The fate of carbon dioxide in water-rich fluids under extreme conditions

PubMed Central

Pan, Ding; Galli, Giulia

2016-01-01

Investigating the fate of dissolved carbon dioxide under extreme conditions is critical to understanding the deep carbon cycle in Earth, a process that ultimately influences global climate change. We used first-principles molecular dynamics simulations to study carbonates and carbon dioxide dissolved in water at pressures (P) and temperatures (T) approximating the conditions of Earth’s upper mantle. Contrary to popular geochemical models assuming that molecular CO2(aq) is the major carbon species present in water under deep Earth conditions, we found that at 11 GPa and 1000 K, carbon exists almost entirely in the forms of solvated carbonate (CO32−) and bicarbonate (HCO3−) ions and that even carbonic acid [H2CO3(aq)] is more abundant than CO2(aq). Furthermore, our simulations revealed that ion pairing between Na+ and CO32−/HCO3− is greatly affected by P-T conditions, decreasing with increasing pressure at 800 to 1000 K. Our results suggest that in Earth’s upper mantle, water-rich geofluids transport a majority of carbon in the form of rapidly interconverting CO32− and HCO3− ions, not solvated CO2(aq) molecules. PMID:27757424

The fate of carbon dioxide in water-rich fluids under extreme conditions.

PubMed

Pan, Ding; Galli, Giulia

2016-10-01

Investigating the fate of dissolved carbon dioxide under extreme conditions is critical to understanding the deep carbon cycle in Earth, a process that ultimately influences global climate change. We used first-principles molecular dynamics simulations to study carbonates and carbon dioxide dissolved in water at pressures ( P ) and temperatures ( T ) approximating the conditions of Earth's upper mantle. Contrary to popular geochemical models assuming that molecular CO 2 (aq) is the major carbon species present in water under deep Earth conditions, we found that at 11 GPa and 1000 K, carbon exists almost entirely in the forms of solvated carbonate ([Formula: see text]) and bicarbonate ([Formula: see text]) ions and that even carbonic acid [H 2 CO 3 (aq)] is more abundant than CO 2 (aq). Furthermore, our simulations revealed that ion pairing between Na + and [Formula: see text]/[Formula: see text] is greatly affected by P - T conditions, decreasing with increasing pressure at 800 to 1000 K. Our results suggest that in Earth's upper mantle, water-rich geofluids transport a majority of carbon in the form of rapidly interconverting [Formula: see text] and [Formula: see text] ions, not solvated CO 2 (aq) molecules.

Phase diagram and high-pressure boundary of hydrate formation in the carbon dioxide-water system.

PubMed

Manakov, Andrej Yu; Dyadin, Yuriy A; Ogienko, Andrey G; Kurnosov, Alexander V; Aladko, Eugeny Ya; Larionov, Eduard G; Zhurko, Fridrih V; Voronin, Vladimir I; Berger, Ivan F; Goryainov, Sergei V; Lihacheva, Anna Yu; Ancharov, Aleksei I

2009-05-21

Experimental investigation of the phase diagram of the system carbon dioxide-water at pressures up to 2.7 GPa has been carried out in order to explain earlier controversial results on the decomposition curves of the hydrates formed in this system. According to X-ray diffraction data, solid and/or liquid phases of water and CO2 coexist in the system at room temperature within the pressure range from 0.8 to 2.6 GPa; no clathrate hydrates are observed. The results of neutron diffraction experiments involving the samples with different CO2/H2O molar ratios, and the data on the phase diagram of the system carbon dioxide-water show that CO2 hydrate of cubic structure I is the only clathrate phase present in this system under studied P-T conditions. We suppose that in the cubic structure I hydrate of CO2 multiple occupation of the large hydrate cavities with CO2 molecules takes place. At pressure of about 0.8 GPa this hydrate decomposes into components indicating the presence of the upper pressure boundary of the existence of clathrate hydrates in the system.

Stratospheric nitrogen dioxide in the vicinity of soufriere, st. Vincent.

PubMed

Romick, G J; Murcray, D G; Williams, W J

1982-06-04

In April 1979, measurements of nitrogen dioxide in the upper atmosphere were made near Soufriere Volcano by twilight optical-absorption techniques. The derived value of 5 x 10(15) molecules per square centimeter column implies an enhancement of 25 percent over earlier abundances measured in the same latitudinal regions. This enhancement may represent the normal stratospheric variability of nitrogen dioxide in the equatorial region but in any case may be considered an upper limit to the volcano's effect on the total nitrogen dioxide abundance.

Diffusive shunting of gases and other molecules in the renal vasculature: physiological and evolutionary significance.

PubMed

Ngo, Jennifer P; Ow, Connie P C; Gardiner, Bruce S; Kar, Saptarshi; Pearson, James T; Smith, David W; Evans, Roger G

2016-11-01

Countercurrent systems have evolved in a variety of biological systems that allow transfer of heat, gases, and solutes. For example, in the renal medulla, the countercurrent arrangement of vascular and tubular elements facilitates the trapping of urea and other solutes in the inner medulla, which in turn enables the formation of concentrated urine. Arteries and veins in the cortex are also arranged in a countercurrent fashion, as are descending and ascending vasa recta in the medulla. For countercurrent diffusion to occur, barriers to diffusion must be small. This appears to be characteristic of larger vessels in the renal cortex. There must also be gradients in the concentration of molecules between afferent and efferent vessels, with the transport of molecules possible in either direction. Such gradients exist for oxygen in both the cortex and medulla, but there is little evidence that large gradients exist for other molecules such as carbon dioxide, nitric oxide, superoxide, hydrogen sulfide, and ammonia. There is some experimental evidence for arterial-to-venous (AV) oxygen shunting. Mathematical models also provide evidence for oxygen shunting in both the cortex and medulla. However, the quantitative significance of AV oxygen shunting remains a matter of controversy. Thus, whereas the countercurrent arrangement of vasa recta in the medulla appears to have evolved as a consequence of the evolution of Henle's loop, the evolutionary significance of the intimate countercurrent arrangement of blood vessels in the renal cortex remains an enigma. Copyright © 2016 the American Physiological Society.

Volatile molecule PuO 3 observed from subliming plutonium dioxide

NASA Astrophysics Data System (ADS)

Ronchi, C.; Capone, F.; Colle, J. Y.; Hiernaut, J. P.

2000-06-01

Mass spectrometric measurements of effusing vapours over PuO 2 and (U, Pu)O 2 indicate the presence of volatile PuO 3 (g) molecules. The formation of plutonium trioxide vapour is due to a chemical process involving oxygen adsorbed during oxidation of the sample. Although in the examined samples, the fraction of trioxide effusing in vacuo was of the order of 0.02 ppm of the plutonium content, under steady-state oxidation conditions it has been shown that the process can have a relevant effect on the sublimation rate of the dioxide.

