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NASA NTRS1997

Determination of ammonia in ethylene using ion mobility spectrometry

A simple procedure to analyze ammonia in ethylene by ion mobility spectrometry is described. The spectrometer is operated with a silane polymer membrane., 63Ni ion source, H+ (H2O)n reactant ion, and nitrogen drift and source gas. Ethylene containing parts per billion (ppb) (v/v) concentrations of ammonia is pulled across the membrane and diffuses into the spectrometer. Preconcentration or preseparation is unnecessary, because the ethylene in the spectrometer has no noticeable effect on the analytical results. Ethylene does not polymerize in the radioactive source. Ethylene's flammability is negated by the nitrogen inside the spectrometer. Response to ammonia concentrations between 200 ppb and 1.5 ppm is near linear, and a detection limit of 25 ppb is calculated.

NASA Discipline Environmental Health↗

NASA NTRS2004

Polyimide/Carbon Nanotube Composite Films for Electrostatic Charge Mitigation

Low color, space environmentally durable polymeric films with sufficient electrical conductivity to mitigate electrostatic charge (ESC) build-up have potential applications on large, deployable, ultra-light weight Gossamer spacecraft as thin film membranes on antennas, solar sails, thermal/optical coatings, multi-layer insulation blankets, etc.. The challenge has been to develop a method to impart robust electrical conductivity into these materials without increasing solar absorptivity (alpha ) or decreasing optical transparency or film flexibility. Since these spacecraft will require significant compaction prior to launch, the film portion of the spacecraft will require folding. The state-of-the-art clear, conductive coating (e.g. indium-tin-oxide, ITO) is brittle and cannot tolerate folding. In this report, doping a polymer with single-walled carbon nanotubes (SWNTs) using two different methods afforded materials with good flexibility and surface conductivities in the range sufficient for ESC mitigation. A coating method afforded materials with minimal effects on the mechanical, optical, and thermo-optical properties as compared to dispersal of SWNTs in the matrix. The chemistry and physical properties of these nanocomposites are discussed.

Smith, Joseph G., Jr.↗

NASA NTRS2000

Technical advance: identification of plant actin-binding proteins by F-actin affinity chromatography

Proteins that interact with the actin cytoskeleton often modulate the dynamics or organization of the cytoskeleton or use the cytoskeleton to control their localization. In plants, very few actin-binding proteins have been identified and most are thought to modulate cytoskeleton function. To identify actin-binding proteins that are unique to plants, the development of new biochemical procedures will be critical. Affinity columns using actin monomers (globular actin, G-actin) or actin filaments (filamentous actin, F-actin) have been used to identify actin-binding proteins from a wide variety of organisms. Monomeric actin from zucchini (Cucurbita pepo L.) hypocotyl tissue was purified to electrophoretic homogeneity and shown to be native and competent for polymerization to actin filaments. G-actin, F-actin and bovine serum albumin affinity columns were prepared and used to separate samples enriched in either soluble or membrane-associated actin-binding proteins. Extracts of soluble actin-binding proteins yield distinct patterns when eluted from the G-actin and F-actin columns, respectively, leading to the identification of a putative F-actin-binding protein of approximately 40 kDa. When plasma membrane-associated proteins were applied to these columns, two abundant polypeptides eluted selectively from the F-actin column and cross-reacted with antiserum against pea annexins. Additionally, a protein that binds auxin transport inhibitors, the naphthylphthalamic acid binding protein, which has been previously suggested to associate with the actin cytoskeleton, was eluted in a single peak from the F-actin column. These experiments provide a new approach that may help to identify novel actin-binding proteins from plants.

Non-NASA Center↗

NASA NTRS1983

The electrochemical fluorination of polymeric materials for high energy density aqueous and non-aqueous battery and fuel cell separators

A computerized system was established and the electrochemical fluorination of trichloroethylene, polyacrylic acid and polyvinyl alcohol in anhydrous hydrogen fluoride was attempted. Both solid substrates as well as membranes were used. Some difficulties were found in handling and analyzing the solid substrates and membranes. Further studies are needed in this area. A microprocessor aided electrochemical fluorination system capable of obtaining highly reproducible experimental results was established.

