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At least 19 records

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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 NTRS1998

Syntheses of Octasubstituted Metal Phthalocyanines for Nonlinear Optics

Many organic materials can be used as nonlinear optical media. Phthalocyanines are of special interest because they show an unusually large third order nonlinear response, they are thermally and photochemically stable and they can be formed into oriented thin films (Langmuir-Blodgett films). They also can be easily complexed by a large variety of metals, which place them at the interface between organics and organometallics, and allows for fine tuning of the macro cycle electronic properties by the coordinated metal and substituent groups. A series of 1,4,8,11,15,18,22,25-octaalkoxy metal-free and metal phthalocyanines and 2,3,9,10,16,17,23,24-octaalkoxy metal phthalocyanines has been synthesized. Their nonlinear optical properties have been measured. The physical properties of all the phthalocyanines synthesized in this work are subject to both acid and solvent effects.

Guo, Huaisong↗

NASA NTRS2003

Synthesis and CV Studies of Dithiol-terminated Metal Terpyridine Complexes

Transition metal coordination complexes possess unique electronic structures that should be a good model for studying electronic transport behavior at a molecular level. The discrete, multiple redox states, low redox potential and the superb ability to establish contact with other molecular and electronic components by coordination chemistry have made this a subject of investigation for their possible application as active electronic components in molecular devices. We present the synthesis and electrochemical characterization of 4'-thioacetylphenyl-2'2:6',2"-terpyridine iron(II) complex and compare it with a model bis-terpyridine iron(II) complex by cyclic voltammetry. With the use of different working electrodes, the behavior of these complexes show different electron transfer rates.

Asano, Sylvia↗

NASA NTRS2020

Metal-Templated Design of Chemically Switchable Protein Assemblies with High-Affinity Coordination Sites

To mimic a hypothetical pathway for protein evolution, we previously tailored a monomeric protein (cyt cb562) for metal-mediated self-assembly, followed by re-design of the resulting oligomers for enhanced stability and metal-based functions. We show that a single hydrophobic mutation on the cyt cb562 surface drastically alters the outcome of metal-directed oligomerization to yield a new trimeric architecture, (TriCyt1)3. This nascent trimer was redesigned into second and third-generation variants (TriCyt2)3 and (TriCyt3)3 with increased structural stability and preorganization for metal coordination. The three TriCyt variants combined furnish a unique platform to 1) provide tunable coupling between protein quaternary structure and metal coordination, 2) enable the construction of metal/pH-switchable protein oligomerization motifs, and 3) generate a robust metal coordination site that can coordinate all mid-to-late first-row transition-metal ions with high affinity.

Albert Kakkis↗

NASA NTRS1982

Production of metal particles and clusters

The feasibility of producing novel metals or metal clusters in a low gravity environment was studied. The production of coordinately unsaturated metal carbonyls by thermolysis or photolysis of stable metal carbonyls has the potential to generate novel catalysts by this technique. Laser irradiation of available metal carbonyls was investigated. It is found that laser induced decomposition of metal carbonyls is feasible for producing a variety of coordinately unsaturated species. Formation of clustered species does occur but is hampered by weak metal-metal bonds.

