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At least 19 records

What is the Best Alternative to Diagonalization of the Hamiltonian in Large Scale Semiempirical Calculations?

Recently, several linear scaling approaches have been introduced which replace the time dominating diagonalization step in semiempirical methods, enabling practical calculations to be performed, on very large molecules. This paper compares the accuracy and performance of pseudodiagonalization (PD), conjugate gradient density matrix search (CG-DMS), the Chebyshev polynomial expansion method (CEM), and purification of the density matrix (PDM) as linear scaling substitutions for diagonalization. The scaling, speed, and reliability of these methods are compared for AMI single point energy calculations on polyglycine chains (up to 20,000 atoms), water clusters (up to 12,300 atoms), and nucleic acids (up to 6300 atoms).

Daniels, Andrew D.↗

Quantitation of promethazine and metabolites in urine samples using on-line solid-phase extraction and column-switching

A chromatographic method for the quantitation of promethazine (PMZ) and its three metabolites in urine employing on-line solid-phase extraction and column-switching has been developed. The column-switching system described here uses an extraction column for the purification of PMZ and its metabolites from a urine matrix. The extraneous matrix interference was removed by flushing the extraction column with a gradient elution. The analytes of interest were then eluted onto an analytical column for further chromatographic separation using a mobile phase of greater solvent strength. This method is specific and sensitive with a range of 3.75-1400 ng/ml for PMZ and 2.5-1400 ng/ml for the metabolites promethazine sulfoxide, monodesmethyl promethazine sulfoxide and monodesmethyl promethazine. The lower limits of quantitation (LLOQ) were 3.75 ng/ml with less than 6.2% C.V. for PMZ and 2.50 ng/ml with less than 11.5% C.V. for metabolites based on a signal-to-noise ratio of 10:1 or greater. The accuracy and precision were within +/- 11.8% in bias and not greater than 5.5% C.V. in intra- and inter-assay precision for PMZ and metabolites. Method robustness was investigated using a Plackett-Burman experimental design. The applicability of the analytical method for pharmacokinetic studies in humans is illustrated.

NASA Center JSC↗

Water-Based Coating Simplifies Circuit Board Manufacturing

The Structures and Materials Division at Glenn Research Center is devoted to developing advanced, high-temperature materials and processes for future aerospace propulsion and power generation systems. The Polymers Branch falls under this division, and it is involved in the development of high-performance materials, including polymers for high-temperature polymer matrix composites; nanocomposites for both high- and low-temperature applications; durable aerogels; purification and functionalization of carbon nanotubes and their use in composites; computational modeling of materials and biological systems and processes; and developing polymer-derived molecular sensors. Essentially, this branch creates high-performance materials to reduce the weight and boost performance of components for space missions and aircraft engine components. Under the leadership of chemical engineer, Dr. Michael Meador, the Polymers Branch boasts world-class laboratories, composite manufacturing facilities, testing stations, and some of the best scientists in the field.

Source record↗

Solidification processing

The solidification processing activities are reported. The following topics are studied: behavior of semisolid metals, purification and strengthening by fractional melting, continuous casting, control of ingot surface quality, and metal matrix composites. Formation of deoxidation products in steels is also investigated. Rapid solidification, crystal growth, experimental and mathematical modeling of solidification processes are explored.