Stratospheric nitrogen dioxide in the vicinity of Soufriere, St. Vincent

NASA Technical Reports Server (NTRS)

Romick, G. J.; Murcray, D. G.; Williams, W. J.

1982-01-01

In April 1979, measurements of nitrogen dioxide in the upper atmosphere were made near Soufriere Volcano by twilight optical-absorption techniques. The derived value of 5 x 10 to the 15th molecules per square centimeter column implies an enhancement of 25 percent over earlier abundances measured in the same latitudinal regions. This enhancement may represent the normal stratospheric variability of nitrogen dioxide in the equatorial region, but in any case may be considered an upper limit to the volcano's effect on the total nitrogen dioxide abundance.

Triple-Pulse Integrated Path Differential Absorption Lidar for Carbon Dioxide Measurement - Novel Lidar Technologies and Techniques with Path to Space

NASA Technical Reports Server (NTRS)

Singh, Upendra N.; Refaat, Tamer F.; Petros, Mulugeta

2017-01-01

The societal benefits of understanding climate change through identification of global carbon dioxide sources and sinks led to the desired NASA's active sensing of carbon dioxide emissions over nights, days, and seasons (ASCENDS) space-based missions of global carbon dioxide measurements. For more than 15 years, NASA Langley Research Center (LaRC) have developed several carbon dioxide active remote sensors using the differential absorption lidar (DIAL) technique operating at the two-micron wavelength. Currently, an airborne two-micron triple-pulse integrated path differential absorption (IPDA) lidar is under development. This IPDA lidar measures carbon dioxide as well as water vapor, the dominant interfering molecule on carbon dioxide remote sensing. Advancement of this triple-pulse IPDA lidar development is presented.

The Thermal Decomposition of Some Organic Lead Compounds

DTIC Science & Technology

1957-11-01

either of salicylic anhydride or of its pyrolysis fragments which are reported to be a mixture of carbon dioxide , phenol and phenyl salicylate. Other...7) have studied the decomposition of the mono-salicylate in vacuo at 400°C. and have found that one molecule of carbon dioxide is evolved per...of lead nitrate and nitrosalicylic acid, though seme of the latter is decarboxylated with evolution of carbon dioxide . These points are considered

Novel Technique and Technologies for Active Optical Remote Sensing of Greenhouse Gases

NASA Technical Reports Server (NTRS)

Singh, Upendra N.; Refaat, Tamer F.; Petros, Mulugeta

2017-01-01

The societal benefits of understanding climate change through identification of global carbon dioxide sources and sinks led to the desired NASA's active sensing of carbon dioxide emissions over nights, days, and seasons (ASCENDS) space-based missions of global carbon dioxide measurements. For more than 15 years, NASA Langley Research Center (LaRC) have developed several carbon dioxide active remote sensors using the differential absorption lidar (DIAL) technique operating at the two-micron wavelength. Currently, an airborne two-micron triple-pulse integrated path differential absorption (IPDA) lidar is under development. This IPDA lidar measures carbon dioxide as well as water vapor, the dominant interfering molecule on carbon dioxide remote sensing. Advancement of this triple-pulse IPDA lidar development is presented.

Reusable photocatalytic titanium dioxide-cellulose nanofiber films

Treesearch

Alexandra Snyder; Zhenyu Bo; Robert Moon; Jean-Christophe Rochet; Lia Stanciu

2013-01-01

Titanium dioxide (TiO2) is a well-studied photocatalyst that is known to break down organic molecules upon ultraviolet (UV) irradiation. Cellulose nanofibers (CNFs) act as an attractive matrix material for the suspension of photocatalytic particles due to their desirable mechanical and optical properties. In this work, TiO2...

Photoproduction of halogens using platinized TiO2

NASA Technical Reports Server (NTRS)

Reichman, B.; Byvik, C. E.

1981-01-01

Unlike electrolysis of halide salt solutions, technique using powdered titanium dioxide catalyst requires no external power other than ultraviolet radiation source. Semiconductor powders photocatalyze and photosynthesize many useful reactions; applications are production of halogen molecules, oxidation of hazardous materials in wastewater, and conversion of carbon monoxide to carbon dioxide.

PENTACARBON DIOXIDE (C{sub 5}O{sub 2}) FORMATION AND ITS ROLE AS A TRACER OF SOLAR SYSTEM EVOLUTION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Förstel, Marko; Maksyutenko, Pavlo; Kaiser, Ralf I.

2016-02-20

Carbon monoxide is the second most abundant molecule on icy grains in the interstellar medium. These grains are under the influence of ionizing radiation, which induces the chemical reaction within the ice. Here we report the first observation of subliming pentacarbon dioxide (C{sub 5}O{sub 2}) after irradiation of pure carbon monoxide ice with energetic electrons. Our results show that pentacarbon dioxide is a stable reaction product in a carbon monoxide matrix that survives the sublimation in star-forming regions at sublimation temperatures of 175 K. Along with carbon suboxide (C{sub 3}O{sub 2}), this molecule can serve as a powerful tracer ofmore » the temperature history of formerly carbon monoxide rich ices in molecular clouds and star-forming regions.« less

Enzyme microheterogeneous hydration and stabilization in supercritical carbon dioxide.

PubMed

Silveira, Rodrigo L; Martínez, Julian; Skaf, Munir S; Martínez, Leandro

2012-05-17

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

Carbon dioxide conversion over carbon-based nanocatalysts.

PubMed

Khavarian, Mehrnoush; Chai, Siang-Piao; Mohamed, Abdul Rahman

2013-07-01

The utilization of carbon dioxide for the production of valuable chemicals via catalysts is one of the efficient ways to mitigate the greenhouse gases in the atmosphere. It is known that the carbon dioxide conversion and product yields are still low even if the reaction is operated at high pressure and temperature. The carbon dioxide utilization and conversion provides many challenges in exploring new concepts and opportunities for development of unique catalysts for the purpose of activating the carbon dioxide molecules. In this paper, the role of carbon-based nanocatalysts in the hydrogenation of carbon dioxide and direct synthesis of dimethyl carbonate from carbon dioxide and methanol are reviewed. The current catalytic results obtained with different carbon-based nanocatalysts systems are presented and how these materials contribute to the carbon dioxide conversion is explained. In addition, different strategies and preparation methods of nanometallic catalysts on various carbon supports are described to optimize the dispersion of metal nanoparticles and catalytic activity.