Mcmanus, S. P.↗

NASA NTRS1989

Non-noble electrocatalysts for alkaline fuel cells

Carbons activated with macrocyclics have attracted increasing attention as alternative electrocatalysts for oxygen reduction. Initial activity of these catalysts is good, but performance declines rapidly. Pyrolyzing the macrocyclic on the carbon support leads to enhanced stability and the catalysts retain good activity. The approach described is designed to develop bulk doped catalysts with similar structures to pyrolyzed macrocyclic catalysts. The transition metal and coordinated ligands are dispersed throughout the bulk of the conductive carbon skeleton. Two approaches to realizing this concept are being pursued, both involving the doping of carbon precursors. In one approach, the precursor is a solid phase carbon-containing ion-exchange resin. The precursor is doped with a transition metal and/or nitrogen, and the resulting mixture is pyrolyzed. In the other approach, the precursor is a gas-phase hydrocarbon. This is introduced with a transition metal species and nitrogen species into a reactor and pyrolyzed. Several studies have been conducted to determine if there is a synergistic effect between the transition metal and nitrogen and the effect of different methods of introducing the metal-nitrogen (M-N) coordination on performance. One approach was to introduce the metal and nitrogen separately, for example, by sequentially doping FeCl3 and NH4OH into the resin. Catalysts were prepared from an undoped ion-exchange resin, a resin doped only with N, a resin doped only with Fe, and a resin doped with both Fe and N. Introduction of nitrogen alone has no beneficial effect on the performance of the catalysts. The introduction of the Fe alone significantly improves the performance in both the high and low current density regions. When both Fe and N are introduced, the performance at lower current densities (catalytic activity) is increased beyond that of the Fe-doped carbon, but the performance at higher current densities is similar to the carbon containing only Fe. Catalysts prepared from resins-Fe(bipy)3SO4 precursors have performance that is only slightly less then CoTMPP adsorbed and pyroloyzed on Vulcan XC-72. Their performance is much better than carbons which have had the N and Fe introduced separately.

Sarangapani, S.↗

NASA NTRS1979

Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution

In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

Beck, M.↗

NASA NTRS1980

Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3)

A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.

Sheridan, P. S.↗

NASA NTRS1985

Enhanced Raman spectroscopic study of the coordination chemistry of malononitrile on copper surfaces - Removal of nu(C=N) degeneracy through pi-coordination

Surface-enhanced Raman spectroscopy has been used to study the molecular interactions of malononitrile with copper electrode surfaces. The doubly degenerate CN stretching frequency at 2263/cm is removed when malononitrile adsorbs on copper. Two nu(CN) bands are observed at 2096 and 2204/cm at -0.6 V(SCE). The result shows that only one CN group is pi-coordinated with Cu, which contributes to the observed large shift (-167/cm) in nu(CN). The other CN group is not coordinated to the metal surface.

Loo, B. H.↗

NASA NTRS1986

Spacecraft dielectric material properties and spacecraft charging

The physics of spacecraft charging is reviewed, and criteria for selecting and testing semiinsulating polymers (SIPs) to avoid charging are discussed and illustrated. Chapters are devoted to the required properties of dielectric materials, the charging process, discharge-pulse phenomena, design for minimum pulse size, design to prevent pulses, conduction in polymers, evaluation of SIPs that might prevent spacecraft charging, and the general response of dielectrics to space radiation. SIPs characterized include polyimides, fluorocarbons, thermoplastic polyesters, poly(alkanes), vinyl polymers and acrylates, polymers containing phthalocyanine, polyacene quinones, coordination polymers containing metal ions, conjugated-backbone polymers, and 'metallic' conducting polymers. Tables summarizing the results of SIP radiation tests (such as those performed for the NASA Galileo Project) are included.

Frederickson, A. R.↗

NASA NTRS1992

Young globular clusters in the Milky Way Galaxy

Ruprecht 106 and Pal 12 are two known globular clusters in the Milky Way that are unequivocally younger than other clusters of similar metallicity. The Galactic coordinates of Ruprecht 106 place it near to the Magellanic Stream in projection, suggesting a tidal capture from the Magellanic Clouds. It is demonstrated that a family of orbits for both clusters can be constructed that are consistent with this capture hypothesis and that these then lead to a prediction of 3 milliarcseconds per year for the proper motions of both Ruprecht 106 and Pal 12.

Lin, D. N. C.↗

NASA NTRS1975

Moessbauer studies in zinc-manganese ferrites for use in measuring small velocities and accelerations with great precision

Mossbauer spectroscopy was used for a systematic study of the magnetic behavior of manganese and zinc in mixed ferrites. It was observed that Zn2+ has preference to substitute Mn2+ at interstitial sites where the metal ions are tetrahedrally coordinated with four oxygen neighbors. The internal magnetic hyperfine field at the tetrahedral iron site is larger than that at the octahedral site. The relaxation effects were observed to play an important role as the zinc contents were increased, while the spin-correlation time and the magnetic field were observed to decrease in strength. It is concluded that Mossbauer effect data on complex materials, when used in conjunction with other data, can provide useful insight into the origin of the microscopic properties of magnetic materials.

