytic activity for coal-liquid upgrading applications, such as carbon-coated alumina membranes, will also be investigated.

  14. Organic Electrolyte Permselective Membranes.

    DTIC Science & Technology

    ORGANIC SOLVENTS), (*STORAGE BATTERIES, (*BATTERY SEPARATORS, MEMBRANES ), (* MEMBRANES , TRANSPORT PROPERTIES), LITHIUM, COPPER COMPOUNDS, DIFFUSION, CHLORIDES, IONS, ELECTRODIALYSIS , ION EXCHANGE RESINS.

  15. Metal Ion Sensor with Catalytic DNA in a Nanofluidic Intelligent Processor

    DTIC Science & Technology

    2011-12-01

    significant advance for materials engineering . Solving the problem of bonding PMMA to the polycarbonate membranes created leak-free devices with the capa...ER-1459 Metal Ion Sensor with Catalytic DNA in a Nanofluidic Intelligent Processor Donald M. Cropek Construction Engineering Research Laboratory...U.S. Army Engineer Research and Development Center 2902 Newmark Drive PO Box 9005 Champaign, IL 61826-9005 Tulika S. Dalavoy, Paul W. Bohn, Yi Lu

  16. Electrocatalytic hydrocracking. Final report

    SciTech Connect

    Vaart, D.R. van der

    1992-06-01

    This report describes an electrocatalytic method for the chemical addition of hydrogen to a model hydrocarbon compound. In the method, hydrogen formed by water electrolysis at the counter electrode of an electrochemical cell is delivered via conduction through a proton-conducting solid electrolyte. The working electrode of the cell is, at the same time, a hydrocracking catalyst and therefore promotes the reaction of the hydrogen with the hydrocarbon. This process would have clear and distinct advantages over conventional hydroprocessing technologies in that the hydrogen concentration at the catalyst surface could be controlled and maintained by the applied electromotive force. This control would allow operation of the electrocatalytic reactor at ambient pressures instead of the extremely high hydrogen partial pressures required of conventional reactors. In addition, the direct delivery of hydrogen to the catalyst surface should inhibit coke formation and thus prolong the life of the catalyst. Finally, hydrogen utilization efficiencies should be greatly improved since the hydrogen is delivered directly to the reaction site thereby eliminating hydrogen solubility loss in the effluent stream. This report details the demonstration of (a) the ability of a solid electrolyte to perform as a catalyst, (b) the conduction of hydrogen through a solid electrolyte and (c) the simultaneous exploitation of these two properties. Hence, the essential concept of electrocatalytic hydrocracking has been demonstrated. An objective of future work in this area should be to determine whether the hydrocracking or hydrogenation reactions are actually enhanced during the electrocatalytic process when compared to the conventional catalytic process.

  17. Revolutionary systems for catalytic combustion and diesel catalytic particulate traps.

    SciTech Connect

    Stuecker, John Nicholas; Witze, Peter O.; Ferrizz, Robert Matthew; Cesarano, Joseph, III; Miller, James Edward

    2004-12-01

    This report is a summary of an LDRD project completed for the development of materials and structures conducive to advancing the state of the art for catalyst supports and diesel particulate traps. An ancillary development for bio-medical bone scaffolding was also realized. Traditionally, a low-pressure drop catalyst support, such as a ceramic honeycomb monolith, is used for catalytic reactions that require high flow rates of gases at high-temperatures. A drawback to the traditional honeycomb monoliths under these operating conditions is poor mass transfer to the catalyst surface in the straight-through channels. ''Robocasting'' is a unique process developed at Sandia National Laboratories that can be used to manufacture ceramic monoliths with alternative 3-dimensional geometries, providing tortuous pathways to increase mass transfer while maintaining low-pressure drops. These alternative 3-dimensional geometries may also provide a foundation for the development of self-regenerating supports capable of trapping and combusting soot particles from a diesel engine exhaust stream. This report describes the structures developed and characterizes the improved catalytic performance that can result. The results show that, relative to honeycomb monolith supports, considerable improvement in mass transfer efficiency is observed for robocast samples synthesized using an FCC-like geometry of alternating rods. Also, there is clearly a trade-off between enhanced mass transfer and increased pressure drop, which can be optimized depending on the particular demands of a given application. Practical applications include the combustion of natural gas for power generation, production of syngas, and hydrogen reforming reactions. The robocast lattice structures also show practicality for diesel particulate trapping. Preliminary results for trapping efficiency are reported as well as the development of electrically resistive lattices that can regenerate the structure by combusting the

  18. NMR Reveals Double Occupancy of Quinone-type Ligands in the Catalytic Quinone Binding Site of the Na+-translocating NADH:Quinone Oxidoreductase from Vibrio cholerae*

    PubMed Central

    Nedielkov, Ruslan; Steffen, Wojtek; Steuber, Julia; Möller, Heiko M.

