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At least 55 records · Page 3

Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic devices.

Kim, Jae-Woo↗

Maturity of the Bosch CO2 reduction technology for Space Station application

The Bosch process, which catalytically reduces CO2 with H2 to solid carbon and water, is a promising technique for the reduction of the CO2 removed from the Space Station atmosphere and the subsequent water formation for O2 recovery. A Bosch engineering subsystem prototype CO2 reduction unit was developed to demonstrate the feasibility of the Bosch process as a viable technology for Space Station application. A man-rated prototype unit is then described as part of the ECLSS Technology Demonstrator Program. The goal was to develop a Bosch subsystem that not only meets the performance requirements of two 60 person-day carbon cartridge capacities, but also satisfies inherent man-rated requirements such as offgassing characteristics, fail-safe operation, and ease of maintainability. It is concluded that the technology is at a state of maturity directly applicable to flight status for the NASA Space Station program.

Wagner, Robert C.↗

Physical-Chemical Solid Waste Processing for Space Missions at Ames Research Center

As space missions become longer in duration and reach out to more distant locations such as Mars, solids waste processing progresses from storage technologies to reclamation technologies. Current low Earth orbit technologies consist of store-and dispose to space or return to Earth. Fully regenerative technologies recycle wastes. The materials reclaimed from waste can be used to provide the basic materials to support plant growth for food including carbon dioxide, water, and nutrients. Other products can also be reclaimed from waste such as hydrocarbons and activated carbon. This poster describes development at Ames Research Center of a process to make activated carbon from space mission wastes and to make an incineration system that produces clean flue gas. Inedible biomass and feces contain hydrocarbons in a form that can be pyrolyzed and converted to activated carbon. The activated carbon can then be used to clean up contaminants from various other life support systems; in particular, the activated carbon can be used regeneratively to remove NOx from incinerator flue gas. Incinerator flue gas can also be cleaned up by the use of reductive and oxidative catalysts. A catalytic incinerator flue gas cleanup system has been developed at ARC that produces flue gas clean enough (with the exception of carbon dioxide) to meet the Space Minimum Allowable Concentration limits for human exposure.

Fisher, John W.↗

Structures of the Nitrogenase Complex Prepared Under Catalytic Turnover Conditions

The enzyme nitrogenase couples adenosine triphosphate (ATP) hydrolysis to the multielectron reduction of atmospheric dinitrogen into ammonia. Despite extensive research, the mechanistic details of ATP-dependent energy transduction and dinitrogen reduction by nitrogenase are not well understood, requiring new strategies to monitor its structural dynamics during catalytic action. Here, we report cryo–electron microscopy structures of the nitrogenase complex prepared under enzymatic turnover conditions. We observe that asymmetry governs all aspects of the nitrogenase mechanism, including ATP hydrolysis, protein-protein interactions, and catalysis. Conformational changes near the catalytic iron-molybdenum cofactor are correlated with the nucleotide-hydrolysis state of the enzyme.

Hannah L. Rutledge↗

CryoEM Structures of the Nitrogenase Complex During Catalytic Turnover

The enzyme nitrogenase couples adenosine triphosphate (ATP) hydrolysis to the multi-electron reduction of atmospheric dinitrogen into ammonia. Despite extensive research, the mechanistic details of ATP-dependent energy transduction and dinitrogen reduction by nitrogenase are not well understood, requiring new strategies to monitor its structural dynamics during catalytic action. Here we report the cryogenic electron microscopic interrogation of the nitrogenase complex under enzymatic turnover conditions, which has enabled the structural characterization of the nitrogenase reaction intermediates at high resolution for the first time. Our structures show that asymmetry governs all aspects of nitrogenase mechanism including ATP hydrolysis, protein-protein interactions, and catalysis. Furthermore, they reveal several previously unobserved, mechanistically relevant conformational changes near the catalytic iron-molybdenum cofactor that are correlated with the nucleotide-hydrolysis state of the enzyme.

Hannah L. Rutledge↗

Chlorine chemistry in the Antarctic stratosphere - Impact of OClO and Cl2O2 and implications for observations

Theories have been proposed to relate the reduction of O3 during Antarctic spring to catalytic cycles involving chlorine and bromine species. A necessary condition for any chlorine-catalyzed scheme is that a large fraction of the chlorine must be in the form of ClO in the lower stratosphere. It has been suggested that these high levels of ClO could be maintained by fast heterogeneous reactions, whose rates are not known at present. Model calculations based on the above mechanisms predict considerable amounts of OClO and Cl2O2, particularly during the night. Results of calculations of the diurnal variations of ClO, OClO, and Cl2O2 during Antarctic spring are presented for different cases. Results from the calculations suggest that coincident measurements of the total column abundance and diurnal variation of ClO and OClO may help constrain key aspects of the proposed chemical mechanisms. Removal of O3 by the catalytic cycle involving Cl2O2 could be as important as that involving BrO for present levels of chlorine, provided that Cl2O2 photolyzes rapidly to yield Cl and ClO2. It is shown that there is no synergy between these two cycles, since they both compete for the available ClO.