Titanium dioxide in dental enamel as a trace element and its variation with bleaching

PubMed Central

Durán-Sedó, Randall; Herrera-Sancho, Óscar-Andrey

2018-01-01

Background Titanium is a less studied trace element in dental enamel. Literature relates an increased Titanium concentration with a decreased enamel crystal domain size, which in turn is related to a higher color value. The aim of our study was to analyze the effect of tooth bleaching agents on its concentration in dental enamel by means of confocal Raman spectroscopy. Material and Methods Human teeth were randomly distributed in six experimental groups (n=10) and submitted to different bleaching protocols according to the manufacturer´s instructions. Confocal Raman spectroscopy was carried out in order to identify and quantify the presence of titanium dioxide molecules in enamel prior to and during whitening. Statistical analysis included repeated measures analysis of variance (p≤0.05) and Bonferroni pairwise comparisons. Results Titanium dioxide concentration was negatively affected by the longer bleaching protocols (at-home bleaching gels). All in-office whitening products increased significantly the studied molecule (p≤0,05). Conclusions All dental specimens depicted the presence of titanium dioxide as a trace element in dental enamel. Bleaching gels that have to be applied at higher concentrations but for shorter periods of time increase the concentration of titanium dioxide, whilst at-home whitening gels used for longer periods of time despite the lower concentration caused a loss in titanium. Key words:Bleaching, whitening, hydrogen peroxide, carbamide peroxide, Raman spectroscopy, titanium dioxide. PMID:29930771

Titanium dioxide in dental enamel as a trace element and its variation with bleaching.

PubMed

Vargas-Koudriavtsev, Tatiana; Durán-Sedó, Randall; Herrera-Sancho, Óscar-Andrey

2018-06-01

Titanium is a less studied trace element in dental enamel. Literature relates an increased Titanium concentration with a decreased enamel crystal domain size, which in turn is related to a higher color value. The aim of our study was to analyze the effect of tooth bleaching agents on its concentration in dental enamel by means of confocal Raman spectroscopy. Human teeth were randomly distributed in six experimental groups (n=10) and submitted to different bleaching protocols according to the manufacturer´s instructions. Confocal Raman spectroscopy was carried out in order to identify and quantify the presence of titanium dioxide molecules in enamel prior to and during whitening. Statistical analysis included repeated measures analysis of variance ( p ≤0.05) and Bonferroni pairwise comparisons. Titanium dioxide concentration was negatively affected by the longer bleaching protocols (at-home bleaching gels). All in-office whitening products increased significantly the studied molecule ( p ≤0,05). All dental specimens depicted the presence of titanium dioxide as a trace element in dental enamel. Bleaching gels that have to be applied at higher concentrations but for shorter periods of time increase the concentration of titanium dioxide, whilst at-home whitening gels used for longer periods of time despite the lower concentration caused a loss in titanium. Key words: Bleaching, whitening, hydrogen peroxide, carbamide peroxide, Raman spectroscopy, titanium dioxide.

Laser assisted drug delivery: a review of an evolving technology.

PubMed

Sklar, Lindsay R; Burnett, Christopher T; Waibel, Jill S; Moy, Ronald L; Ozog, David M

2014-04-01

Topically applied drugs have a relatively low cutaneous bioavailability. This article reviews the existing applications of laser assisted drug delivery, a means by which the permeation of topically applied agents can be enhanced into the skin. The existing literature suggests that lasers are a safe and effective means of enhancing the delivery of topically applied agents through the skin. The types of lasers most commonly studied in regards to drug delivery are the carbon dioxide (CO2 ) and erbium:yttrium-aluminum-garnet (Er:YAG) lasers. Both conventional ablative and fractional ablative modalities have been utilized and are summarized herein. The majority of the existing studies on laser assisted drug delivery have been performed on animal models and additional human studies are needed. Laser assisted drug delivery is an evolving technology with potentially broad clinical applications. Multiple studies demonstrate that laser pretreatment of the skin can increase the permeability and depth of penetration of topically applied drug molecules for both local cutaneous and systemic applications. © 2014 Wiley Periodicals, Inc.

Trimolecular reactions of uranium hexafluoride with water.

PubMed

Lind, Maria C; Garrison, Stephen L; Becnel, James M

2010-04-08

The hydrolysis reaction of uranium hexafluoride (UF(6)) is a key step in the synthesis of uranium dioxide (UO(2)) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF(6) molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizable barrier of 78.2 kJ x mol(-1), indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO(2) product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF(6) molecules and one water molecule, and (2) the reaction of two water molecules with a single UF(6) molecule. The predicted reaction of two UF(6) molecules with one water molecule displays an interesting "fluorine-shuttle" mechanism, a significant energy barrier of 69.0 kJ x mol(-1) to the formation of UF(5)OH, and an enthalpy of reaction (DeltaH(298)) of +17.9 kJ x mol(-1). The reaction of a single UF(6) molecule with two water molecules displays a "proton-shuttle" mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ x mol(-1) and an exothermic enthalpy of reaction (DeltaH(298)) of -13.9 kJ x mol(-1). The exothermic nature of the overall UF(6) + 2H(2)O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging.

Anisotropic contribution to the van der Waals and the Casimir-Polder energies for CO2 and CH4 molecules near surfaces and thin films

NASA Astrophysics Data System (ADS)

Thiyam, Priyadarshini; Parashar, Prachi; Shajesh, K. V.; Persson, Clas; Schaden, Martin; Brevik, Iver; Parsons, Drew F.; Milton, Kimball A.; Malyi, Oleksandr I.; Boström, Mathias

2015-11-01

In order to understand why carbon dioxide (CO2) and methane (CH4) molecules interact differently with surfaces, we investigate the Casimir-Polder energy of a linearly polarizable CO2 molecule and an isotropically polarizable CH4 molecule in front of an atomically thin gold film and an amorphous silica slab. We quantitatively analyze how the anisotropy in the polarizability of the molecule influences the van der Waals contribution to the binding energy of the molecule.

Study of carbon dioxide gas treatment based on equations of kinetics in plasma discharge reactor

NASA Astrophysics Data System (ADS)

Abedi-Varaki, Mehdi

2017-08-01

Carbon dioxide (CO2) as the primary greenhouse gas, is the main pollutant that is warming earth. CO2 is widely emitted through the cars, planes, power plants and other human activities that involve the burning of fossil fuels (coal, natural gas and oil). Thus, there is a need to develop some method to reduce CO2 emission. To this end, this study investigates the behavior of CO2 in dielectric barrier discharge (DBD) plasma reactor. The behavior of different species and their reaction rates are studied using a zero-dimensional model based on equations of kinetics inside plasma reactor. The results show that the plasma reactor has an effective reduction on the CO2 density inside the reactor. As a result of reduction in the temporal variations of reaction rate, the speed of chemical reactions for CO2 decreases and very low concentration of CO2 molecules inside the plasma reactor is generated. The obtained results are compared with the existing experimental and simulation findings in the literature.