Liu, C. C.↗

NASA NTRS2007

Multi-Functional Sandwich Composites for Spacecraft Applications: An Initial Assessment

Current spacecraft implement relatively uncoupled material and structural systems to address a variety of design requirements, including structural integrity, damage tolerance, radiation protection, debris shielding and thermal insulation. This investigation provided an initial assessment of multi-functional sandwich composites to integrate these diverse requirements. The need for radiation shielding was addressed through the selection of polymeric constituents with high hydrogen content. To provide increased damage tolerance and debris shielding, manufacturing techniques were developed to incorporate transverse stitching reinforcement, internal layers, and a self-healing ionomer membrane. To assess the effects of a space environment, thermal expansion behavior of the candidate foam materials was investigated under a vacuum and increasing temperature. Finally, a thermal expansion model was developed for foam under vacuum conditions and its predictive capability assessed.

Adams, Daniel O.↗

NASA NTRS1994

Production of RNA by a polymerase protein encapsulated within phospholipid vesicles

Catalyzed polymerization reactions represent a primary anabolic activity of all cells. It can be assumed that early cells carried out such reactions, in which macromolecular catalysts were encapsulated within some type of boundary membrane. In the experiments described here, we show that a template-independent RNA polymerase (polynucleotide phosphorylase) can be encapsulated in dimyristoyl phosphatidylcholine vesicles without substrate. When the substrate adenosine diphosphate (ADP) was provided externally, long-chain RNA polymers were synthesized within the vesicles. Substrate flux was maximized by maintaining the vesicles at the phase transition temperature of the component lipid. A protease was introduced externally as an additional control. Free enzyme was inactivated under identical conditions. RNA products were visualized in situ by ethidium bromide fluorescence. The products were harvested from the liposomes, radiolabeled, and analyzed by polyacrylamide gel electrophoresis. Encapsulated catalysts represent a model for primitive cellular systems in which an RNA polymerase was entrapped within a protected microenvironment.

Non-NASA Center↗

NASA NTRS1994

The growth of zeolites A, X and mordenite in space

Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of supersaturation, and this gel undergoes a continuous 'polymerization' type reaction during nucleation and growth. Generally, for structure characterization and diffusion studies, which are useful in evaluating zeolites for improving yield in petroleum refining as well as for many of the proposed new applications (e.g., catalytic membranes, molecular electronics, chemical sensors) large zeolites (greater than 100 to 1000 times normal size) with minimum lattice defects are desired. Presently, the lack of understanding of zeolite nucleation and growth precludes the custom design of zeolites for these or other uses. It was hypothesized that the microgravity levels achieved in an orbiting spacecraft could help to isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation, which occurs since zeolites are twice as dense as the solution from which they are formed. This was expected to promote larger crystals by allowing growing crystals a longer residence time in a high-concentration nutrient field. Thus it was hypothesized that the microgravity environment of Earth orbit would allow the growth of large, more defect-free zeolite crystals in high yield.

Sacco, Albert, Jr.↗

NASA NTRS1998

Identification of sucrose synthase as an actin-binding protein

Several lines of evidence indicate that sucrose synthase (SuSy) binds both G- and F-actin: (i) presence of SuSy in the Triton X-100-insoluble fraction of microsomal membranes (i.e. crude cytoskeleton fraction); (ii) co-immunoprecipitation of actin with anti-SuSy monoclonal antibodies; (iii) association of SuSy with in situ phalloidin-stabilized F-actin filaments; and (iv) direct binding to F-actin, polymerized in vitro. Aldolase, well known to interact with F-actin, interfered with binding of SuSy, suggesting that a common or overlapping binding site may be involved. We postulate that some of the soluble SuSy in the cytosol may be associated with the actin cytoskeleton in vivo.

Non-NASA Center↗

NASA NTRS2000

The actin cytoskeleton may control the polar distribution of an auxin transport protein

The gravitropic bending of plants has long been linked to the changes in the transport of the plant hormone auxin. To understand the mechanism by which gravity alters auxin movement, it is critical to know how polar auxin transport is initially established. In shoots, polar auxin transport is basipetal (i.e., from the shoot apex toward the base). It is driven by the basal localization of the auxin efflux carrier complex. One mechanism for localizing this efflux carrier complex to the basal membrane may be through attachment to the actin cytoskeleton. The efflux carrier protein complex is believed to consist of several polypeptides, including a regulatory subunit that binds auxin transport inhibitors, such as naphthylphthalamic acid (NPA). Several lines of experimentation have been used to determine if the NPA binding protein interacts with actin filaments. The NPA binding protein has been shown to partition with the actin cytoskeleton during detergent extraction. Agents that specifically alter the polymerization state of the actin cytoskeleton change the amount of NPA binding protein and actin recovered in these cytoskeletal pellets. Actin-affinity columns were prepared with polymers of actin purified from zucchini hypocotyl tissue. NPA binding activity was eluted in a single peak from the actin filament column. Cytochalasin D, which fragments the actin cytoskeleton, was shown to reduce polar auxin transport in zucchini hypocotyls. The interaction of the NPA binding protein with the actin cytoskeleton may localize it in one plane of the plasma membrane, and thereby control the polarity of auxin transport.

