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At least 145 records · Page 8

Plasma-Assisted Chemical-Looping Combustion: Low-Temperature Methane and Ethylene Oxidation with Nickel Oxide

The chemical reaction network of low-temperature plasma-assisted oxidation of methane (CH 4 ) and ethylene (C 2 H 4 ) with nickel oxide (NiO) was investigated in a heated plasma reactor through time-dependent species measurements by electron-ionization molecular beam mass spectrometry (EI-MBMS). Methane (ethylene) oxidation by NiO was explored in temperature ranges from 300-700 °C (300-500 °C) and 300-800 °C (300-600°C) for the plasma and non-plasma conditions, respectively. Significant enhancement of methane oxidation was observed with plasma between 400 and 500 °C, where no oxidation was observed under non-plasma conditions. For the oxidation of methane at higher temperatures three different oxidation stages were observed: I) a period of complete oxidation, II) a period of incomplete CO oxidation, and III) a period of carbon buildup. For the C 2 H 4 experiments, and unlike the CH 4 experiments, the plasma resulted in a significant amount of new intermediate oxygenated species, such as CH 2 O, CH 3 OH, C 2 H 4 O, and C 2 H 6 O. Carbon deposits were observed under both methane and ethylene conditions and verified by X-ray photoelectron spectroscopy (XPS). ReaxFF simulations were performed for the oxidation of CH 4 and C 2 H 4 in a non-plasma environment. The simulated intermediates and products largely agree with the species measured in the experiments, though the predicted intermediate oxygenated species such as CH 2 O and C 2 H 6 O were not observed in experiments under non-plasma conditions. A reaction pathway analysis for CH 4 and C 2 H 4 reacting with NiO was created based on the observed species from the MBMS spectra, along with ReaxFF simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Process innovations to enable viable enzymatic poly(ethylene terephthalate) recycling

Enzymatic depolymerization of poly(ethylene terephthalate) (PET) has received considerable attention for closed-loop polyester recycling. However, current approaches for enzymatic PET recycling face challenges to achieve commercial viability with lower environmental impacts compared with virgin polyester manufacturing. Here, in this study, we present multiple process innovations for enzymatic PET recycling that enable economic and environmental feasibility. We show that substrate amorphization through extrusion and quenching is energy-efficient and enables near-quantitative enzymatic conversion in 50 h. Using ammonium hydroxide for pH control and thermolysis of the isolated diammonium terephthalate salt reduces the acid and base consumption by >99%, lowering annual operating expenses by 74%. Fed-batch processing increased ethylene glycol concentration, leading to a 65% reduction in energy consumption for ethylene glycol recovery. These improvements were modeled in an optimal process, with recycled PET estimated to be US$\$$1.51 kg -1 relative to US domestic virgin PET at US$\$$1.87 kg -1 and eliminating key life cycle obstacles to scale this technology.

36 MATERIALS SCIENCE↗

Catalytic Conversion of Ethylene to Value-added Materials (Final Report)

The general goal of the work was to develop new late metal Ni(II)- and Pd(II)-based catalysts and processes to convert ethylene and other readily available α-olefins via polymerization and oligomerization reactions to an array of new value-added materials with high efficiency. An emphasis was placed on invention of new catalysts and processes guided by rational design and detailed mechanistic studies. These investigations have generated new knowledge which may underpin technological advances directed towards new and more efficient methods for utilizing ethylene and α-olefins derived from ethylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermocatalytic Ethylene Production using Targeted RF Induction Heating

Ethylene, a key building block in the petrochemical industry is a top five chemical in annual production and the second highest energy consuming chemical per weight. Industrial-scale production of ethylene remains an energy consuming process and is conventionally practiced by steam cracking of ethane or naphtha feedstocks. Our project using Targeted RF Induction Heating aims to optimize the heating of the catalyst to improve energy efficiency (>50%). Induction heating also improves ethylene low-temperature yield, selectivity, and stability that will increase catalyst lifetime by >20% and result in a >15% decrease in operational costs.