Products of anaerobic phloroglucinol degradation by Coprococcus sp. Pe15.

PubMed

Tsai, C G; Gates, D M; Ingledew, W M; Jones, G A

1976-02-01

Under anaerobic conditions, resting cell suspensions of Coprococcus sp. Pe15 degraded 1 molecule of phloroglucinol to 2 molecules of acetic acid and 2 molecules of carbon dioxide. The organism metabolized the flavonoids rhamnetin and quercetin anaerobically in 20% rumen fluid medium but failed to grow under similar conditions at the expense of any of 39 other aromatic or flavonoid compounds tested.

Hadfield with the Reassembled Amine Swingbed in the U.S. Lab

NASA Image and Video Library

2013-03-20

ISS035-E-006230 (20 March 2013) --- Expedition 35 Commander Chris Hadfield in Harmony Node 2 aboard the Earth-orbiting International Space Station examines his work after reassembling the amine swing bed into its locker chassis. This device examines whether a vacuum-regenerated amine system can effectively remove carbon dioxide from the space station atmosphere using a smaller, more efficient vacuum regeneration system. The goal is to recover carbon dioxide from the atmosphere, and separate the dioxide from the carbon, so that the oxygen molecules can be used for crew life support.

Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

DOEpatents

Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2011-02-01

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Systems including catalysts in porous zeolite materials within a reactor for use in synthesizing hydrocarbons

DOEpatents

Rolllins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID

2012-07-24

Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

A challenge for green chemistry: designing molecules that readily dissolve in carbon dioxide.

PubMed

Beckman, E J

2004-09-07

Carbon dioxide is a green yet feeble solvent whose full potential won't be realized until we develop a more thorough understanding of its solvent behavior at the molecular level. Fortunately, advances in molecular modeling coupled with experiments are rapidly improving our understanding of CO(2)'s behavior, permitting design of new, more sustainable "CO(2)-philes".

Water and Carbon Dioxide Adsorption at Olivine Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

2013-11-14

Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbonmore » dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.« less

Controlled functionalization of nanoparticles & practical applications

NASA Astrophysics Data System (ADS)

Rashwan, Khaled

With the increasing use of nanoparticles in both science and industry, their chemical modification became a significant part of nanotechnology. Unfortunately, most commonly used procedures provide just randomly functionalized materials. The long-term objective of our work is site- and stoichiometrically-controlled functionalization of nanoparticles with the utilization of solid supports and other nanostructures. On the examples of silica nanoparticles and titanium dioxide nanorods, we have obtained results on the solid-phase chemistry, method development, and modeling, which advanced us toward this goal. At the same time, we explored several applications of nanoparticles that will benefit from the controlled functionalization: imaging of titanium-dioxide-based photocatalysts, bioimaging by fluorescent nanoparticles, drug delivery, assembling of bone implants, and dental compositions. Titanium dioxide-based catalysts are known for their catalytic activity and their application in solar energy utilization such as photosplitting of water. Functionalization of titanium dioxide is essential for enhancing bone-titanium dioxide nanotube adhesion, and, therefore, for its application as an interface between titanium implants and bones. Controlled functionalization of nanoparticles should enhance sensitivity and selectivity of nanoassemblies for imaging and drug delivery applications. Along those lines, we studied the relationship between morphology and surface chemistry of nanoparticles, and their affinity to organic molecules (salicylic and caffeic acid) using Langmuir adsorption isotherms, and toward material surfaces using SEM- and TEM-imaging. We focused on commercial samples of titanium dioxide, titanium dioxide nanorods with and without oleic acid ligands, and differently functionalized silica nanoparticles. My work included synthesis, functionalization, and characterization of several types of nanoparticles, exploring their application in imaging, dentistry, and bone implant construction. Significant part of my experimental efforts was devoted to the solid-phase method development using model organic molecules, as well as affinity of nanoparticles to the functional groups and surfaces that can be used as linkages for constructing functional nanodevices.

Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres

NASA Technical Reports Server (NTRS)

Hooker, M. W.; Rast, H. E.; Rogers, D. K.

1989-01-01

For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.

Investigation of the SERS Spectra of Hydroquinone Molecule Adsorbed on Titanium Dioxide

NASA Astrophysics Data System (ADS)

Polubotko, A. M.; Chelibanov, V. P.

2018-01-01

The paper analyzes the SERS spectrum of hydroquinone adsorbed on nanoparticles of titanium dioxide (TiO2). It is seen that the enhancement is stronger for a larger mean size of nanoparticles that is in agreement with an electrostatic approximation. In addition, it is found that there are the lines, which are forbidden in usual Raman spectra. There is also an enhancement caused both by the normal and tangential components of the electric field. This result is in agreement with the theory of SERS on semiconductor and dielectric substrates. The discovery of the forbidden lines indicates on the sufficiently large role of the strong quadrupole light-molecule interaction in such a system.

TiO2 nanocomposite for the controlled release of drugs against pathogens causing wound infections

NASA Astrophysics Data System (ADS)

Devanand Venkatasubbu, G.; Nagamuthu, S.; Anusuya, T.; Kumar, J.; Chelliah, Ramachandran; Rani Ramakrishnan, Sudha; Antony, Usha; Khan, Imran; Oh, Deog-Hwan

2018-02-01

Chitosan titanium dioxide nanocomposite has been used for wound healing. Titanium dioxide (TiO2) nanoparticles are synthesised and made in to nanocomposite along with chitosan. Curcumin nanoparticles are synthesised. Three different drugs with antimicrobial activity are incorporated into the chitosan/TiO2nanocomposite. Ciprofloxacin, amoxicillin and curcumin nanoparticles are incorporated within the chitosan/TiO2 nanoparticles. The nanoparticles and nanocomposite are characterized with XRD, FTIR, TEM and SEM. Drug loading was found to be around 45% for all the three drug molecules. The drug release profile shows a controlled release of drug molecules from the nanocomposite. Antibacterial studies shows a good inhibition of bacterial species by the nanocomposites.

Substituent influence on the structural, vibrational and electronic properties of 2,5-dihydrothiophene-1,1-dioxide by experimental and DFT methods.