Source record↗

Working Toward Nanotube Composites

One of the most attractive applications of single-wall carbon nanotubes (SWNT) is found in the area of structural materials. Nanotubes have a unique combination of high strength, modulus, and elongation to failure, and therefore have potential to significantly enhance the mechanical properties of today's composites. This is especially attractive for the aerospace industry looking for any chance to save weight. This is why NASA has chosen to tackle this difficult application of SWNT. Nanotube properties differ significantly from that of conventional carbon fibers, and a whole new set of problems, including adhesion and dispersion in the adhesive polymer matrix, must be resolved in order to engineer superior composite materials. From recent work on a variety of applications it is obvious that the wide range of research in nanotubes will lead to advances in physics, chemistry, and engineering. However, the possibility of ultralightweight structures is what causes dreamers to really get excited. One of the important issues in composite engineering is aspect ratio of the fibers, since it affects load transfer in composites. Nanotube length was a gray area for years, since they are formed in bundles, making it impossible to monitor individual nanotube length. Even though bundles are observed to be tens and hundreds of microns long, they can be built of relatively short tubes weakly bound by Van der Waals forces. Nanotube length can be affected by subsequent purification and ultrasound processing, which has been necessary in order to disperse nanotubes and introduce them into a polymer matrix. Some calculations show that nanotubes with 10(exp 5) aspect ratio may be necessary to achieve good load transfer. We show here that nanotubes produced in our laser system are as much as tens of microns long and get cut into lengths of hundreds of nanometers during ultrasound processing. Nanotube length was measured by AFM on pristine nanotube specimens as well, as after sonication. In each case great care was taken to measure individual nanotubes, rather than bundles. Pristine nanotubes were collected on quartz substrates placed directly in the laser oven and exposed for 0.5 s. This results in an equal mix of bundles and individual nanotubes. Nanotube length measurements were limited practically by the lateral span of the AFM scanner, but nanotube length is certainly in excess of 20 micrometers.

Arepalli, Sivaram↗

Multiple Epstein-Barr virus infections in healthy individuals

We employed a newly developed genotyping technique with direct representational detection of LMP-1 gene sequences to study the molecular epidemiology of Epstein-Barr virus (EBV) infection in healthy individuals. Infections with up to five different EBV genotypes were found in two of nine individuals studied. These results support the hypothesis that multiple EBV infections of healthy individuals are common. The implications for the development of an EBV vaccine are discussed.

Evaluation Studies↗

Carbon Nanotube Purification and Functionalization

Carbon nanotubes have the potential to significantly enhance the mechanical, thermal, and electrical properties of polymers. However, dispersion of carbon nanotubes in a polymer matrix is hindered by the electrostatic forces that cause them to agglomerate. Chemical modification of the nanotubes is necessary to minimize these electrostatic forces and promote adhesion between the nanotubes and the polymer matrix. In a collaborative research program between Clark Atlanta University, Rice University, and NASA Glenn Research Center several approaches are being explored to chemically modify carbon nanotubes. The results of this research will be presented.

Lebron, Marisabel↗

Trace Element and Isotopic Evidence for Bennu's Primitive Provenance

The delivery of material from asteroid (101955) Bennu by NASA’s OSIRIS-REx mission provides the opportunity to investigate some of the most pristine material from the early Solar System [1]. Our team at Lawrence LivermoreNational Laboratory (LLNL) utilized the equivalent of 5.0 mg from Bennu sampleOREX-803015-100 to quantify the major and trace element contents and investigate major element isotopics (Ca, Ti, Cr, Fe, and Ni). Our 5.0 mg aliquot ofOREX-803015-100 was a subsample of dissolved homogenized material representing 20.66 mg [2]. A separate 5.0 mg aliquot was sent to ETH Zürich and is discussed in a companion abstract [3]. Before any chemical separation on our 5.0 mg aliquot, the equivalent of 0.5 mg was removed and analyzed for elemental abundances at LLNL using a ThermoScientific Element XR. Our data agree exceptionally well with those reported by[2], showing that Bennu is primitive and compositionally similar to CI chondrites, Ryugu [4], and the solar photosphere [5]. The remaining ~4.5 mg underwent purification procedures to chemically isolate and purify Ca, Ti, Cr, Fe, and Ni from one another and the sample matrix. Their isotopic compositions were measured on either the Triton TIMS (Ca) at JohnsonSpace Center in Houston, Neoma MC-ICPMS (Ti, Cr) at LLNL, or the Neptune MC-ICPMS (Fe, Ni) at LLNL. Results from the Ca, Ti, Cr, Fe, and Ni isotopic compositions suggest that Bennu is closely related to CI chondrites—consistent with conclusions from elemental composition [2] and oxygen isotopics [6]reported for Bennu. The major element isotope compositions that we will present demonstrate that Bennu likely formed in a similar region of the SolarSystem as CI chondrites and potentially at a similar time of Solar System evolution.