Escue, W. T.↗

NASA NTRS1979

Spectra of Fe-Ti silicate glasses - Implications to remote-sensing of planetary surfaces

Optical spectra of synthetic Fe-Ti silicate glasses and the temperature variations of the spectral features were investigated. The spectra are assigned to absorptions due to crystal field (CF) transitions in Ti(3+), Fe(2+) in octahedral coordination, and Fe(2+) in tetrahedral coordination, and to metal-metal and oxygen-metal charge transfer (CT) transitions which contribute to the near ultraviolet absorption edge. Temperature variations of the optical bands have been studied to explore implications for remote sensing. Caution is urged in the use of the absorption edge as a measure of TiO2 concentrations on planetary surfaces and in regolith samples.

Nolet, D. A.↗

NASA NTRS2016

Relating FTS Catalyst Properties to Performance

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of γ-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.

Zirconia↗

NASA NTRS2002

Characterization of iron, manganese, and copper synthetic hydroxyapatites by electron paramagnetic resonance spectroscopy

The incorporation of micronutrients (e.g., Fe, Mn, Cu) into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in NASA's Advanced Life Support (ALS) program for long-duration space missions. Separate Fe3+ (Fe-SHA), Mn2+ (Mn-SHA), and Cu2+ (Cu-SHA) containing SHA materials were synthesized by a precipitation method. Electron paramagnetic resonance (EPR) spectroscopy was used to determine the location of Fe3+, Mn2+, and Cu2+ ions in the SHA structure and to identify other Fe(3+)-, Mn(2+)-, and Cu(2+)-containing phases that formed during precipitation. The EPR parameters for Fe3+ (g=4.20 and 8.93) and for Mn2+ (g=2.01, A=9.4 mT, D=39.0 mT and E=10.5 mT) indicated that Fe3+ and Mn2+ possessed rhombic ion crystal fields within the SHA structure. The Cu2+ EPR parameters (g(z)=2.488, A(z)=5.2 mT) indicated that Cu2+ was coordinated to more than six oxygens. The rhombic environments of Fe3+ and Mn2+ along with the unique Cu2+ environment suggested that these metals substituted for the 7 or 9 coordinate Ca2+ in SHA. The EPR analyses also detected poorly crystalline metal oxyhydroxides or metal-phosphates associated with SHA. The Fe-, Mn-, and Cu-SHA materials are potential slow release sources of Fe, Mn, and Cu for ALS and terrestrial cropping systems.

NASA Center JSC↗

NASA NTRS2023

Temperature Effect on Silicate Melt-Sulfide-Metal Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

The reduced nature of Mercury, enstatite chondrites, and the aubrite parent bodies (APB) have raised many questions regarding the geochemical behavior of typically lithophile, heat-producing, and rare-earth elements (REE) in magmas at low oxygen fugacity (fO2). Due to decreasing O availability at these low fO2, and an abundance of S(sup 2(-)), sulfur (S) acts as an important anion that changes the partitioning behavior of many elements and modifies the physical properties of silicate melts. Preliminary observations suggest that major and minor elements exhibit different geochemical affinities in highly reduced, S-rich systems compared to terrestrial rocks. The speciation and bonding environment of S, dictated by P/T/fO2 conditions, may strongly influence the degree to which S affects partitioning behavior. Here we investigate the partitioning behavior of major, minor, and trace elements between silicate melt, sulfide melt, and metal as well as the coordination chemistry of S in highly reduced silicate melts. Our work is focused on investigating solely the entropy-dependent temperature effect on partitioning of elements for which we currently have MESSENGER data (K, Na, Th, U, Si, Mg, Fe, Ti, Ca, Al, Cr, Mn, S, Cl) as well as a host of geochemically relevant trace elements such as REEs (P, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb). Previous studies in which temperature, pressure, and fO2 were co-varied found that as fO2 decreases, heat-producing elements U and Th become more chalcophile, while K becomes less chalcophile. Concurrently, nominally lithophile elements Mg and Ca become more chalcophile and were observed as minor elements in exsolved sulfides and bonded with S species in silicate melt. These studies, however, could not disentangle entropic effects from changes in the fO2. New temperature-dependent partitioning data from our work will be used to determine which elements are most likely to retain their lithophile character and hence be incorporated into silicates, and which elements are likely contained within the sulfide (chalcophile) and metal core (siderophile), setting the stage for the thermal and magmatic evolution of reduced planetary bodies.