PubMed

Arjunan, V; Thirunarayanan, S; Durga Devi, G; Mohan, S

2015-11-05

Spectroscopic and theoretical quantum chemical studies of 2,5-dihydrothiophene-1,1-dioxide and 3-methyl-2,5-dihydrothiophene-1,1-dioxide have been carried out by FTIR and FT-Raman spectral techniques along with B3LYP methods. The geometry of the compounds have been optimised by B3LYP method with 6-311++G(∗∗) and cc-pVTZ basis sets. The geometrical parameters obtained at B3LYP levels have been compared with the experimental values. Molecular electrostatic potential surface, total electron density distribution and frontier molecular orbital are constructed at B3LYP/cc-pVTZ level to understand the electronic properties. The charge density distribution and sites of chemical reactivity of the molecules have been obtained by mapping electron density isosurface with electrostatic potential surfaces. Natural bond orbital analysis of the molecules are carried out and the occupancies and the atomic hybrid contributions are calculated. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of humidity on CO2 gas sensors based on polyetherimide polymer film

NASA Astrophysics Data System (ADS)

Kang, Ting; Xie, Guangzhong; Zhou, Yong; Xie, Tao; Tai, Huiling

2014-09-01

Quartz Crystal Microbalance (QCM) coated with polyetherimide (PEI) by spin coating method was applied for carbon dioxide (CO2) gas detection at room temperature in this study. The experiments were performed in dry and humid air atmospheres, and the results revealed that the prepared CO2 sensor in moisture circumstance exhibited a larger sensing response than that at dry condition. An enhanced sensing response took place for CO2 detection with the existence of water molecules. The effect of different humidity on QCM sensor performances was investigated as well in this paper. A curve, which displayed a proportional relationship between sensing response and water vapor concentration, was obtained. Moreover, the relevant sensing mechanisms were investigated.

Analyzing adsorption characteristics of CO2, N2 and H2O in MCM-41 silica by molecular simulation

NASA Astrophysics Data System (ADS)

Chang, Shing-Cheng; Chien, Shih-Yao; Chen, Chieh-Li; Chen, Cha'o.-Kuang

2015-03-01

The adsorption characteristics of carbon dioxide, nitrogen and water molecules in MCM-41 mesoporous molecular sieve have been investigated by the molecular simulation. We evaluate the pressure-adsorption isotherms and adsorption density profiles under variant gas pressure, operating temperature and mesopore radius of MCM-41 by the grand canonical Monte Carlo simulation. According to the calculated adsorption energy distributions, the adsorption mechanisms of gas in MCM-41 are mainly divided into three types, namely "surface adsorption" on the pore wall, "multilayer adsorption" on the adsorbed gas molecules and "molecular self-aggregation" near the pore center. In addition, the adsorption characteristics of water molecules in MCM-41 are found to be quite different from those of carbon dioxide and nitrogen due to the hydrogen bonds effect. The results indicate that the MCM-41 is practicable in engineering application for the capture, storage, and re-use of water molecules, since it is temperature-sensitive and can achieve significant adsorption loadings within a small range of pressure values via the capillary condensation phenomena.

Geoengineering with Charged Droplets

NASA Astrophysics Data System (ADS)

Gokturk, H.

2011-12-01

Water molecules in a droplet are held together by intermolecular forces generated by hydrogen bonding which has a bonding energy of only about 0.2 eV. One can create a more rugged droplet by using an ion as a condensation nucleus. In that case, water molecules are held together by the interaction between the ion and the dipole moments of the water molecules surrounding the ion, in addition to any hydrogen bonding. In this research, properties of such charged droplets were investigated using first principle quantum mechanical calculations. A molecule which exhibits positive electron affinity is a good candidate to serve as the ionic condensation nucleus, because addition of an electron to such a molecule creates an energetically more stable state than the neutral molecule. A good example is the oxygen molecule (O2) where energy of O2 negative (O2-) ion is lower than that of the neutral O2 by about 0.5 eV. Examples of other molecules which have positive electron affinity include ozone (O3), nitrogen dioxide (NO2) and sulfur oxides (SOx, x=1-3). Atomic models used in the calculations consisted of a negative ion of one of the molecules mentioned above surrounded by water molecules. Calculations were performed using the DFT method with B3LYP hybrid functional and Pople type basis sets with polarization and diffuse functions. Energy of interaction between O2- ion and the water molecule was found to be ~0.7 eV. This energy is an order of magnitude greater than the thermal energy of even the highest temperatures encountered in the atmosphere. Once created, charged rugged droplets can survive in hot and dry climates where they can be utilized to create humidity and precipitation. The ion which serves as the nucleus of the droplet can attract not only water molecules but also other dipolar gases in the atmosphere. Such dipolar gases include industrial pollutants, for example nitrogen dioxide (NO2) or sulfur dioxide (SO2). Energy of interaction between O2- ion and pollutant molecules was calculated to be ~0.5 eV for NO2 and ~0.9 eV for SO2. These values are comparable to that of water, hence charged droplets have the potential to serve as scavengers of pollutants in the atmosphere. The charged droplet can also interact with quadrupolar gases depending on the charge distribution of the gas. A quadrupole of interest is carbon dioxide (CO2) where oxygens are slightly negative and carbon is slightly positive in a neutral molecule. When CO2 is in the vicinity of a negative ion, the carbon atom gets attracted to the ion, whereas oxygens are repelled from it. This interaction distorts the linear geometry of CO2, turning it into a small dipole. Energy of interaction between O2- ion and CO2 was calculated to be ~0.3 eV which is smaller than those of the above mentioned dipoles, but still significantly greater than the typical thermal energy at 25 C (~0.03 eV). One can expect the diffusion of atmospheric CO2 into the droplets to be enhanced due to the charge. Hence such droplets can help capture the CO2 in the atmosphere and sequester it simply as rain. Charged droplets can be created using electrical,optical, thermal or other means. A method which utilizes solar energy will be described in the presentation.

Gas separation device based on electrical swing adsorption

DOEpatents

Judkins, Roddie R.; Burchell, Timothy D.

1999-10-26

A method and apparatus for separating one constituent, especially carbon dioxide, from a fluid mixture, such as natural gas. The fluid mixture flows through an adsorbent member having an affinity for molecules of the one constituent, the molecules being adsorbed on the adsorbent member. A voltage is applied to the adsorbent member, the voltage imparting a current flow which causes the molecules of the one constituent to be desorbed from the adsorbent member.