Greg Brennecka↗

Calcium-stimulated autophosphorylation site of plant chimeric calcium/calmodulin-dependent protein kinase

The existence of two molecular switches regulating plant chimeric Ca(2+)/calmodulin-dependent protein kinase (CCaMK), namely the C-terminal visinin-like domain acting as Ca(2+)-sensitive molecular switch and calmodulin binding domain acting as Ca(2+)-stimulated autophosphorylation-sensitive molecular switch, has been described (Sathyanarayanan, P. V., Cremo, C. R., and Poovaiah, B. W. (2000) J. Biol. Chem. 275, 30417-30422). Here we report the identification of Ca(2+)-stimulated autophosphorylation site of CCaMK by matrix-assisted laser desorption ionization time of flight-mass spectrometry. Thr(267) was confirmed as the Ca(2+)-stimulated autophosphorylation site by post-source decay experiments and by site-directed mutagenesis. The purified T267A mutant form of CCaMK did not show Ca(2+)-stimulated autophosphorylation, autophosphorylation-dependent variable calmodulin affinity, or Ca(2+)/calmodulin stimulation of kinase activity. Sequence comparison of CCaMK from monocotyledonous plant (lily) and dicotyledonous plant (tobacco) suggests that the autophosphorylation site is conserved. This is the first identification of a phosphorylation site specifically responding to activation by second messenger system (Ca(2+) messenger system) in plants. Homology modeling of the kinase and calmodulin binding domain of CCaMK with the crystal structure of calcium/calmodulin-dependent protein kinase 1 suggests that the Ca(2+)-stimulated autophosphorylation site is located on the surface of the kinase and far from the catalytic site. Analysis of Ca(2+)-stimulated autophosphorylation with increasing concentration of CCaMK indicates the possibility that the Ca(2+)-stimulated phosphorylation occurs by an intermolecular mechanism.

Non-NASA Center↗

Expression of spicule matrix protein gene SM30 in embryonic and adult mineralized tissues of sea urchin Hemicentrotus pulcherrimus

We have isolated a cDNA clone for spicule matrix protein, SM30, from sea urchin Hemicentrotus pulcherrimus and have studied the expression of this gene in comparison with that of another spicule matrix protein gene, SM50. In cultured micromeres as well as in intact embryos transcripts of SM30 were first detectable around the onset of spicule formation and rapidly increased with the growth of spicules, which accompanied accumulation of glycosylated SM30 protein(s). When micromeres were cultured in the presence of Zn2+, spicule formation and SM30 expression were suppressed, while both events resumed concurrently after the removal of Zn2+ from the culture medium. Expression of SM50, in contrast, started before the appearance of spicules and was not sensitive to Zn2+. Differences were also observed in adult tissues; SM30 mRNA was detected in spines and tube feet but not in the test, while SM50 mRNA was apparent in all of these mineralized tissues at similar levels. These results strongly suggest that the SM30 gene is regulated by a different mechanism to that of the SM50 gene and that the products of these two genes are differently involved in sea urchin biomineralization. A possible role of SM30 protein in skeleton formation is discussed.

