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NASA NTRS1996

Redox-mediated activation of latent transforming growth factor-beta 1

Transforming growth factor beta 1 (TGF beta) is a multifunctional cytokine that orchestrates response to injury via ubiquitous cell surface receptors. The biological activity of TGF beta is restrained by its secretion as a latent complex (LTGF beta) such that activation determines the extent of TGF beta activity during physiological and pathological events. TGF beta action has been implicated in a variety of reactive oxygen-mediated tissue processes, particularly inflammation, and in pathologies such as reperfusion injury, rheumatoid arthritis, and atherosclerosis. It was recently shown to be rapidly activated after in vivo radiation exposure, which also generates reactive oxygen species (ROS). In the present studies, the potential for redox-mediated LTGF beta activation was investigated using a cell-free system in which ROS were generated in solution by ionizing radiation or metal ion-catalyzed ascorbate reaction. Irradiation (100 Gray) of recombinant human LTGF beta in solution induced 26% activation compared with that elicited by standard thermal activation. Metal-catalyzed ascorbate oxidation elicited extremely efficient recombinant LTGF beta activation that matched or exceeded thermal activation. The efficiency of ascorbate activation depended on ascorbate concentrations and the presence of transition metal ions. We postulate that oxidation of specific amino acids in the latency-conferring peptide leads to a conformation change in the latent complex that allows release of TGF beta. Oxidative activation offers a novel route for the involvement of TGF beta in tissue processes in which ROS are implicated and endows LTGF beta with the ability to act as a sensor of oxidative stress and, by releasing TGF beta, to function as a signal for orchestrating the response of multiple cell types. LTGF beta redox sensitivity is presumably directed toward recovery of homeostasis; however, oxidation may also be a mechanism of LTGF beta activation that can be deleterious during disease mechanisms involving chronic ROS production.

Non-NASA Center↗

NASA NTRS1977

The new applications of sputtering and ion plating

The potential industrial applications of sputtering and ion plating are strictly governed by the unique features these methods possess. The outstanding features of each method, the resultant coating characteristics and the various sputtering modes and configurations are discussed. New, more complex coatings and deposits can be developed such as graded composition structures (metal-ceramic seals), laminated and dispersion strengthened composites which improve the mechanical properties and high temperature stability. Specific industrial areas where future effort of sputtering and ion plating will concentrate to develop intricate alloy or compound coatings and solve difficult problem areas are discussed.

Spalvins, T.↗

NASA NTRS1977

The new applications of sputtering and ion plating

Spalvins, T.↗

NASA NTRS2008

Split-Block Waveguide Polarization Twist for 220 to 325 GHz

A split-block waveguide circuit that rotates polarization by 90 has been designed with WR-3 input and output waveguides, which are rectangular waveguides used for a nominal frequency range of 220 to 325 GHz. Heretofore, twisted rectangular waveguides equipped with flanges at the input and output have been the standard means of rotating the polarizations of guided microwave signals. However, the fabrication and assembly of such components become difficult at high frequency due to decreasing wavelength, such that twisted rectangular waveguides become impractical at frequencies above a few hundred gigahertz. Conventional twisted rectangular waveguides are also not amenable to integration into highly miniaturized subassemblies of advanced millimeter- and submillimeter-wave detector arrays now undergoing development. In contrast, the present polarization- rotating waveguide can readily be incorporated into complex integrated waveguide circuits such as miniaturized detector arrays fabricated by either conventional end milling of metal blocks or by deep reactive ion etching of silicon blocks. Moreover, the present split-block design can be scaled up in frequency to at least 5 THz. The main step in fabricating a splitblock polarization-rotating waveguide of the present design is to cut channels having special asymmetrically shaped steps into mating upper and lower blocks (see Figure 1). The dimensions of the steps are chosen to be consistent with the WR-3 waveguide cross section, which is 0.864 by 0.432 mm. The channels are characterized by varying widths with constant depths of 0.432, 0.324, and 0.216 mm and by relatively large corner radii to facilitate fabrication. The steps effect both a geometric transition and the corresponding impedance-matched electromagnetic-polarization transition between (1) a WR-3 rectangular waveguide oriented with the electric field vector normal to the block mating surfaces and (2) a corresponding WR-3 waveguide oriented with its electric field vector parallel to the mating surfaces of the blocks. A prototype has been built and tested. Figure 2 presents test results indicative of good performance over nearly the entire WR-3 waveguide frequency band.