Oxidation of Hydrocarbons on the Surface of Tin Dioxide Chemical Sensors

PubMed Central

Teterycz, Helena; Halek, Patryk; Wiśniewski, Kamil; Halek, Grzegorz; Koźlecki, Tomasz; Polowczyk, Izabela

2011-01-01

The paper presents the results of our investigation on the effect of the molecular structure of organic vapors on the characteristics of resistive chemical gas sensors. The sensors were based on tin dioxide and prepared by means of thick film technology. The electrical and catalytic examinations showed that the abstraction of two hydrogen atoms from the organic molecule and formation of a water in result of reaction with a chemisorbed oxygen ion, determine the rate of oxidation reactions, and thus the sensor performance. The rate of the process depends on the order of carbon atoms and Lewis acidity of the molecule. Therefore, any modification of the surface centers of a sensor material, modifies not only the sensor sensitivity, but also its selectivity. PMID:22163855

Unravelling the influence of carbon dioxide on the adsorptive recovery of butanol from fermentation broth using ITQ-29 and ZIF-8.

PubMed

Martin-Calvo, Ana; Van der Perre, Stijn; Claessens, Benjamin; Calero, Sofia; Denayer, Joeri F M

2018-04-18

The vapor phase adsorption of butanol from ABE fermentation at the head space of the fermenter is an interesting route for the efficient recovery of biobutanol. The presence of gases such as carbon dioxide that are produced during the fermentation process causes a stripping of valuable compounds from the aqueous into the vapor phase. This work studies the effect of the presence of carbon dioxide on the adsorption of butanol at a molecular level. With this aim in mind Monte Carlo simulations were employed to study the adsorption of mixtures containing carbon dioxide, butanol and ethanol. Molecular models for butanol and ethanol that reproduce experimental properties of the molecules such as polarity, vapor-liquid coexistence or liquid density have been developed. Pure component isotherms and heats of adsorption have been computed and compared to experimental data to check the accuracy of the interacting parameters. Adsorption of butanol/ethanol mixtures has been studied in absence and presence of CO2 on two representative materials, a pure silica LTA zeolite and a hydrophobic metal-organic framework ZIF-8. To get a better understanding of the molecular mechanism that governs the adsorption of the targeted mixture in the selected materials, the distribution of the molecules inside the structures was analyzed. The combination of these features allows obtaining a deeper understanding of the process and to identify the role of carbon dioxide in the butanol purification process.

New Wind in Old Sails: Novel Applications of Triphos-based Transition Metal Complexes as Homogeneous Catalysts for Small Molecules and Renewables Activation.

PubMed

Mellone, Irene; Bertini, Federica; Gonsalvi, Luca; Guerriero, Antonella; Peruzzini, Maurizio

2015-01-01

Recent developments in the coordination chemistry and applications of Ru-triphos [triphos = 1,1,1-tris-(diphenylphosphinomethyl)ethane] systems are reviewed, highlighting their role as active and selective homogenous catalysts for small molecule activation, biomass conversions and in carbon dioxide utilization-related processes.

Catalyst Substrates Remove Contaminants, Produce Fuel

NASA Technical Reports Server (NTRS)

2012-01-01

A spacecraft is the ultimate tight building. We don t want any leaks, and there is very little fresh air coming in, says Jay Perry, an aerospace engineer at Marshall Space Flight Center. As a result, there is a huge potential for a buildup of contaminants from a host of sources. Inside a spacecraft, contaminants can be introduced from the materials that make spacecraft components, electronics boxes, or activities by the crew such as food preparation or cleaning. Humans also generate contaminants by breathing and through the body s natural metabolic processes. As part of the sophisticated Environmental Control and Life Support System on the International Space Station (ISS), a trace contaminant control system removes carbon dioxide and other impurities from the cabin atmosphere. To maintain healthy levels, the system uses adsorbent media to filter chemical contaminant molecules and a high-temperature catalytic oxidizer to change the chemical structure of the contaminants to something more benign, usually carbon dioxide and water. In the 1990s, while researching air quality control technology for extended spaceflight travel, Perry and others at Marshall were looking for a regenerable process for the continuous removal of carbon dioxide and trace chemical contaminants on long-duration manned space flights. At the time, the existing technology used on U.S. spacecraft could only be used once, which meant that a spacecraft had to carry additional spare parts for use in case the first one was depleted, or the spacecraft would have to return to Earth to exchange the components.

Self-assembly of (perfluoroalkyl)alkanes on a substrate surface from solutions in supercritical carbon dioxide.

PubMed

Gallyamov, Marat O; Mourran, Ahmed; Tartsch, Bernd; Vinokur, Rostislav A; Nikitin, Lev N; Khokhlov, Alexei R; Schaumburg, Kjeld; Möller, Martin

2006-06-14

Toroidal self-assembled structures of perfluorododecylnonadecane and perfluorotetradecyloctadecane have been deposited on mica and highly oriented pyrolytic graphite surfaces by exposure of the substrates to solutions of the (pefluoroalkyl)alkanes in supercritical carbon dioxide. Scanning force microscopy (SFM) images have displayed a high degree of regularity of these self-assembled nanoobjects regarding size, shape, and packing in a monolayer. Analysis of SFM images allowed us to estimate that each toroidal domain has an outer diameter of about 50 nm and consists of several thousands of molecules. We propose a simple model explaining the clustering of the molecules to objects with a finite size. The model based on the close-packing principles predicts formation of toroids, whose size is determined by the molecular geometry. Here, we consider the amphiphilic nature of the (perfluoroalkyl)alkane molecules in combination with incommensurable packing parameters of the alkyl- and the perfluoralkyl-segments to be a key factor for such a self-assembly.

40 CFR 415.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... CATEGORY Titanium Dioxide Production Subcategory § 415.223 Effluent limitations guidelines representing the... to this subpart and producing titanium dioxide by the sulfate process must achieve the following..., any existing point source subject to this subpart and producing titanium dioxide by the chloride...

40 CFR 415.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... CATEGORY Titanium Dioxide Production Subcategory § 415.223 Effluent limitations guidelines representing the... to this subpart and producing titanium dioxide by the sulfate process must achieve the following..., any existing point source subject to this subpart and producing titanium dioxide by the chloride...

Gas exchange

MedlinePlus Videos and Cool Tools

... network of tiny blood vessels called capillaries, which are located in the walls of the alveoli. The ... time, the carbon dioxide molecules in the alveoli are blown out of the body with the next ...

Formation of solvate structures by the ortho-, meta-, and para-isomers of hydroxybenzoic acid in supercritical fluid

NASA Astrophysics Data System (ADS)

Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Petrenko, V. E.