Colon-Mercado, Hector R.↗

Atmospheric chemistry of ethane and ethylene

It is shown by a study of ethane and ethylene photochemistry that the loss of ethane is controlled by OH in the troposphere and Cl in the stratosphere. Ethane observations indicating free Cl concentrations below 30 km that are only 10% of the value predicted by the present model calculations cannot be explained by heterogeneous aerosol concentration processes, and contradict current stratospheric photochemistry. The chemical destruction of ethane and ethylene leads to the generation of such compounds as carbon monoxide and formaldehyde, and it is found that the tropospheric concentrations of the latter are enhanced by nearly a factor of three for an ethylene mixing ratio of 2 ppb.

Aikin, A. C.↗

Theoretical study of the bonding of the first-row transition-metal positive ions to ethylene

Ab initio calculations were performed to study the bonding of the first-row transition-metal ions with ethylene. While Sc(+) and Ti(+) insert into the pi bond of ethylene to form a three-membered ring, the ions V(+) through Cu(+) form an electrostatic complex with ethylene. The binding energies are compared with those from experiment and with those of comparable calculations performed previously for the metal-acetylene ion systems.

Sodupe, M.↗

Heat-transfer tests of aqueous ethylene glycol solutions in an electrically heated tube

As part of an investigation of the cooling characteristics of liquid-cooled engines, tests were conducted with an electrically heated single-tube heat exchanger to determine the heat-transfer characteristics of an-e-2 ethylene glycol and other ethylene glycol-water mixtures. Similar tests were conducted with water and commercial butanol (n-butyl alcohol) for check purposes. The results of tests conducted at an approximately constant liquid-flow rate of 0.67 pound per second (Reynolds number, 14,500 to 112,500) indicate that at an average liquid temperature 200 degrees f, the heat-transfer coefficients obtained using water, nominal (by volume) 30 percent-70 percent and 70 percent-30 percent glycol-water mixtures are approximately 3.8, 2.8, and 1.4 times higher, respectively, than the heat-transfer coefficients obtained using an-e-2 ethylene glycol.

Bernardo, Everett↗

Effects of microgravity and clinorotation on stress ethylene production in two starchless mutants of Arabidopsis thaliana

Starch filled plastids termed amyloplasts, contained within columella cells of the root caps of higher plant roots, are believed to play a statolith-like role in the gravitropic response of roots. Plants having amyloplasts containing less starch exhibit a corresponding reduction in gravitropic response. We have observed enhanced ethylene production by sweet clover (Melilotus alba L.) seedlings grown in the altered gravity condition of a slow rotating clinostat, and have suggested that this is a stress response resulting from continuous gravistimulation rather than as a result of the simulation of a microgravity condition. If so, we expect that plants deficient in starch accumulation in amyloplasts may produce less stress ethylene when grown on a clinostat. Therefore, we have grown Arabidopsis thaliana in the small, closed environment of the Fluid Processing Apparatus (FPA). In this preliminary report we compare stationary plants with clinorotated and those grown in microgravity aboard Discovery during the STS-63 flight in February 1995. In addition to wildtype, two mutants deficient in starch biosynthesis, mutants TC7 and TL25, which are, respectively, deficient in the activity of amyloplast phosphoglucomutase and ADP-glucose pyrophosphorylase, were grown for three days before being fixed within the FPA. Gas samples were aspirated from the growth chambers and carbon dioxide and ethylene concentations were measured using a gas chromatograph. The fixed tissue is currently undergoing further morphologic and microscopic characterization.