Ward, John↗

NASA NTRS1988

Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

Isenberg, Arnold O.↗

NASA NTRS2022

Overcoming Universal Restrictions on Metal Selectivity by Protein Design

Selective metal coordination is central to the functions of metalloproteins:1,2 each metalloprotein must pair with its cognate metallocofactor to fulfl its biological role3 . However, achieving metal selectivity solely through a three-dimensional protein structure is a great challenge, because there is a limited set of metal-coordinating amino acid functionalities and proteins are inherently fexible, which impedes steric selection of metals3,4 . Metal-binding afnities of natural proteins are primarily dictated by the electronic properties of metal ions and follow the Irving–Williams series5 (Mn2+ < Fe2+ < Co2+ < Ni2+ Zn2+) with few exceptions6,7 . Accordingly, metalloproteins overwhelmingly bind Cu2+ and Zn2+ in isolation, regardless of the nature of their active sites and their cognate metal ions1,3,8 . This led organisms to evolve complex homeostatic machinery and non-equilibrium strategies to achieve correct metal speciation1,3,8–10. Here we report an artifcial dimeric protein, (AB)2, that thermodynamically overcomes the Irving–Williams restrictions in vitro and in cells, favouring the binding of lower-Irving–Williams transition metals over Cu2+, the most dominant ion in the Irving–Williams series. Counter to the convention in molecular design of achieving specifcity through structural preorganization, (AB)2 was deliberately designed to be fexible. This fexibility enabled (AB)2 to adopt mutually exclusive, metal-dependent conformational states, which led to the discovery of structurally coupled coordination sites that disfavour Cu2+ ions by enforcing an unfavourable coordination geometry. Aside from highlighting fexibility as a valuable element in protein design, our results illustrate design principles for constructing selective metal sequestration agents.

Tae Su Choi↗

NASA NTRS1983

Interaction of metal ions and amino acids - Possible mechanisms for the adsorption of amino acids on homoionic smectite clays

A semiempirical molecular orbital method is used to characterize the binding of amino acids to hexahydrated Cu(2+) and Ni(2+), a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays. Five alpha-amino acids, beta-alanine, and gamma-aminobutyric acid were used to investigate the metal ion and amino acid specificity in binding. It was assumed that the alpha, beta, and gamma-amino acids would bind as bidentate anionic ligands, forming either 1:1 or 1:2 six-coordinated five, six, and seven-membered-ring chelate complexes, respectively. Energies of complex formation, optimized geometries, and electron and spin distribution were determined; and steric constraints of binding of the amino acids to the ion-exchanged cations in the interlamellar spacing of a clay were examined. Results indicate that hexahydrated Cu(2+) forms more stable complexes than hexahydrated Ni(2+) with all the amino acids studied. However, among these amino acids, complex formation does not favor the adsorption of the biological subset. Calculated energetics of complex formation and steric constraints are shown to predict that 1:1 rather than 1:2 metal-amino acid complexes are generally favored in the clay.

Gupta, A.↗

NASA NTRS1981

Midlatitude sporadic-E layers

Rocket borne probes and incoherent scatter radar were demonstrated to be effective methods of studying the structure of midlatitude sporadic E layers. Layers are formed when metal ions are converged vertically in a wind shear to produce a local enhancement of electron density. Rocket and radar observations show that the layers may occassionally have complex structure produced by an unstable wind shear. The partial transparency to radio waves of sporadic E layers is shown to be due to localized regions of high electron density.

Smith, L. G.↗

NASA NTRS1990

Recovery of precious metals in space

This program is proceeding along the lines compatible with the objective of developing feasible separation and recovery processes for precious metals in a space environment. Efficient, compact, solvent extraction systems (both single and multistage) capable of high selectivity and rapid equilibration that are based on chelate and ion pair complexes are being explored. Two research projects were undertaken: (1) study of the time-dependent aspects of the formation of Pd(2) extractable chelate complexes; and (2) development of a multistage countercurrent distribution process for the separation and recovery of Pd(2) and Pt(2) ions.

Freiser, H.↗

NASA NTRS1981

Aluminum ions enhance polyimide adhesive

Adding complexed aluminum ions raises useful temperature of polyimide adhesive without embrittling it or reducing long term stability. Adhesives may be applied to prepared substrate surface without supports. Possible substrates are metal, composite, or polymeric film. Adhesive is excellent where bond flexibility is required.

St.clair, A. K.↗

NASA NTRS1992

Recovery and separation of precious metals from space

During the past year a viable procedure centered around centrifugal partition chromatography (CPC), a multistage liquid-liquid partitioning technique for the separation of precious metals (Pt, Pd, Rh, Ir, Os, Ru), was developed. Stable and inexpensive ligands that can be readily recycled to achieve the separations of the precious metals were identified. The separation methods developed so far yield three separate fractions: Pt, Pd, and Rh-Ir. The Rh-Ir pair can be separated in a subsequent run. The total amount of precious metals separated in a single experiment varied from 1 to 50 mg. The factors affecting the efficiencies of these separations were studied. The kinetics of the decomposition of the complex and the ion pair have a major bearing on these efficiencies, with slow kinetics resulting in poor efficiencies. The methods for the improvement of the efficiencies were also investigated. For example, significant improvement in the efficiencies and separation times for Pt and Pd were achieved by the use of chloride gradient in the mobile phase. Two papers were published and talks were presented on our work at the FACSS meeting in Anaheim, Oct. 1991, and at the Pittsburgh Conference in New Orleans, Mar. 1992.