    2013-01-01

    The sodium ion-translocating NADH:quinone oxidoreductase (Na+-NQR) from the pathogen Vibrio cholerae exploits the free energy liberated during oxidation of NADH with ubiquinone to pump sodium ions across the cytoplasmic membrane. The Na+-NQR consists of four membrane-bound subunits NqrBCDE and the peripheral NqrF and NqrA subunits. NqrA binds ubiquinone-8 as well as quinones with shorter prenyl chains (ubiquinone-1 and ubiquinone-2). Here we show that the quinone derivative 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone (DBMIB), a known inhibitor of the bc1 and b6f complexes found in mitochondria and chloroplasts, also inhibits quinone reduction by the Na+-NQR in a mixed inhibition mode. Tryptophan fluorescence quenching and saturation transfer difference NMR experiments in the presence of Na+-NQR inhibitor (DBMIB or 2-n-heptyl-4-hydroxyquinoline N-oxide) indicate that two quinone analog ligands are bound simultaneously by the NqrA subunit with very similar interaction constants as observed with the holoenzyme complex. We conclude that the catalytic site of quinone reduction is located on NqrA. The two ligands bind to an extended binding pocket in direct vicinity to each other as demonstrated by interligand Overhauser effects between ubiquinone-1 and DBMIB or 2-n-heptyl-4-hydroxyquinoline N-oxide, respectively. We propose that a similar spatially close arrangement of the native quinone substrates is also operational in vivo, enhancing the catalytic efficiency during the final electron transfer steps in the Na+-NQR. PMID:24003222

  19. How Membrane-Active Peptides Get into Lipid Membranes.

    PubMed

    Sani, Marc-Antoine; Separovic, Frances

    2016-06-21

    The structure-function relationship for a family of antimicrobial peptides (AMPs) from the skin of Australian tree frogs is discussed and compared with that of peptide toxins from bee and Australian scorpion venoms. Although these membrane-active peptides induce a similar cellular fate by disrupting the lipid bilayer integrity, their lytic activity is achieved via different modes of action, which are investigated in relation to amino acid sequence, secondary structure, and membrane lipid composition. In order to better understand what structural features govern the interaction between peptides and lipid membranes, cell-penetrating peptides (CPPs), which translocate through the membrane without compromising its integrity, are also discussed. AMPs possess membrane lytic activities that are naturally designed to target the cellular membrane of pathogens or competitors. They are extremely diverse in amino acid composition and often show specificity against a particular strain of microbe. Since our antibiotic arsenal is declining precariously in the face of the rise in multiantibiotic resistance, AMPs increasingly are seen as a promising alternative. In an effort to understand their molecular mechanism, biophysical studies of a myriad of AMPs have been reported, yet no unifying mechanism has emerged, rendering difficult the rational design of drug leads. Similarly, a wide variety of cytotoxic peptides are found in venoms, the best known being melittin, yet again, predicting their activity based on a particular amino acid composition or secondary structure remains elusive. A common feature of these membrane-active peptides is their preference for the lipid environment. Indeed, they are mainly unstructured in solution and, in the presence of lipid membranes, quickly adsorb onto the surface, change their secondary structure, eventually insert into the hydrophobic core of the membrane bilayer, and finally disrupt the bilayer integrity. These steps define the molecular

  20. Topological entropy of catalytic sets: Hypercycles revisited

    NASA Astrophysics Data System (ADS)

    Sardanyés, Josep; Duarte, Jorge; Januário, Cristina; Martins, Nuno

    2012-02-01

    The dynamics of catalytic networks have been widely studied over the last decades because of their implications in several fields like prebiotic evolution, virology, neural networks, immunology or ecology. One of the most studied mathematical bodies for catalytic networks was initially formulated in the context of prebiotic evolution, by means of the hypercycle theory. The hypercycle is a set of self-replicating species able to catalyze other replicator species within a cyclic architecture. Hypercyclic organization might arise from a quasispecies as a way to increase the informational containt surpassing the so-called error threshold. The catalytic coupling between replicators makes all the species to behave like a single and coherent evolutionary multimolecular unit. The inherent nonlinearities of catalytic interactions are responsible for the emergence of several types of dynamics, among them, chaos. In this article we begin with a brief review of the hypercycle theory focusing on its evolutionary implications as well as on different dynamics associated to different types of small catalytic networks. Then we study the properties of chaotic hypercycles with error-prone replication with symbolic dynamics theory, characterizing, by means of the theory of topological Markov chains, the topological entropy and the periods of the orbits of unimodal-like iterated maps obtained from the strange attractor. We will focus our study on some key parameters responsible for the structure of the catalytic network: mutation rates, autocatalytic and cross-catalytic interactions.