Non-NASA Center↗

NASA NTRS1995

Hydroxycinnamic acid-derived polymers constitute the polyaromatic domain of suberin

Suberin is an abundant, complex, intractable, plant cell wall polymeric network that forms both protective and wound-healing layers. Its function is, therefore, critical to the survival of all vascular plants. Its chemical structure and biosynthesis are poorly defined, although it is known to consist of both aromatic and aliphatic domains. While the composition of the aliphatic component has been fairly well characterized, that of the phenolic component has not. Using a combination of specific carbon-13 labeling techniques, and in situ solid state 13C NMR spectroscopic analysis, we now provide the first direct evidence for the nature of the phenolic domain of suberin and report here that it is almost exclusively comprised of a covalently linked, hydroxycinnamic acid-derived polymeric matrix.

NASA Discipline Plant Biology↗

NASA NTRS2012

Radiation Shielding System Using a Composite of Carbon Nanotubes Loaded with Electropolymers

Single-wall carbon nanotubes (SWCNTs) coated with a hydrogen-rich, electrically conducting polymer such as polyethylene, receive and dissipate a portion of incoming radiation pulse energy to electrical signals that are transmitted along the CNT axes, and are received at energy-dissipating terminals. In this innovation, an array of highly aligned nanowires is grown using a strong electric field or another suitable orientation procedure. Polyethylene (PE), polymethymlethacrylate (PMMA), or other electrically conducting polymer is spin-coated onto the SWCNTs with an average thickness of a few hundred nanometers to a few tenths of micrometers to form a PE/SWCNT composite. Alternatively, the polymer is spin-coated onto the nanowire array or an anodized alumina membrane (AAM) to form a PE/metal core shell structure, or PE can be electropolymerized using the SWCNTs or the metal nanowires as an electrode to form a PE/SWCNT core shell structure. The core shell structures can be extruded as anisotropic fibers. A monomer can be polymerized in the presence of SWCNTs to form highly cross-linked PE/SWCNT films. Alternatively, Pb colloid solution can be impregnated into a three-dimensional PE/SWCNT nanostructure to form a PW/SWCNT/Pb composite structure. A face-centered cubic (FCC) arrangement provides up to 12 interconnection channels connected to each core, with transverse channel dimensions up to 20 nm, with adequate mechanical compressive strength, and with an associated electrical conductivity of around 3 Seimens/cm for currents ranging from 0.01 to 10 mA. This threedimensional nanostructure is used as a host material to house appropriate radiation shielding material such as hydrogen- rich polymer/CNT structures, metal nanoparticles, and nanowires. Thicknesses of this material required to attenuate 10 percent, 50 percent, and 90 percent of an incident beam (gamma, X-ray, ultraviolet, neutron, proton, and electron) at energies in the range of 0 440 MeV are being determined, for example, by measuring fluence rate reduction. For example, a radiation field arrives first at an exposed surface of the innovation and produces an associated first electric field within the metal-like fingers of the three-dimensional nanostructure. This field is intensified near the exposed tips of the fingers, and this intensified field generates an intensified second electric field near the adjacent exposed tips of the coated CNSs. This generates an associated electrical current in the CNSs, and the associated electropolymer coating. The current is received by the second substrate transport component and is transported to the dissipation mechanism located contiguously to the second substrate.

McKay, Chris↗

NASA NTRS2014

De Novo Synthesis and Functional Study of Primitive Polypeptides in the Prebiotic Protein World