Rodriguez, Jose M.↗

Structural Basis for Flip-Flop Action of Thiamin-Dependent Enzymes Revealed by Crystal Structure of Human Pyruvate Dehydrogenase

The biologically active derivative of vitamin B1; thiamin pyrophosphate; is used as cofactor by many enzymes that perform a wide range of catalytic functions in the pathways of energy production. In alpha2beta2-heterotetrameric human pyruvate dehydrogenase, the first catalytic component enzyme of human pyruvate dehydrogenase complex, this cofactor is used to cleave the C(sup alpha)-C(=0) bond of pyruvate followed by reductive acetyl transfer to lipoyl-dihydrolipoamide acetyltransferase, the second catalytic component of the complex. The dynamic nonequivalence of two, otherwise chemically equivalent, catalytic sites have puzzled researchers from earlier functional studies of this enzyme. In order to gain insight into the mechanism of action of this enzyme, we determined the crystal structure of the holoform of human pyruvate dehydrogenase at 1.958, resolution. We propose a kinetic model for the flip-flop action of this enzyme through the concerted approx. 2A, shuttle-like motion of the heterodimers. The similarity of thiamin pyrophosphate binding in human pyruvate dehydrogenase and other functionally related enzymes suggests this newly defined mechanism of shuttle-like motion of domains to be common for the family of thiamin pyrophosphate-dependent enzymes.

Ciszak, Ewa↗

A Chemical Approach to Carbon Dioxide Utilization on Mars

We describe several novel proposals for CO2 reduction through chemical, photochemical, and photoelectrochemical means. The approach involves coupled catalytic cycles to simultaneously produce oxygen and carbon monoxide. Efficient metal catalysts and photocatalysts are to be used for both halfreactions: (1) the reduction of CO2 to CO; and (2) the evolution of O2. Photolytic reduction of CO2 to CO and oxygen can occur under mild conditions using a series of recently synthesized trinuclear nickel catalysts. Nickel cluster catalysts hold great promise because of the proven ability of nickel cluster materials to catalyze the reduction of CO2 to CO.

Hepp, Aloysius F.↗

Advanced technology for controlling pollutant emissions from supersonic cruise aircraft

Gas turbine engine combustor technology for the reduction of pollutant emissions is summarized. Variations of conventional combustion systems and advanced combustor concepts are discussed. Projected results from far term technology efforts aimed at applying the premixed prevaporized and catalytic combustion techniques to aircraft combustion systems indicate a potential for significant reductions in pollutant emission levels.

Duerr, R. A.↗

A study for hypergolic vapor sensor development

The use of an electrochemical technique for MMH and N02 measurement was investigated. Specific MMH and N02 electrochemical sensors were developed. Experimental techniques for preparation, handling, and analysis of hydrazine's vapor mixtures at ppb and ppm levels were developed. Two approaches to N02 instrument design were evaluated including specific adsorption and specific electrochemical reduction. Two approaches to hydrazines monitoring were evaluated including catalytic conversion to N0 with subsequent N0 detection and direct specific electrochemical oxidation. Two engineering prototype MMH/N02 monitors were designed and constructed.

Stetter, J. R.↗

Self-organizing biochemical cycles

I examine the plausibility of theories that postulate the development of complex chemical organization without requiring the replication of genetic polymers such as RNA. One conclusion is that theories that involve the organization of complex, small-molecule metabolic cycles such as the reductive citric acid cycle on mineral surfaces make unreasonable assumptions about the catalytic properties of minerals and the ability of minerals to organize sequences of disparate reactions. Another conclusion is that data in the Beilstein Handbook of Organic Chemistry that have been claimed to support the hypothesis that the reductive citric acid cycle originated as a self-organized cycle can more plausibly be interpreted in a different way.

NASA Discipline Exobiology↗

New potentials for conventional aircraft when powered by hydrogen-enriched gasoline

Overall system efficiency and performance of a Beech Model 20 Duke aircraft was studied to provide analytical representations of an aircraft piston engine system, including all essential components required for onboard hydrogen generation. Lower emission levels and a 20% reduction in fuel consumption may be obtained by using a catalytic hydrogen generator, incorporated as part of the air induction system, to generate hydrogen by breaking down small amounts of the aviation gasoline used in the normal propulsion system. This hydrogen is then mixed with gasoline and compressed air from the turbocharger before entering the engine combustion chamber. The special properties of the hydrogen-enriched gasoline allow the engine to operate at ultra lean fuel/air ratios, resulting in higher efficiencies.

Menard, W. A.↗

Viscous shock-layer solutions with nonequilibrium chemistry for hypersonic flows past slender bodies

Laminar nonequilibrium heat transfer to slender vehicles is discussed, with heating-rate results presented as a ratio of the noncatalytic to the corresponding fully catalytic value to illustrate the maximum potential for a heating reduction in dissociated nonequilibrium flow at a given flight condition. Larger blunted cone half-angles are shown to produce the most significant nonequilibrium effects at distances beyond 100 nose radii, except in the fore-cone region. Increasing nose bluntness is found to produce large reductions in the ratio for the smaller cone angles at relatively large downstream surface lengths. It is noted that the nose radius and freestream density are not independent scaling parameters in nonequilibrium flow.