2017-04-01

The solvate structures formed by the ortho-, meta-, and para-isomers of hydroxybenzoic acid ( o-HBA, m-HBA, and p-HBA) with a polar co-solvent (methanol at a concentration of 0.030 and 0.035 mole fractions) in supercritical carbon dioxide at a constant density of 0.7 g/cm3 and temperatures of 318 and 328 K have been studied by the classic molecular dynamics. It has been determined that a stable hydrogen-bonded complex with the co-solvent forms via the hydrogen of the carboxyl group for all isomers. The probability of this complex existence is high at all temperatures and concentrations. In the o-HBA molecule, the other functional groups are engaged in the intramolecular hydrogen bond, but not involved in interactions with methanol. It has been found that m-HBA and p-HBA can be involved in hydrogen bonds with methanol via hydroxyl hydrogen and oxygen atoms; they are characterized by the presence of one more co-solvent molecule (rarely, two molecules) in their solvation shell and intermittent formations/breakages of hydrogen bonds via other functional groups. These bonds are far less stable, and their formation is sensitive to change of temperature and co-solvent concentration. It has been concluded that the degree of selective solvation of m-HBA and p-HBA by co-solvent molecules is approximately the same, but the rate of structural rearrangements in the nearest environment of m-HBA is higher than that of p-HBA.

Collision and radiative processes in emission of atmospheric carbon dioxide

NASA Astrophysics Data System (ADS)

Smirnov, B. M.

2018-05-01

The peculiarities of the spectroscopic properties of CO2 molecules in air due to vibration-rotation radiative transitions are analyzed. The absorption coefficient due to atmospheric carbon dioxide and other atmospheric components is constructed within the framework of the standard atmosphere model, on the basis of classical molecular spectroscopy and the regular model for the spectroscopy absorption band. The radiative flux from the atmosphere toward the Earth is represented as that of a blackbody, and the radiative temperature for emission at a given frequency is determined with accounting for the local thermodynamic equilibrium, a small gradient of the tropospheric temperature and a high optical thickness of the troposphere for infrared radiation. The absorption band model with an absorption coefficient averaged over the frequency and line-by-line model are used for evaluating the radiative flux from the atmosphere to the Earth which values are nearby for these models and are equal W m‑2 for the contemporary concentration of atmospheric CO2 molecules and W m‑2 at its doubled value. The absorption band model is not suitable to calculate the radiative flux change at doubling of carbon dioxide concentration because averaging over oscillations decreases the range where the atmospheric optical thickness is of the order of one, and just this range determines this change. The line-by-line method gives the change of the global temperature K as a result of doubling the carbon dioxide concentration. The contribution to the global temperature change due to anthropogenic injection of carbon dioxide in the atmosphere, i.e. resulted from combustion of fossil fuels, is approximately 0.02 K now.

75 FR 81471 - Approval and Promulgation of Air Quality Implementation Plans; Minnesota; Sulfur Dioxide SIP...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-28

... Promulgation of Air Quality Implementation Plans; Minnesota; Sulfur Dioxide SIP Revision for Marathon Petroleum... October 6, 2009, Minnesota submitted a request for a sulfur dioxide State Implementation Plan revision for... installation of new boilers and a sulfur recovery unit and changes to three existing heaters. Overall, this...

Hemoglobin

DTIC Science & Technology

1993-03-08

affinity, which is less at low levels of hemoglobin saturation, increases markedly as fractional saturation increases. Thus, high affinity for 02 at... diphosphoglycerate (2,3-DPG), and carbon dioxide (Co 2). Since they are linked to 02 binding, they are called oxygen-linked effectors. The oxygen...hemoglobin molecule because of the negative charge of the ions. 2,3- Diphosphoglycerate is a molecule formed during the breakdown of sugar in normal human

Production of long chain alkyl esters from carbon dioxide and electricity by a two-stage bacterial process.

PubMed

Lehtinen, Tapio; Efimova, Elena; Tremblay, Pier-Luc; Santala, Suvi; Zhang, Tian; Santala, Ville

2017-11-01

Microbial electrosynthesis (MES) is a promising technology for the reduction of carbon dioxide into value-added multicarbon molecules. In order to broaden the product profile of MES processes, we developed a two-stage process for microbial conversion of carbon dioxide and electricity into long chain alkyl esters. In the first stage, the carbon dioxide is reduced to organic compounds, mainly acetate, in a MES process by Sporomusa ovata. In the second stage, the liquid end-products of the MES process are converted to the final product by a second microorganism, Acinetobacter baylyi in an aerobic bioprocess. In this proof-of-principle study, we demonstrate for the first time the bacterial production of long alkyl esters (wax esters) from carbon dioxide and electricity as the sole sources of carbon and energy. The process holds potential for the efficient production of carbon-neutral chemicals or biofuels. Copyright © 2017 Elsevier Ltd. All rights reserved.

Communication: Photoinduced carbon dioxide binding with surface-functionalized silicon quantum dots.

PubMed

Douglas-Gallardo, Oscar A; Sánchez, Cristián Gabriel; Vöhringer-Martinez, Esteban

2018-04-14

Nowadays, the search for efficient methods able to reduce the high atmospheric carbon dioxide concentration has turned into a very dynamic research area. Several environmental problems have been closely associated with the high atmospheric level of this greenhouse gas. Here, a novel system based on the use of surface-functionalized silicon quantum dots (sf-SiQDs) is theoretically proposed as a versatile device to bind carbon dioxide. Within this approach, carbon dioxide trapping is modulated by a photoinduced charge redistribution between the capping molecule and the silicon quantum dots (SiQDs). The chemical and electronic properties of the proposed SiQDs have been studied with a Density Functional Theory and Density Functional Tight-Binding (DFTB) approach along with a time-dependent model based on the DFTB framework. To the best of our knowledge, this is the first report that proposes and explores the potential application of a versatile and friendly device based on the use of sf-SiQDs for photochemically activated carbon dioxide fixation.

Imaging metal-like monoclinic phase stabilized by surface coordination effect in vanadium dioxide nanobeam

PubMed Central

Li, Zejun; Wu, Jiajing; Hu, Zhenpeng; Lin, Yue; Chen, Qi; Guo, Yuqiao; Liu, Yuhua; Zhao, Yingcheng; Peng, Jing; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2017-01-01

In correlated systems, intermediate states usually appear transiently across phase transitions even at the femtosecond scale. It therefore remains an open question how to determine these intermediate states—a critical issue for understanding the origin of their correlated behaviour. Here we report a surface coordination route to successfully stabilize and directly image an intermediate state in the metal-insulator transition of vanadium dioxide. As a prototype metal-insulator transition material, we capture an unusual metal-like monoclinic phase at room temperature that has long been predicted. Coordinate bonding of L-ascorbic acid molecules with vanadium dioxide nanobeams induces charge-carrier density reorganization and stabilizes metallic monoclinic vanadium dioxide, unravelling orbital-selective Mott correlation for gap opening of the vanadium dioxide metal–insulator transition. Our study contributes to completing phase-evolution pathways in the metal-insulator transition process, and we anticipate that coordination chemistry may be a powerful tool for engineering properties of low-dimensional correlated solids. PMID:28613281