Gallegos, Gregory L.↗

ESCA Study of Poly (Vinylidene Fluoride) Tetrafluoroethylene - Ethylene Copolymer and Polyethylene Exposed to Atomic Oxygen

The ESCA (electron spectroscopy for chemical analysis) spectra of films of poly(vinylidene fluoride) (PVDF), tetrafluoroethylene-ethylene copolymer (TFE/ET) and polyethylene (PE) exposed to atomic oxygen (O(P-3)), in or out of the glow of a radio-frequency O2 plasma, were compared. ESCA spectra of PE films exposed to (O(P-3)) in low Earth orbit (LEO) on the STS-8 Space Shuttle were also examined. Apart from O(P-3)-induced surface recession (etching), the various polymer films exhibited surface oxidation, which proceeded towards equilibrium saturation oxygen levels. The maximum surface oxygen uptakes for in-glow or out-of-glow exposures were in the order: PE greater than TFE/ET greater than PVDF; for PE itself, the oxygen uptakes were in the order: in glow greater than out of glow greater than LEO. Given prior ESCA data on poly(vinyl fluoride) and polytetrafluoroethylene films exposed to O(P-3), the extent of surface oxidation is seen to decrease regularly with increase in fluorine substitution in a family of ethylene-type polymers. (Keywords: ESCA; poly(vinylidene fluoride); tetrafluoroethylene ethylene copolymer; polyethylene; atomic oxygen; radio-frequency oxygen plasma; low Earth orbit)

Golub, Morton A.↗

The interaction of microgravity and ethylene on the ultrastructure cell and Ca2+ localization in soybean hook hypocotyl

Calcium ions are secondary messenger in numerous cellular processes of plant grown at 1 g. Ca2+ are connected with oxygen atoms, of pectin carboxy groups and/or with H(+)-groups of protein (Roux and Slocum, 1982; Hepler and Wayne, 1985). The influence of altered gravity on the calcium balance in some cells is established. The increased synthesis of ethylene in plant grown in microgravity caused the change of the structural-functional organization of cell (Hensel and Iversen, 1980; Hilaire et al., 1996). Available data put the new question: how do high ethylene level and microgravity influence on the redistribution of Ca2+ in cell of seedling in early stage of growth? Therefore, the goal of our data was the comparable study of the cell ulltrastructure and localization of Ca2+ in hook hypocotyl of soybean seedling under interaction of microgravity and ethylene.

STS-87 Shuttle Project↗

Biochemical and functional analysis of CTR1, a protein kinase that negatively regulates ethylene signaling in Arabidopsis

CTR1 encodes a negative regulator of the ethylene response pathway in Arabidopsis thaliana. The C-terminal domain of CTR1 is similar to the Raf family of protein kinases, but its first two-thirds encodes a novel protein domain. We used a variety of approaches to investigate the function of these two CTR1 domains. Recombinant CTR1 protein was purified from a baculoviral expression system, and shown to possess intrinsic Ser/Thr protein kinase activity with enzymatic properties similar to Raf-1. Deletion of the N-terminal domain did not elevate the kinase activity of CTR1, indicating that, at least in vitro, this domain does not autoinhibit kinase function. Molecular analysis of loss-of-function ctr1 alleles indicated that several mutations disrupt the kinase catalytic domain, and in vitro studies confirmed that at least one of these eliminates kinase activity, which indicates that kinase activity is required for CTR1 function. One missense mutation, ctr1-8, was found to result from an amino acid substitution within a new conserved motif within the N-terminal domain. Ctr1-8 has no detectable effect on the kinase activity of CTR1 in vitro, but rather disrupts the interaction with the ethylene receptor ETR1. This mutation also disrupts the dominant negative effect that results from overexpression of the CTR1 amino-terminal domain in transgenic Arabidopsis. These results suggest that CTR1 interacts with ETR1 in vivo, and that this association is required to turn off the ethylene-signaling pathway.