DNA, RNA and proteins within a lipid-bound membrane are the core components of life, but the order of their appearance during the origin of life is still under debate. The widely accepted RNA World hypothesis states that RNA likely emerged prior to proteins and DNA since RNA can serve both replicative and catalytic roles. While biochemists have reproduced the synthesis, polymerization, and replication of nucleotides and RNA under controlled prebiotic conditions, it is clear that such complex organic molecules were are not present in significant amounts in the the starting prebiotic material on Earth either from endogenous production or meteoritic input. In contrast, amino acids are naturally abundant in various prebiotic contexts such as carbonaceous chondrites and Urey-Miller type experiments, and many studies have demonstrated that under plausible prebiotic conditions amino acids could condense or polymerize to give rise to short peptides. These findings support the basis of a Protein World hypothesis for life, however little has been done to study the functions of such primitive peptides. Here we present our novel synthetic biology-based approach to the de novo synthesis of billions of primitive peptidesproteins derived from a limited set of naturally abundant proteinogenic amino acids such as glycine, alanine, aspartic acid, glutamic acid, valine and serine. Of these peptides, the ones with divalent metal-binding capability are of particular interest and will be screened and identified. Certain divalent metals were likely present in prebiotic environments. Not only do they coordinate well with amino acids, but they also catalyze reactions, which are difficult to achieve in organic chemistry. Since D-chiral and non-proteinogenic amino acids are also abundant in the universe and may provide insight into the pathway by which life developed, we will also discuss methods to analyze primitive peptides consisting of these amino acids and D-chiral and non-proteinogenic amino acids. By understanding this naturalistic pathway, we will be able to better understand how life developed here on Earth. Since these amino acids are abundant in universe, this work provide insight into pathways by which life developed on Earth and, by extension, the probability of life arising elsewhere.

Fujishima, Kosuke↗

NASA NTRS2017

Nanotube Film Electrode and an Electroactive Device Fabricated with the Nanotube Film Electrode and Methods for Making Same

Disclosed is a single wall carbon nanotube (SWCNT) film electrode (FE), all-organic electroactive device systems fabricated with the SWNT-FE, and methods for making same. The SWCNT can be replaced by other types of nanotubes. The SWCNT film can be obtained by filtering SWCNT solution onto the surface of an anodized alumina membrane. A freestanding flexible SWCNT film can be collected by breaking up this brittle membrane. The conductivity of this SWCNT film can advantageously be higher than 280 S/cm. An electroactive polymer (EAP) actuator layered with the SWNT-FE shows a higher electric field-induced strain than an EAP layered with metal electrodes because the flexible SWNT-FE relieves the restraint of the displacement of the polymeric active layer as compared to the metal electrode. In addition, if thin enough, the SWNT-FE is transparent in the visible light range, thus making it suitable for use in actuators used in optical devices.

Kang, Jin Ho↗

NASA NTRS2018

Methods for Making an Electroactive Device Fabricated with a Nanotube Film Electrode

Kang, Jin Ho↗

NASA NTRS1987

Tubulinlike protein from Spirochaeta bajacaliforniensis

Tubulin proteins are the fundamental subunits of all polymeric microtubule-based eukaryotic structures. Long, hollow structures each composed of 13 protofilaments as revealed by electron microscopy, microtubules (240 angstroms in diameter) are nearly ubiquitous in eukaryotes. These proteins have been the subject of intense biochemical and biophyiscal interest since the early 1970s and are of evolutionary interest as well. If tubulin-based structures (i.e., neurotubules, mitotic spindle tubules, centrioles, kinetosomes, axonemes, etc.) evolved from spirochetes by way of motility symbioses, tubulin homologies with spirochete proteins should be detectable. Tubulin proteins are widely thought to be limited to eukaryotes. Yet both azotobacters and spirochetes have shown immunological cross-reactivity with antitubulin antibodies. In neither of these studies was tubulin isolated nor any specific antigen identified as responsible for the immunoreactivity. Furthermore, although far less uniform in structure than eukaryotic microtubules, various cytoplasmic fibers and tubules (as seen by electron microscopy) have been reported in several types of prokaryotes (e.g., Spirochaeta; large termite spirochetes; treponemes; cyanobacteria; and Azotobacter. This work forms a part of our long-range study of the possible prokaryotic origin of tubulin and microtubules. Spirochetes are helically shaped gram-negative motile prokaryotes. They differ from all other bacterial in that the position of their flagella is periplasmic: their flagella lie between the inner and outer membranes of the gram-negative cell wall. Some of the largest spirochetes have longitudinally aligned 240 angstrom microtubules. Unfortunately, in spite of many attempts, all of the larger spirochetes (family Pillotaceae) with well-defined cytoplasmic tubules and antitubulin immunoreactivity are not cultivable. However, a newly described spirochete species (Spirochaeta bajacaliforniensis) possessing cytoplasmic fibers displays antitubulin immunoreactivity in whole-cell preparations. Since preliminary observations suggested that Spirochaeta bajacaliforniensis proteins may be related to eukaryotic tubulins, their characterization was undertaken. Brain tubulin can be purified by utilizing its ability to polymerize at warm temperatures and to depolymerize in the cold. After several cycles of sedimentation and redissolution the microtubule fraction is comprised of 75% tubulin and 20% high molecular mass microtubule-associated proteins (MAPs). In this paper we report that components of cell lysates, prepared from a spirochete that contains cytoplasmic fibers (Spirochaeta bajacaliforniensis), also exhibit the property of temperature-dependent cyclical sedimentation. Additionally we report the identification and characterization of the polypeptide responsible for cross-reactivity with antitubulin antiserum.