NASA Discipline Musculoskeletal↗

5' modification of duplex DNA with a ruthenium electron donor-acceptor pair using solid-phase DNA synthesis

Incorporation of metalated nucleosides into DNA through covalent modification is crucial to measurement of thermal electron-transfer rates and the dependence of these rates with structure, distance, and position. Here, we report the first synthesis of an electron donor-acceptor pair of 5' metallonucleosides and their subsequent incorporation into oligonucleotides using solid-phase DNA synthesis techniques. Large-scale syntheses of metal-containing oligonucleotides are achieved using 5' modified phosporamidites containing [Ru(acac)(2)(IMPy)](2+) (acac is acetylacetonato; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (3) and [Ru(bpy)(2)(IMPy)](2+) (bpy is 2,2'-bipyridine; IMPy is 2'-iminomethylpyridyl-2'-deoxyuridine) (4). Duplexes formed with the metal-containing oligonucleotides exhibit thermal stability comparable to the corresponding unmetalated duplexes (T(m) of modified duplex = 49 degrees C vs T(m) of unmodified duplex = 47 degrees C). Electrochemical (3, E(1/2) = -0.04 V vs NHE; 4, E(1/2) = 1.12 V vs NHE), absorption (3, lambda(max) = 568, 369 nm; 4, lambda(max) = 480 nm), and emission (4, lambda(max) = 720 nm, tau = 55 ns, Phi = 1.2 x 10(-)(4)) data for the ruthenium-modified nucleosides and oligonucleotides indicate that incorporation into an oligonucleotide does not perturb the electronic properties of the ruthenium complex or the DNA significantly. In addition, the absence of any change in the emission properties upon metalated duplex formation suggests that the [Ru(bpy)(2)(IMPy)](2+)[Ru(acac)(2)(IMPy)](2+) pair will provide a valuable probe for DNA-mediated electron-transfer studies.

Non-NASA Center↗

Temporal expression and immunogold localization of Plodia interpunctella granulosis virus structural proteins

Monospecific antisera were produced against four structural proteins (VP12, VP17, VP31, and granulin) of the Plodia interpunctella granulosis virus using polypeptides derived by sodium dodecyl sulfate-polyacrylamide gel electrophoresis or acid extraction. The antisera were shown to be specific on immunoblots of SDS-PAGE separated granulosis virus and were further used to detect structural proteins in infected fat body lysates. Immunoblots of fat body lysates from early stages of infection indicated that VP12, VP17, VP31, and granulin were expressed by 2.5 days post-infection. Immunogold labeling of the virus using the monospecific antisera and electron microscopy confirmed earlier reports that granulin is located in the protein matrix, V17 is an envelope protein, and VP31 is a capsid protein.

Non-NASA Center↗

Feasibility study: Atmospheric general circulation experiment, volume 1

The atmospheric general circulation experiment (AGCE) uses a rotating fluid flow cell assembly. The key technical areas affecting the feasibility of the design and operation of the AGCE are investigated. The areas investigated include materials for the flow cell assembly, thermal design, high voltage power supply design, effective retrieval and handling of experiment data and apparatus configuration. Several materials, DMSO and m-tolunitrile, were selected as candidate fluids for the flow cell principally for their high dielectric constant which permits the high voltage power supply design to be held to 15 kV and still simulate terrestrial gravity. Achievement of a low dissipation factor in the fluid to minimize internal heating from the applied electrical field depends strongly on purification and handling procedures. The use of sapphire as the outer hemisphere for the flow cell provides excellent viewing conditions without a significant impact on attaining the desired thermal gradients. Birefringent effects from sapphire can be held to acceptably low limits. Visualization of flow fluid is achieved through the motion of a dot matrix formed by photochromic dyes. Two dyes found compatible with the candidate fluids are spiropyran and triarylmethane. The observation of the dot motion is accomplished using a flying spot scanner.

