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At least 631 records · Page 35

Catalysis of the Oligomerization of O-Phospho-Serine, Aspartic Acid, or Glutamic Acid by Cationic Micelles

Treatment of relatively concentrated aqueous solutions of O-phospho-serine (50 mM), aspartic acid (100 mM) or glutamic acid (100 mM) with carbonyldiimidazole leads to the formation of an activated intermediate that oligomerizes efficiently. When the concentration of amino acid is reduced tenfold, few long oligomers can be detected. Positively-charged cetyltrimethyl ammonium bromide micelles concentrate the negatively-charged activated intermediates of the amino acids at their surfaces and catalyze efficient oligomerization even from dilute solutions.

Boehler, Christof↗

Thrust Enhancement in Hypervelocity Nozzles by Chemical Catalysis

In the hypersonic flight regime, the air-breathing supersonic combustion ramjet (scramjet) has been shown to be a viable propulsion system. The current designs of scramjet engines provide performance benefits only up to a Mach number of 14. Performance losses increase rapidly as the Mach number increases. To extend the applicability of scram'jets beyond Mach 14, research is being conducted in the area of inlet and wave drag reduction, skin-friction and heat-transfer reduction, nozzle loss minimization, low-loss mixing, and combustion enhancement. For high Mach number applications, hydrogen is the obvious fuel choice because of its high energy content per unit mass in comparison with conventional fuels. These flight conditions require engines to operate at supersonic internal velocities, high combustor temperatures, and low static pressures. The high static temperature condition enhances the production of radicals such as H and OH, and the low-pressure condition slows the reaction rates, particularly the recombination reactions. High-temperature and low-pressure constraints, in combination with a small residence time, result in a radical-rich exhaust gas mixture exiting the combustor. At high Mach number conditions (due to low residence time), H and OH do not have enough time to recombine ; thus, a significant amount of energy is lost as these high-energy free radical are exhausted. The objective of the present study is to conduct a flowfield analysis for a typical nozzle geometry for NASP-type vehicle to assess for thrust enhancement in hypervelocity nozzles by substituting small amount of phosphine for hydrogen.

Singh, D. J.↗

Two-Photon Laser-Induced Fluorescence O and N Atoms for the Study of Heterogeneous Catalysis in a Diffusion Reactor

Advanced laser-based diagnostics have been developed to examine catalytic effects and atom/surface interactions on thermal protection materials. This study establishes the feasibility of using laser-induced fluorescence for detection of O and N atom loss in a diffusion tube to measure surface catalytic activity. The experimental apparatus is versatile in that it allows fluorescence detection to be used for measuring species selective recombination coefficients as well as diffusion tube and microwave discharge diagnostics. Many of the potential sources of error in measuring atom recombination coefficients by this method have been identified and taken into account. These include scattered light, detector saturation, sample surface cleanliness, reactor design, gas pressure and composition, and selectivity of the laser probe. Recombination coefficients and their associated errors are reported for N and O atoms on a quartz surface at room temperature.

Pallix, Joan B.↗

Formation of Amino Acid Thioesters for Prebiotic Peptide Synthesis: Catalysis By Amino Acid Products

The origin of life can be described as a series of events in which a prebiotic chemical process came increasingly under the control of its catalytic products. In our search for this prebiotic process that yielded catalytic takeover products (such as polypeptides), we have been investigating a reaction system that generates peptide-forming amino acid thioesters from formaldehyde, glycolaldehyde, and ammonia in the presence of thiols. As shown below, this model process begins by aldol condensation of formaldehyde and glycolaldehyde to give trioses and releases. These sugars then undergo beta-dehydration yielding their respective alpha-ketoaldehydes. Addition of ammonia to the alpha-ketoaldehydes yields imines which can either: (a) rearrange in the presence of thesis to give amino acid thioesters or (be react with another molecule of aldehyde to give imidazoles. This 'one-pot' reaction system operates under mild aqueous conditions, and like modem amino acid biosynthesis, uses sugar intermediates which are converted to products by energy-yielding redox reactions. Recently, we discovered that amino acids, such as the alanine reaction product, catalyze the first and second steps of the process. In the presence of ammonia the process also generates other synthetically useful products, like the important biochemical -- pyruvic acid.