Zoby, E. V.↗

Demonstration of an Ultra-Short Channel Metal Monolith Catalytic Reactor for Trace Contaminant Control Applications

The International Space Station (ISS) Trace Contaminant Control Subassembly (TCCS) design is based upon proven, highly reliable technology. However, because its core unit operations rely upon expendable activated charcoal and an indirectly heated high temperature catalyst, annual logistics mass, crew time, and power consumption requirements are significant. To address this situation, a unique catalytic reactor design has been developed which is suitable for retrofit into the TCCS's high temperature catalytic oxidizer (HTCO) assembly. The unique design, which employs a metallic, ultra-short channel length monolith (USCM) catalyst substrate, was tested in a flight-like TCCS HTCO assembly to investigate its performance characteristics. Test results indicate that retrofitting the TCCS with a USCM-based catalytic reactor is feasible and that it may provide significant reductions in logistics mass, crew time, and power consumption. Savings indicated by test results are up to 81% for annual logistics, 56% for crew time, and 77% for startup transient duration. In addition, its demonstrated ability to operate in a power saving mode provides up to a 43% savings in average power consumption. A summary of the USCM demonstration test objectives, approach, results, and specific benefits to the TCCS's process economics are presented,

Perry, J. L↗

Investigation of a para-ortho hydrogen reactor for application to spacecraft sensor cooling

The utilization of solid hydrogen in space for sensor and instrument cooling is a very efficient technique for long term cooling or for cooling at high heat rates. The solid hydrogen can provide temperatures as low as 7 to 8 K to instruments. Vapor cooling is utilized to reduce parasitic heat inputs to the 7 to 8 K stage and is effective in providing intermediate cooling for instrument components operating at higher temperatures. The use of solid hydrogen in place of helium may lead to weight reductions as large as a factor of ten and an attendent reduction in system volume. The results of an investigation of a catalytic reactor for use with a solid hydrogen cooling system is presented. Trade studies were performed on several configurations of reactor to meet the requirements of high reactor efficiency with low pressure drop. Results for the selected reactor design are presented for both liquid hydrogen systems operating at near atmospheric pressure and the solid hydrogen cooler operating as low as 1 torr.

Nast, T. C.↗

A viscous shock-layer analysis of 2-D and axisymmetric flows

Results are obtained for cylindrical leading edges of proposed transatmospheric vehicles by employing a 2D viscous shock-layer code for nonequilibrium and perfect gas flows. The accuracy and efficiency of the planar code is verified through detailed comparisons with other predictions. It is found to be as accurate and robust as its axisymmetric counterpart. This study includes results for nose radii ranging from 0.01 to 2.0 ft and half-angles of 5 and 6 deg for both cylindrically-blunted wedges and spherically blunted cones (included for comparison). Some results are presented as a ratio of the noncatalytic to the corresponding fully catalytic heating value to illustrate the maximum potential for a heating reduction in dissociated nonequilibrium flows. This ratio and the individual heating rates are smaller for cylindrically-blunted wedges with small nose radii, relative to the spherically-blunted cones (at the same radius). Therefore, a larger potential exists for heating reduction in cylindrically-blunted as compared with the spherically-blunted surfaces for finite-rate chemistry.

Gupta, Roop N.↗

Viscous Shock-Layer Analysis of Two-Dimensional and Axisymmetric Flows

Results are obtained for cylindrical leading edges of proposed transatmospheric vehicles by employing a two-dimensional viscous shock-layer code for nonequilibrium gas flows. The accuracy and efficiency of the planar code is verified through detailed comparisons with other predictions. This study includes results for 6-deg half-angle bodies with nose radii ranging from 0.01 to 2.0 ft for both cylindrically blunted wedges and spherically blunted cones (included for comparison). Some results are presented as a ratio of the noncatalytic to the corresponding fully catalytic heating value to illustrate the maximum potential for a heating reduction in dissociated nonequilibrium flows. Generally, this ratio and the individual heating rates are smaller for cylindrically blunted wedges with small nose radii as compared to the spherically blunted cones (for the same nose radius). Therefore, a larger potential exists for heating reduction in cylindrically blunted as compared with the spherically blunted surfaces. However, the results presented at higher altitudes (where the slip effects become important) show that the spherically, blunted nose gives lower stagnation-point heating due to stronger merged shock-layer effects as compared with a cylindrically blunted nose.

Gupta, Roop N.↗

Non-noble electrocatalysts for alkaline fuel cells

The doping of solid phase precursors followed by pyrolysis or the copyrolysis of gas phase precursors has allowed us to produce catalysts with good activity toward oxygen reduction. Efforts are currently underway to better understand the reasons for the catalytic activity of the bulk doped catalysts with a view toward further improving their activity.

Sarangapani, S.↗