Homsey, R. J.↗

Urban Biomining Meets Printable Electronics: End-To-End at Destination Biological Recycling and Reprinting

Space missions rely utterly on metallic components, from the spacecraft to electronics. Yet, metals add mass, and electronics have the additional problem of a limited lifespan. Thus, current mission architectures must compensate for replacement. In space, spent electronics are discarded; on earth, there is some recycling but current processes are toxic and environmentally hazardous. Imagine instead an end-to-end recycling of spent electronics at low mass, low cost, room temperature, and in a non-toxic manner. Here, we propose a solution that will not only enhance mission success by decreasing upmass and providing a fresh supply of electronics, but in addition has immediate applications to a serious environmental issue on the Earth. Spent electronics will be used as feedstock to make fresh electronic components, a process we will accomplish with so-called 'urban biomining' using synthetically enhanced microbes to bind metals with elemental specificity. To create new electronics, the microbes will be used as 'bioink' to print a new IC chip, using plasma jet electronics printing. The plasma jet electronics printing technology will have the potential to use martian atmospheric gas to print and to tailor the electronic and chemical properties of the materials. Our preliminary results have suggested that this process also serves as a purification step to enhance the proportion of metals in the 'bioink'. The presence of electric field and plasma can ensure printing in microgravity environment while also providing material morphology and electronic structure tunabiity and thus optimization. Here we propose to increase the TRL level of the concept by engineering microbes to dissolve the siliceous matrix in the IC, extract copper from a mixture of metals, and use the microbes as feedstock to print interconnects using mars gas simulant. To assess the ability of this concept to influence mission architecture, we will do an analysis of the infrastructure required to execute this concept on Mars, and additional opportunities it could offer mission design from the biological and printing technologies. In addition, we will do an analysis of the impact of this technology for terrestrial applications addressing in particular environmental concerns and availability of metals.

Space mission↗

NASA Tech Briefs, August 2009

Topics covered include: Aligning a Receiving Antenna Array to Reduce Interference; Collecting Ground Samples for Balloon-Borne Instruments; Tethered Pyrotechnic Apparatus for Acquiring a Ground Sample; Enhanced Video-Oculography System; Joint Carrier-Phase Synchronization and LDPC Decoding; Dual-Polarization, Sideband-Separating, Balanced Receiver for 1.5 THz Modular Battery Charge Controller; Efficient Multiplexer FPGA Block Structures Based on G4FETs; VLSI Microsystem for Rapid Bioinformatic Pattern Recognition; Low-Noise Amplifier for 100 to 180 GHz; Improved Fabrication of Ceramic Matrix Composite/Foam Core Integrated Structures; Inert Welding/Brazing Gas Filters and Dryers; Fabricating Copper Nanotubes by Electrodeposition; Reducing Aerodynamic Drag on Empty Open Cargo Vehicles; Rotary Percussive Auto-Gopher for Deep Drilling and Sampling; More About Reconfigurable Exploratory Robotic Vehicles; Thermostatic Valves Containing Silicone-Oil Actuators; Improving Heat Flux Performance of Flat Surface in Spray-Cooling Systems; Treating Fibrous Insulation to Reduce Thermal Conductivity; Silica-Aerogel Composites Opacified with La(sub0.7)Sr(sub0.3)MnO3; Cyclic Oxidation Behavior of CuCrAl Cold-Sprayed Coatings for Reusable Launch Vehicles; Ceramic Fiber Structures for Cryogenic Load-Bearing Applications; Elastomer Reinforced with Carbon Nanotubes; Biologically Inspired Purification and Dispersion of SWCNTs; A Technique for Adjusting Eigenfrequencies of WGM Resonators; Low-Pressure, Field-Ionizing Mass Spectrometer; Modifying Operating Cycles to Increase Stability in a LITS; Chamber for Simulating Martian and Terrestrial Environments; Algorithm for Detecting a Bright Spot in an Image; Extreme Programming: Maestro Style; Adaptive Behavior for Mobile Robots; Protocol for Communication Networking for Formation Flying; Planning Complex Sequences Using Compressed Representations; and Self-Supervised Learning of Terrain Traversability from Proprioceptive Sensors.