Freiser, H.↗

NASA NTRS1991

Recovery of precious metals from space

The overall objective is to develop efficient and economical separation and recovery methods for the platinum group and other precious metals. The separation of Pd(II) from Pt(II), Ir(III), and Rh(III) with trioctylphosphine oxide (TOPO) in heptane using centrifugal partition chromatography (CPC) was investigated. Activities to achieve this objective focussed on selection and evaluation of extraction systems for the PGM and modification of selected systems for multistage operation with a view to scaling up to desired macro levels. On the basis of preliminary evaluation of a series of simple metal complexing agents and chelating agents, the TOPO in heptane was selected as a likely system for isolating of Pd(II) and Pt(II) from the other PGM. A multistage apparatus capable of configuration as a simple rugged device, a centrifugal partition chromatograph (CPC), was shown to be effective. The extraction of Pd(II) was studied by CPC and batch solvent extraction. The distribution ratios for Pd(II) determined by both methods agree well. In low HCl concentrations (less than 0.1 M), the extracted species was PdCl2.(TOPO)2, irrespective of the chloride concentration, while at acid concentrations above 0.1 M, the Pd was extracted as the ion pair, 2(TOPO.H+).(PdCl4)2-. Base line separation of Pd(II) and Pt(II) in CPC was obtained under a variety of chloride and HCl concentration. It was demonstrated that the efficiency of CPC for metal separation was limited by chemical kinetic factors rather than instrumental factors, strongly suggesting that dramatic improvements can be achieved by studying reaction kinetics of formation and dissociation of the extractable metal complex.

Freiser, Henry↗

NASA NTRS2012

Solar Ion Sputter Deposition in the Lunar Regolith: Experimental Simulation Using Focused-Ion Beam Techniques

As regions of the lunar regolith undergo space weathering, their component grains develop compositionally and microstructurally complex outer coatings or "rims" ranging in thickness from a few 10 s to a few 100's of nm. Rims on grains in the finest size fractions (e.g., <20 m) of mature lunar regoliths contain optically-active concentrations of nm size metallic Fe spherules, or "nanophase Fe(sup o)" that redden and attenuate optical reflectance spectral features important in lunar remote sensing. Understanding the mechanisms for rim formation is therefore a key part of connecting the drivers of mineralogical and chemical changes in the lunar regolith with how lunar terrains are observed to become space weathered from a remotely-sensed point of view. As interpreted based on analytical transmission electron microscope (TEM) studies, rims are produced from varying relative contributions from: 1) direct solar ion irradiation effects that amorphize or otherwise modify the outer surface of the original host grain, and 2) nanoscale, layer-like, deposition of extrinsic material processed from the surrounding soil. This extrinsic/deposited material is the dominant physical host for nanophase Fe(sup o) in the rims. An important lingering uncertainty is whether this deposited material condensed from regolith components locally vaporized in micrometeorite or larger impacts, or whether it formed as solar wind ions sputtered exposed soil and re-deposited the sputtered ions on less exposed areas. Deciding which of these mechanisms is dominant, or possibility exclusive, has been hampered because there is an insufficient library of chemical and microstructural "fingerprints" to distinguish deposits produced by the two processes. Experimental sputter deposition / characterization studies relevant to rim formation have particularly lagged since the early post-Apollo experiments of Hapke and others, especially with regard to application of TEM-based characterization techniques. Here we report on a novel design for simulating solar ion sputter deposition in the lunar regolith, with characterization of the resulting sputter deposits by an array of advanced analytical TEM techniques.

Christoffersen, R.↗

NASA NTRS1981

Ion beam deposited protective films

Sputter deposition of adherent thin films on complex geometric surfaces by ion beam sources is examined in order to evaluate three different types of protective coatings for die materials. In the first experiment, a 30 cm diameter argon ion source was used to sputter deposit adherent metallic films up to eight microns thick on H-13 steel, and a thermal fatigue test specimen sputter deposited with metallic coatings one micron thick was immersed in liquid aluminum and cooled by water for 15,000 cycles to simulate operational environments. Results show that these materials do protect the steel by reducing thermal fatigue and thereby increasing die lifetime. The second experiment generated diamond-like carbon films using a dual beam ion source system that directed an eight cm argon ion source beam at the substrates. These films are still in the process of being evaluated for crystallinity, hardness and infrared absorption. The third experiment coated a fiber glass beam shield incorporated in the eight-cm diameter mercury ion thruster with molybdenum to ensure proper electrical and thermal properties. The coating maintained its integrity even under acceleration tests.