Weber, Arthur L.↗

Influence of Catalysis and Oxidation on Slug Calorimeter Measurements in Arc Jets

Arc jet tests play a critical role in the characterization and certification of thermal protection materials and systems (TPS). The results from these arc jet tests feed directly into computational models of material response and aerothermodynamics to predict the performance of the TPS in flight. Thus the precise knowledge of the plasma environment to which the test material is subjected, is invaluable. As one of the environmental parameters, the heat flux is commonly measured. The measured heat flux is used to determine the plasma enthalpy through analytical or computational models. At NASA Ames Research Center (ARC), slug calorimeters of a geometrically similar body to the test article are routinely used to determine the heat flux. A slug calorimeter is a thermal capacitance-type calorimeter that uses the temperature rise in a thermally insulated slug to determine the heat transfer rate, see Figure 1(left). Current best practices for measuring the heat flux with a slug calorimeter are described in ASTM E457 - 96. Both the calorimeter body and slug are made of Oxygen Free High Conductivity Copper, and are cleaned before each run.

Nawaz, Anuscheh↗

Surface Catalysis and Oxidation on Stagnation Point Heat Flux Measurements in High Enthalpy Arc Jets

Heat flux sensors are routinely used in arc jet facilities to determine heat transfer rates from plasma plume. The goal of this study is to assess the impact of surface composition changes on these heat flux sensors. Surface compositions can change due to oxidation and material deposition from the arc jet. Systematic surface analyses of the sensors were conducted before and after exposure to plasma. Currently copper is commonly used as surface material. Other surface materials were studied including nickel, constantan gold, platinum and silicon dioxide. The surfaces were exposed to plasma between 0.3 seconds and 3 seconds. Surface changes due to oxidation as well as copper deposition from the arc jets were observed. Results from changes in measured heat flux as a function of surface catalycity is given, along with a first assessment of enthalpy for these measurements. The use of cupric oxide is recommended for future heat flux measurements, due to its consistent surface composition arc jets.

Nawaz, Anuscheh↗

Polydentate ligands and their complexes for molecular catalysis

Embodiments of the present disclosure relate generally to novel achiral and chiral sulfur-, nitrogen- and phosphorus-containing ligands, designated as NNS-type, P(O)NS-type, PNS-type, SNNS-type, SNNP(O)-type, or SNNP-type polydentate ligands and transition metal complexes of these ligands, including iridium complexes having PNS-type and NNS-type ligands. The catalysts derived from these ligands and transition metal complexes may be used in a wide range of catalytic reactions, including hydrogenation and transfer hydrogenation of unsaturated organic compounds, dehydrogenation of alcohols and boranes, various dehydrogenative couplings, chemoselective hydrogenation of α,β-unsaturated alcohols, and other catalytic transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof

Catalysts prepared from abundant, cost effective metals, such as cobalt, nickel, chromium, manganese, iron, and copper, and containing one or more neutrally charged ligands (e.g., monodentate, bidentate, and/or polydentate ligands) and methods of making and using thereof are described herein. Exemplary ligands include, but are not limited to, phosphine ligands, nitrogen-based ligands, sulfur-based ligands, and/or arsenic-based ligands. In some embodiments, the catalyst is a cobalt-based catalyst or a nickel-based catalyst. The catalysts described herein are stable and active at neutral pH and in a wide range of buffers that are both weak and strong proton acceptors. While its activity is slightly lower than state of the art cobalt-based water oxidation catalysts under some conditions, it is capable of sustaining electrolysis at high applied potentials without a significant degradation in catalytic current. This enhanced robustness gives it an advantage in industrial and large-scale water electrolysis schemes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