Non-NASA Center↗

Relative rates for plasma homo- and copolymerizations of olefins in a homologous series of fluorinated ethylenes

It is well known that the rate of plasma polymerization, or deposition rate, of a given monomer depends on various plasma process parameters, e.g., monomer flow rate, pressure, power, frequency (DC, rf or microwave), location of the substrate in the reactor, reactor geometry or configuration, and temperature. In contrast, little work has been done to relate deposition rates to monomer structures for a homologous series of monomers where the rates are obtained under identical plasma process parameters. For the particular series of fluorinated ethylenes (C2HxF4-x; x = 0-4), deposition rates were reported for ethylene (ET), vinyl fluoride, vinylidene fluoride and tetrafluoroethylene (TFE), but for plasma polymerizations carried out under different discharge conditions, e.g., pressure, current density, and electrode temperature. Apparently, relative deposition rates were reported for only two members of that series (ET, x = 4, and TFE, x = 0) for which the plasma polymerizations were conducted under identical conditions. We now present relative deposition rates for both homopolymerizations and copolymerizations of the entire series of fluorinated ethylenes (x = 0-4). Our interest in such rates stems from prior work on the plasma copolymerization of ET and TFE in which it was found that the deposition rates for the plasma copolymers, when plotted versus mol % TFE in the ET/TFE feed stock, followed a concave-downward curve situated above the straight line joining the deposition rates for the plasma homopolymers. This type of plot (observed also for an argon-ET/TFE plasma copolymerization) indicated a positive interaction between ET and TFE such that each monomer apparently "sensitized" the plasma copolymerization of the other. Since the shape of that plot is not altered if mol % TFE is replaced by F/C, the fluorine-to-carbon ratio, this paper aims (1) to show how the relative deposition rates for plasma copolymers drawn from all pairs of monomers in the C2HxF4-x series, as well as the deposition rates for the individual plasma homopolymers, vary with F/C ratios of the monomers or monomer blends, and (2) to see if those rates give rise to a common plot.

NASA Center ARC↗

The role of ethylene in the development of constant-light injury of potato and tomato

The role of ethylene in the development of constant-light injury of potato (Solanum tuberosum L.) and tomato (Lycopersicon esculentum Mill.) was investigated. In one study, silver thiosulfate (STS) was applied to the foliage of four potato cultivars growing under constant light. Leaf area and shoot dry mass of 'Kennebec' and 'Superior', cultivars normally injured by constant light, were greater (P < 0.05) than those of control plants given foliar applications of distilled water. Examination of STS-treated 'Kennebec' leaflets revealed significantly less injury (necrotic spotting and reduced starch content) than the water-treated controls. 'Norland' and 'Denali', cultivars tolerant of constant light, exhibited no differences in growth between treatments. In a second study, injury (necrotic spotting and reduced starch content) was induced in leaflets of 'Denali' when exposed to spray applications of 0.5 mmol L-1 ethephon or air containing 0.5 to 0.8 microL L-1 ethylene. In a third study, three genotypes of 'Ailsa Craig' tomato were grown under constant light. Leaves of the normal 'Ailsa Craig' exhibited epinasty, reduced chlorophyll concentration, and reduced starch content. Leaves of a mutant 'Ailsa Craig', containing the Never ripe mutation, did not exhibit epinasty but exhibited the same amount of reduced chlorophyll concentration and starch content as normal plants. Leaves of a transgenic 'Ailsa Craig', containing an antisense gene of 1-aminocyclopropane 1-carboxylate (ACC) oxidase, were epinastic, but chlorophyll concentration and starch content were greater than in leaves of normal and mutant plants. These results suggest that transgenic plants were more tolerant of constant light than the other genotypes. Evidence from these studies indicates that ethylene, combined with constant light, has an important role in the development of constant-light injury.

