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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

Peptide conjugates with polyaromatic hydrocarbons can benefit the activity of catalytic RNAs

Early stages of life likely employed catalytic RNAs (ribozymes) in many functions that are today filled by proteins. However, the earliest life forms must have emerged from heterogenous chemical mixtures, which included amino acids, short peptides, and many other compounds. Here we explored whether the presence of short peptides can help the emergence of catalytic RNAs. To do this, we conducted an in vitro selection for catalytic RNAs from randomized sequence in the presence of ten different peptides with a prebiotically plausible length of eight amino acids. This in vitro selection generated dozens of ribozymes, one of them with ∼900-fold higher activity in the presence of one specific peptide. Unexpectedly, the beneficial peptide had retained its N-terminal Fmoc protection group, and this group was required to benefit ribozyme activity. The same, or higher benefit resulted from peptide conjugates with prebiotically plausible polyaromatic hydrocarbons (PAHs) such as fluorene and naphthalene. This shows that PAH-peptide conjugates can act as potent cofactors to enhance ribozyme activity. The results are discussed in the context of the origin of life.

Kevin J. Sweeney↗

Cellular localization of Na(+), K(+)-ATPase in the mammalian vestibular system

Two different, but complementary, procedures for cellular localization of Na+, K+-ATPase in the guinea pig vestibular system were employed. One of these techniques, devised by Stirling, depends upon the well documented ability of the specific inhibitor ouabain to bind selectively to Na+,K+-ATPase, blocking catalytic activity. Microdisected vestibular tissues are incubated with tritium-labelled (3H-) ouabain, and regions with a high concentration of Na+,K+-ATPase are subsequently identified by light microscope autoradiography. A second method, originated by Ernst, detects inorganic phosphate released from an artificial substrate (nitrophenyl phosphate) by catalytic activity of the enzyme. In the presence of strontium ion, phosphate is precipitated near regions of high activity, then converted to a product which may finally be visualized in the electron microscope. This cytochemical enzymatic reaction is inhibited by ouabain.

Kerr, T. P.↗

Non-equilibrium stagnation region aerodynamic heating of hypersonic glide vehicles

A simple method of predicting aerodynamic heating and corresponding radiation equilibrium surface temperature-time histories for critical locations on space shuttle orbiter-type vehicles is presented. The method is based on a generalization of correlation equations developed earlier by Rosner for predicting the energy transfer and radiation equilibrium temperatures of surfaces with arbitrary catalytic activity and total hemispheric emittance. Recently obtained experimental data for O and N atom recombination probabilities on candidate material surfaces above 1000 K are used to assess nonequilibrium effects for a range of nose radii and a specific space shuttle re-entry trajectory. It is concluded that low catalytic activity will be especially important in locations of large effective nose radii by both increasing oxidation-resistant coating lifetime and reducing energy transfer into the vehicle.

Rosner, D. E.↗

Formation of RNA oligomers on montmorillonite: site of catalysis

Certain montmorillonites catalyze the self condensation of the 5'-phosphorimidazolide of nucleosides in pH 8 aqueous electrolyte solutions at ambient temperatures leading to formation of RNA oligomers. In order to establish the nature of the sites on montmorillonite responsible for this catalytic activity, oligomerization reactions were run with montmorillonites which had been selectively modified (I) at the edges by (a) fluoride treatment, (b) silylation, (c) metaphosphate treatment of the anion exchange sites (II) in the interlayer by (a) saturation with quaternary alkylammonium ions of increasing size, (b) aluminum polyoxo cations. High pressure liquid chromatography, HPLC, analysis of condensation products for their chain lengths and yields indicated that modification at the edges did not affect the catalytic activity to a significant extent, while blocking the interlayer strongly inhibited product formation.

NASA Discipline Exobiology↗

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation. Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium).

Prakash, Jai↗

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Prakash, Jai↗

Making Fuel-Cell Electrodes By Electrodeposition

Electrodes for direct oxidation of methanol in fuel cells fabricated in process involving room-temperature electro-chemical deposition of platinum-alloy catalysts on commercially available high-surface-area carbon support structures containing polytetrafluoroethylene (PTFE). Process takes 30 to 50 minutes and results in electrodes catalytically active as prepared; no need for additional activation step. Composition of catalytic platinum alloy and sizes of particles in catalytic layers on electrodes varied by changing operating conditions during electrodeposition; process affords additional flexibility in design of electrocatalysts.

Narayanan, Sekharipuram R.↗

Method of maintaining activity of hydrogen-sensing platinum electrode

Three-electrode hydrogen sensor containing a platinum electrode maintained in a highly catalytic state, operates with a minimal response time and maximal sensitivity to the hydrogen gas being sensed. Electronic control and readout circuitry reactivates the working electrode of the sensor to a state of maximal catalytic activity.

Harman, J. N., III↗

Characterization of Truncated Tumor-Associated NADH Oxidase (ttNOX)

Bacterial, plant and animal cells possess novel surface proteins that exhibit both NADH oxidation (NOX) or hydroquinone and protein disulfide-thiol interchange. These enzymatic activities alternate to yield oscillating patterns wjth period lengths of approximately 24 minutes. The catalytic period of NOX proteins are temperature compensated and gravity responsive. We report the cloning, expression and characterization of truncated tumor-associated NADH oxidase (ttNOX), in which the membrane spanning region has been deleted. The cDNA (originated from HeLa cells) was cloned into pET-34b and pET-14b (Novagen) vectors for E. coli expression. Optimized expression and purification protocols yielded greater than 300mg per liter of culture with greater than 95% purity. Circular dichroism data was collected from a 2.7mg/ml solution in a 0.1mm cuvette with variable scanning using an Olis RSM CD spectrophotometer. The ellipticity values were scanned from 190 to 260nm. The spectra recorded have characteristics for alpha proteins with band maxima at 216nm and a possible shoulder at 212nm at 12OC and 250 C. Protein crystal screens are in progress and, to date, only small crystals have been observed. The regular periodic oscillatory change in the ttNOX protein is indicative of a possible time-keeping functional role. A single protein possessing alternating catalytic activities, with a potential biological clock function, is unprecedented and structural determination is paramount to understanding this role.

Karr, Laurel J.↗

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.↗