B A Anzures↗

NASA NTRS1999

Source of Global Scale Variations in the Midday Vertical Content of Ionospheric Metal Ions

An analysis of long baseline NIMBUS 7 SBUV (Solar Backscatter UV Spectrometer) observations of the latitudinal variation of the noontime vertical Mg' content above approx. 70 km have revealed seasonal, solar activity and magnetic activity dependencies in the Mg+ content. The distributions were categorized in terms of magnetic coordinates partially because transport processes lifting metallic ions from the main meteor ionization layer below 100 km up into the F- region and down again are controlled by electrodynamical processes. Alternatively, the Nimbus Mg+ distributions may simply be a result of ion/neutral chemistry changes resulting from atmospheric changes and not dynamics. In such a case magnetic control would not dominate the distributions. Using in situ satellite measurements of metal ions from the Atmosphere Explorer satellites in the region above the main meteor layer and published sounding rocket measurements of the main metallic ion layers, the effects of the dynamics on the vertical content are delineated. The consequences of atmospheric changes on the vertical content are explored by separating the Nimbus measurements in a geodetic frame of reference.

Joiner, J.↗

NASA NTRS2013

Wireless Chalcogenide Nanoionic-Based Radio-Frequency Switch

A new nonvolatile nanoionic switch is powered and controlled through wireless radio-frequency (RF) transmission. A thin layer of chalcogenide glass doped with a metal ion, such as silver, comprises the operational portion of the switch. For the switch to function, an oxidizable electrode is made positive (anode) with respect to an opposing electrode (cathode) when sufficient bias, typically on the order of a few tenths of a volt or more, is applied. This action causes the metal ions to flow toward the cathode through a coordinated hopping mechanism. At the cathode, a reduction reaction occurs to form a metal deposit. This metal deposit creates a conductive path that bridges the gap between electrodes to turn the switch on. Once this conductive path is formed, no further power is required to maintain it. To reverse this process, the metal deposit is made positive with respect to the original oxidizable electrode, causing the dissolution of the metal bridge thereby turning the switch off. Once the metal deposit has been completely dissolved, the process self-terminates. This switching process features the following attributes. It requires very little to change states (i.e., on and off). Furthermore, no power is required to maintain the states; hence, the state of the switch is nonvolatile. Because of these attributes the integration of a rectenna to provide the necessary power and control is unique to this embodiment. A rectenna, or rectifying antenna, generates DC power from an incident RF signal. The low voltages and power required for the nanoionic switch control are easily generated from this system and provide the switch with a novel capability to be operated and powered from an external wireless device. In one realization, an RF signal of a specific frequency can be used to set the switch into an off state, while another frequency can be used to set the switch to an on state. The wireless, miniaturized, and nomoving- part features of this switch make it suitable for applications such as integration into garments, RFID (radio-frequency identification) tags, and conformal structures (e.g., aircraft wings, sounding rockets contours, etc). In the case of RFID tags the innovation will provide countermeasures to attempts for identity theft and other uninvited attempts for retrieval of information. It could also be applicable to the automotive industry as well as the aerospace industry for collision avoidance and phased array radar systems, respectively

Nessel, James↗