Non-NASA Center↗

Shoot inversion inhibition of stem elongation in Pharbitis nil: a possible role for ethylene-induced glycoprotein and lignin

Inversion of the upper shoot of Pharbitis nil results in the inhibition of elongation in the inverted stem. The objective of the present study was to determine how shoot inversion-induced gravity stress inhibited elongation and to elucidate the possible role of ethylene-induced glycoprotein and lignin in this process. Determinations of hydroxyproline, peroxidase, phenylalanine ammonia-lyase (PAL), phenol, and lignin content/activity were carried out by appropriate spectrophotometric methods. It was found that inversion and Ethrel treatments of upright shoots caused significant increases in hydroxyproline content, peroxidase, and PAL activity in 12 hours and in phenol and lignin contents in 24 hours. All of these increases except for that of cytoplasmic peroxidase activity were partially reversed by AgNO3, the ethylene action inhibitor. It is concluded that possible cross-linking associated with the accumulation of the ethylene-induced hydroxyproline-rich glycoprotein and lignin may be responsible for the later stages of cessation of elongation in the inverted Pharbitis shoot.

NASA Program Space Biology↗

The role of gravity in apical dominance: effects of clinostating on shoot inversion-induced ethylene production, shoot elongation and lateral bud growth

Shoot inversion-induced release of apical dominance in Pharbitis nil is inhibited by rotating the plant at 0.42 revolutions per minute in a vertical plane perpendicular to the axis of rotation of a horizontal clinostat. Clinostating prevented lateral bud outgrowth, apparently by negating the restriction of the shoot elongation via reduction of ethylene production in the inverted shoot. Radial stem expansion was also decreased. Data from experiments with intact tissue and isolated segments indicated that shoot-inversion stimulates ethylene production by increasing the activity of 1-aminocyclopropane-1-carboxylic acid synthase. The results support the hypothesis that shoot inversion-induced release of apical dominance in Pharbitis nil is due to gravity stress and is mediated by ethylene-induced retardation of the elongation of the inverted shoot.

NASA Discipline Plant Biology↗

Thigmomorphogenesis: the relationship of mechanical perturbation to elicitor-like activity and ethylene production

An extracellular solution obtained from bean (Phaseolus vulgaris L. cv. Resistant Cherokee Wax) stems induced phytoalexin-like substance and ethylene production in a soybean [Glycine max (L.) Merr. cv. Wayne] cotyledon bioassay. The elicitor-like activity for phytoalexin formation and ethylene production was increased by mechanical perturbation of bean stems. Moreover, the application of extracted or known elicitors to bean plants mimicked the effect of mechanical perturbation (i.e., inhibition of stem elongation and enhancement of radial growth). The effects of extract when applied exogenously, on elicitor-like activity in the bioassay as well as stem thickening were decreased by aminoethoxyvinylglycine, an inhibitor of ethylene biosynthesis. These results suggest that elicitor-like substances which are formed in response to mechanical perturbation contribute to the thigmomorphogenesis.

Plants, Medicinal↗

The molecular basis of ethylene signalling in Arabidopsis

The simple gas ethylene profoundly influences plants at nearly every stage of growth and development. In the past ten years, the use of a genetic approach, based on the triple response phenotype, has been a powerful tool for investigating the molecular events that underlie these effects. Several fundamental elements of the pathway have been described: a receptor with homology to bacterial two-component histidine kinases (ETR1), elements of a MAP kinase cascade (CTR1) and a putative transcription factor (EIN3). Taken together, these elements can be assembled into a simple, linear model for ethylene signalling that accounts for most of the well-characterized ethylene mediated responses.

Non-NASA Center↗

Geometric analysis of Arabidopsis root apex reveals a new aspect of the ethylene signal transduction pathway in development

Structurally, ethylene is the simplest phytohormone and regulates multiple aspects of plant growth and development. Its effects are mediated by a signal transduction cascade involving receptors, MAP kinases and transcription factors. Many morphological effects of ethylene in plant development, including root size, have been previously described. In this article a combined geometric and algebraic approach has been used to analyse the shape and the curvature in the root apex of Arabidopsis seedlings. The process requires the fitting of Bezier curves that reproduce the root apex shape, and the calculation of the corresponding curvatures. The application of the method has allowed us to identify significant differences in the root curvatures of ethylene insensitive mutants (ein2-1 and etr1-1) with respect to the wild-type Columbia.

Arabidopsis/genetics/growth & development↗