Mirtich, M. J.↗

NASA NTRS2013

Space Weathering of Lunar Rocks and Regolith Grains

The exposed surfaces of lunar soil grains and lunar rocks become modified and coated over time with a thin rind of material (patina) through complex interactions with the space environment. These interactions encompass many processes including micrometeorite impacts, vapor and melt deposition, and solar wind implantation/sputtering effects that collectively are referred to as "space weathering". Studies of space weathering effects in lunar soils and rocks provide important clues to understanding the origin and evolution of the lunar regolith as well as aiding in the interpretation of global chemical and mineralogical datasets obtained by remote-sensing missions. The interpretation of reflectance spectra obtained by these missions is complicated because the patina coatings obscure the underlying rock mineralogy and compositions. Much of our understanding of these processes and products comes from decades of work on remote-sensing observations of the Moon, the analysis of lunar samples, and laboratory experiments. Space weathering effects collectively result in a reddened continuum slope, lowered albedo, and attenuated absorption features in reflectance spectra of lunar soils as compared to finely comminuted rocks from the same Apollo sites. Space weathering effects are largely surface-correlated, concentrated in the fine size fractions, and occur as amorphous rims on individual soil grains. Rims on lunar soil grains are highly complex and span the range between erosional surfaces modified by solar wind irradiation to depositional surfaces modified by the condensation of sputtered ions and impact-generated vapors. The optical effects of space weathering effects are directly linked to the production of nanophase Fe metal in lunar materials]. The size of distribution of nanophase inclusions in the rims directly affect optical properties given that large Fe(sup o) grains (approx 10 nm and larger) darken the sample (lower albedo) while the tiny Fe(sup o) grains (<5nm) are the primary agent in spectral "reddening". More recent work has focused on the nature and abundance of OH/H2O in the lunar regolith using orbital data and samples analyses. Advances in sample preparation techniques have made possible detailed analyses of patina-coated rock surfaces. Major advances are occurring in quantifying the rates and efficiency of space weathering processes through laboratory experimentation.

Keller, L. P.↗

NASA NTRS1972

SCC of Ti-6Al-4V foil by methanol - Effect of treatments with 2,4-pentanedione and its metal complexes.

The susceptibility of Ti-6Al-4V foil to stress corrosion cracking (SCC) by methanol can be decreased by treatment of the foil with 2,4-pentanedione prior to its immersion in the corroding media. It is assumed that such treatments remove from the protective film formed on the foil by exposure to the atmosphere, certain metal ions whose oxides are more readily penetrated by the ions, Na + and Cl- or Fe(3+) and Cl-, present in the corroding media.

Haney, E. G.↗

NASA NTRS1975

Determination of hydroxide and carbonate contents of alkaline electrolytes containing zinc

A method to prevent zinc interference with the titration of OH- and CO3-2 ions in alkaline electrolytes with standard acid is presented. The Ba-EDTA complex was tested and shown to prevent zinc interference with acid-base titrations without introducing other types of interference. Theoretical considerations indicate that this method can be used to prevent interference by other metals.

Otterson, D. A.↗

NASA NTRS2017

Pt: Ti Diffusion Barrier, Interconnect, and Simultaneous Ohmic Contacts to n- and p-type 4H-SiC

We report the initial results of using co-sputtered Pt:Ti 80:20 at. % composition ratio metallization as a diffusion barrier against gold (Au) and oxygen (O), as an interconnect layer, as well as forming simultaneous ohmic contacts to n-and p-type 4H-SiC. Having a single conductor with such combined multi-functional attributes would appreciably reduce the fabrication costs, processing time and complexity that are inherent in the production of SiC based devices. Auger Electron Spectroscopy, Focused Ion Beam-assisted Field Emission Scanning Electron Microscopy and Energy Dispersive Spectroscopy analyses revealed no Au and O migration to the SiC contact surface and minimal diffusion through the Pt:Ti barrier layer after 15 minutes of exposure at 800 °C in atmosphere, thus offering potential long term stability of the ohmic contacts. Specific contact resistance values of 7 x 10(exp -5) and 7.4 x 10(exp -4) Ω-sq.cm were obtained on the n (N(sub d)=7 x 10(exp 18) per cu.cm and p (N(sub a)=2 x 10(exp 20) per cu. cm) -type 4H-SiC, respectively. The resistivity of 75 μΩ-cm was obtained for the Pt:Ti layer that was sandwiched between two SiO2 layers and annealed in pure O ambient up to 900 °C, which offers promise as a high temperature interconnect metallization.

Simultaneous Ohmic Contact↗