Source record↗

Covisualization by computational optical-sectioning microscopy of integrin and associated proteins at the cell membrane of living onion protoplasts

Using higher-resolution wide-field computational optical-sectioning fluorescence microscopy, the distribution of antigens recognized by antibodies against animal beta 1 integrin, fibronectin, and vitronectin has been visualized at the outer surface of enzymatically protoplasted onion epidermis cells and in depectinated cell wall fragments. On the protoplast all three antigens are colocalized in an array of small spots, as seen in raw images, in Gaussian filtered images, and in images restored by two different algorithms. Fibronectin and vitronectin but not beta 1 integrin antigenicities colocalize as puncta in comparably prepared and processed images of the wall fragments. Several control visualizations suggest considerable specifity of antibody recognition. Affinity purification of onion cell extract with the same anti-integrin used for visualization has yielded protein that separates in SDS-PAGE into two bands of about 105-110 and 115-125 kDa. These bands are again recognized by the visualization antibody, which was raised against the extracellular domain of chicken beta 1 integrin, and are also recognized by an antibody against the intracellular domain of chicken beta 1 integrin. Because beta 1 integrin is a key protein in numerous animal adhesion sites, it appears that the punctate distribution of this protein in the cell membranes of onion epidermis represents the adhesion sites long known to occur in cells of this tissue. Because vitronectin and fibronection are matrix proteins that bind to integrin in animals, the punctate occurrence of antigenically similar proteins both in the wall (matrix) and on enzymatically prepared protoplasts reinforces the concept that onion cells have adhesion sites with some similarity to certain kinds of adhesion sites in animals.

NASA Discipline Plant Biology↗

Enhancement of anion-exchange chromatography of DNA using compaction agents

The use of adsorptive chromatography for preparative nucleic acid separations is often limited by low capacity. The possibility that the adsorbent surface area sterically accessible to nucleic acid molecules could be increased by reducing their radius of gyration with compaction agents has been investigated. The equilibrium adsorption capacity of Q Sepharose anion-exchange matrix for plasmid DNA at 600 mM NaCl was enhanced by up to ca. 40% in the presence of 2.5 mM spermine. In addition, compaction agent selectivity has been demonstrated. Spermine, for example, enhances the adsorption of both plasmid and genomic DNA, spermidine enhances binding only of plasmid, and hexamine cobalt enhances only the binding of genomic DNA. Compaction may be generally useful for enhancing adsorptive separations of nucleic acids.

NASA Discipline Environmental Health↗

Improvements in Production of Single-Walled Carbon Nanotubes

A continuing program of research and development has been directed toward improvement of a prior batch process in which single-walled carbon nanotubes are formed by catalytic disproportionation of carbon monoxide in a fluidized-bed reactor. The overall effect of the improvements has been to make progress toward converting the process from a batch mode to a continuous mode and to scaling of production to larger quantities. Efforts have also been made to optimize associated purification and dispersion post processes to make them effective at large scales and to investigate means of incorporating the purified products into composite materials. The ultimate purpose of the program is to enable the production of high-quality single-walled carbon nanotubes in quantities large enough and at costs low enough to foster the further development of practical applications. The fluidized bed used in this process contains mixed-metal catalyst particles. The choice of the catalyst and the operating conditions is such that the yield of single-walled carbon nanotubes, relative to all forms of carbon (including carbon fibers, multi-walled carbon nanotubes, and graphite) produced in the disproportionation reaction is more than 90 weight percent. After the reaction, the nanotubes are dispersed in various solvents in preparation for end use, which typically involves blending into a plastic, ceramic, or other matrix to form a composite material. Notwithstanding the batch nature of the unmodified prior fluidized-bed process, the fluidized-bed reactor operates in a continuous mode during the process. The operation is almost entirely automated, utilizing mass flow controllers, a control computer running software specific to the process, and other equipment. Moreover, an important inherent advantage of fluidized- bed reactors in general is that solid particles can be added to and removed from fluidized beds during operation. For these reasons, the process and equipment were amenable to modification for conversion from batch to continuous production.

Balzano, Leandro↗