Non-NASA Center↗

NASA NTRS1987

Tubulinlike protein from Spirochaeta bajacaliforniensis

Tubulin proteins are the fundamental subunits of all polymeric microtubule-based eukaryotic structures. Long, hollow structures each composed of 13 protofilaments as revealed by electron microscopy, microtubules (240 angstroms in diameter) are nearly ubiquitous in eukaryotes. These proteins have been the subject of intense biochemical and biophysical interest since the early 1970s and are of evolutionary interest as well. If tubulin-based structures (i.e., neurotubules, mitotic spindle tubules, centrioles, kinetosomes, axonemes, etc.) evolved from spirochetes by way of motility symbioses, tubulin homologies with spirochete proteins should be detectable. Tubulin proteins are widely thought to be limited to eukaryotes. Yet both azotobacters and spirochetes have shown immunological cross-reactivity with anitubulin antibodies. In neither of these studies was tubulin isolated nor any specific antigen identified as responsible for the immunoreactivity. Furthermore, although far less uniform in structure than eukaryotic microtubules, various cytoplasmic fibers and tubules (as seen by electron microscopy) have been reported in several types of prokaryotes (e.g., Spirochaeta; large termite spirochetes; treponemes; cyanobacteria; and Azotobacter. This work forms a part of our long-range study of the possible prokaryotic origin of tubulin and microtubules. Spirochetes are helically shaped gram-negative motile prokaryotes. They differ from all other bacteria in that the position of their flagella is periplasmic: their flagella lie between the inner and outer membranes of the gram-negative cell wall. Some of the largest spirochetes have longitudinally aligned 240 angstroms microtubules. Unfortunately, in spite of many attempts, all of the larger spirochetes (family Pillotaceae) with well-defined cytoplasmic tubules and antitubulin immunoreactivity are not cultivable. However, a newly described spirochete species (Spirochaeta bajacaliforniensis) possessing cytoplasmic fibers displays antitubulin immunoreactivity in whole-cell preparations. Since preliminary observations suggested that Spirochaeta bajacaliforniensis proteins may be related to eukaryotic tubulins, their characterization was undertaken. Brain tubulin can be purified by utilizing its ability to polymerize at warm temperatures and to depolymerize in the cold. After several cycles of sedimentation and redissolution the microtubule fraction is composed of 75% tubulin and 20% high molecular mass microtubule-associated proteins (MAPs). In this paper we report that components of cell lysates, prepared from a spirochete that contains cytoplasmic fibers (Spirochaeta bajacaliforniensis), also exhibit the property of temperature-dependent cyclical sedimentation. Additionally we report the identification and characterization of the polypeptide responsible for cross-reactivity with antitubulin antiserum.

Non-NASA Center↗

NASA NTRS2003

Synthesis and Characterization of Polymers for Fuel Cells Application

The goal of this summer research is to prepare Polymer Exchange Membranes (PEM s) for fuel cell application. Several high temperature polymers such as polybenzimidazoles and polyether ketones were known to possess good high temperature stability and had been investigated by post-sulfonation to yield sulfonated polymers. The research project will involve two approaches: 1. Synthesis of polybenzimidazoles and then react with alkyl sultonse to attach an aliphatic sulfonic groups. 2. Synthesis of monomers containing sulfonic acid units either on a aromatic ring or on an aliphatic chain and then polymerize the monomers to form high molecular weight sulfonate polymers.

Tytko, Stephen F.↗

NASA NTRS2003

Effect of Branching on Rod-coil Polyimides as Membrane Materials for Lithium Polymer Batteries

This paper describes a series of rod-coil block co-polymers that produce easy to fabricate, dimensionally stable films with good ionic conductivity down to room temperature for use as electrolytes for lithium polymer batteries. The polymers consist of short, rigid rod polyimide segments, alternating with flexible, polyalkylene oxide coil segments. The highly incompatible rods and coils should phase separate, especially in the presence of lithium ions. The coil phase would allow for conduction of lithium ions, while the rigid rod phase would provide a high degree of dimensional stability. An optimization study was carried out to study the effect of four variables (degree of branching, formulated molecular weight, polymerization solvent and lithium salt concentration) on ionic conductivity, glass transition temperature and dimensional stability in this system.

Meador, Mary Ann B.↗