Communication: Photoinduced carbon dioxide binding with surface-functionalized silicon quantum dots

NASA Astrophysics Data System (ADS)

Douglas-Gallardo, Oscar A.; Sánchez, Cristián Gabriel; Vöhringer-Martinez, Esteban

2018-04-01

Nowadays, the search for efficient methods able to reduce the high atmospheric carbon dioxide concentration has turned into a very dynamic research area. Several environmental problems have been closely associated with the high atmospheric level of this greenhouse gas. Here, a novel system based on the use of surface-functionalized silicon quantum dots (sf-SiQDs) is theoretically proposed as a versatile device to bind carbon dioxide. Within this approach, carbon dioxide trapping is modulated by a photoinduced charge redistribution between the capping molecule and the silicon quantum dots (SiQDs). The chemical and electronic properties of the proposed SiQDs have been studied with a Density Functional Theory and Density Functional Tight-Binding (DFTB) approach along with a time-dependent model based on the DFTB framework. To the best of our knowledge, this is the first report that proposes and explores the potential application of a versatile and friendly device based on the use of sf-SiQDs for photochemically activated carbon dioxide fixation.

Origin of gasoline-range hydrocarbons and their migration by solution in carbon dioxide in Norton basin, Alaska.

USGS Publications Warehouse

Kvenvolden, K.A.; Claypool, G.E.

1980-01-01

Carbon dioxide from a submarine seep in Norton Sound carries a minor component of gas- and gasoline-range hydrocarbons. The molecular and isotopic compositions of the hydrocarbon gases and the presence of gasoline-range hydrocarbons indicate that these molecules are derived from thermal alteration of marine and/or nonmarine organic matter buried within Norton basin. The gasoline-range hydrocarbon distribution suggests that the hydrocarbon mixture is an immature petroleum-like condensate of lower temperature origin than normal crude oil. The submarine seep provides a natural example in support of a carbon dioxide solution transport mechanism thought to be operative in the migration of hydrocarbons in certain reservoirs.-Authors

Probing the Superfluid Response of para-Hydrogen with a Sulfur Dioxide Dopant.

PubMed

Zeng, Tao; Guillon, Grégoire; Cantin, Joshua T; Roy, Pierre-Nicholas

2013-07-18

We recently presented the first attempt at using an asymmetric top molecule (para-water) to probe the superfluidity of nanoclusters (of para-hydrogen) [ Zeng , T. ; Li , H. ; Roy , P.-N. J. Phys. Chem. Lett. 2013 , 4 , 18 - 22 ]. Unfortunately, para-water could not be used to probe the para-hydrogen superfluid response. We now report a theoretical simulation of sulfur dioxide rotating in para-hydrogen clusters and show that this asymmetric top can serve as a genuine probe of superfluidity. With this probe, we predict that as few as four para-hydrogen molecules are enough to form a superfluid cluster, the smallest superfluid system to date. We also propose the concept of "exchange superfluid fraction" as a more precise measurement. New superfluid scenarios brought about by an asymmetric top dopant and potential experimental measurements are discussed.

Surface force analysis of glycine adsorption on different crystal surfaces of titanium dioxide (TiO2).

PubMed

Ganbaatar, Narangerel; Imai, Kanae; Yano, Taka-Aki; Hara, Masahiko

2017-01-01

Surface force analysis with atomic force microscope (AFM) in which a single amino acid residue was mounted on the tip apex of AFM probe was carried out for the first time at the molecular level on titanium dioxide (TiO 2 ) as a representative mineral surface for prebiotic chemical evolution reactions. The force analyses on surfaces with three different crystal orientations revealed that the TiO 2 (110) surface has unique characteristics for adsorbing glycine molecules showing different features compared to those on TiO 2 (001) and (100). To examine this difference, we investigated thermal desorption spectroscopy (TDS) and the interaction between the PEG cross-linker and the three TiO 2 surfaces. Our data suggest that the different single crystal surfaces would provide different chemical evolution field for amino acid molecules.

Vertical nanopillars for highly localized fluorescence imaging

PubMed Central

Xie, Chong; Hanson, Lindsey; Cui, Yi; Cui, Bianxiao

2011-01-01

Observing individual molecules in a complex environment by fluorescence microscopy is becoming increasingly important in biological and medical research, for which critical reduction of observation volume is required. Here, we demonstrate the use of vertically aligned silicon dioxide nanopillars to achieve below-the-diffraction-limit observation volume in vitro and inside live cells. With a diameter much smaller than the wavelength of visible light, a transparent silicon dioxide nanopillar embedded in a nontransparent substrate restricts the propagation of light and affords evanescence wave excitation along its vertical surface. This effect creates highly confined illumination volume that selectively excites fluorescence molecules in the vicinity of the nanopillar. We show that this nanopillar illumination can be used for in vitro single-molecule detection at high fluorophore concentrations. In addition, we demonstrate that vertical nanopillars interface tightly with live cells and function as highly localized light sources inside the cell. Furthermore, specific chemical modification of the nanopillar surface makes it possible to locally recruit proteins of interest and simultaneously observe their behavior within the complex, crowded environment of the cell. PMID:21368157

Core localization and {sigma}* delocalization in the O 1s core-excited sulfur dioxide molecule

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindgren, Andreas; Kivimaeki, Antti; Sorensen, Stacey L.

Electron-ion-ion coincidence measurements of sulfur dioxide at discrete resonances near the O 1s ionization edge are reported. The spectra are analyzed using a model based upon molecular symmetry and on the geometry of the molecule. We find clear evidence for molecular alignment that can be ascribed to symmetry properties of the ground and core-excited states. Configuration interaction (CI) calculations indicate geometry changes in accord with the measured spectra. For the SO{sub 2} molecule, however, we find that the localized core hole does not produce measurable evidence for valence localization, since the transition dipole moment is not parallel to a breakingmore » {sigma}* O-S bond, in contrast to the case of ozone. The dissociation behavior based upon the CI calculations using symmetry-broken orbitals while fixing a localized core-hole site is found to be nearly equivalent to that using symmetry-adapted orbitals. This implies that the core-localization effect is not strong enough to localize the {sigma}* valence orbital.« less

Effect of Greenhouse Gases Dissolved in Seawater

PubMed Central

Matsunaga, Shigeki

2015-01-01

A molecular dynamics simulation has been performed on the greenhouse gases carbon dioxide and methane dissolved in a sodium chloride aqueous solution, as a simple model of seawater. A carbon dioxide molecule is also treated as a hydrogen carbonate ion. The structure, coordination number, diffusion coefficient, shear viscosity, specific heat, and thermal conductivity of the solutions have been discussed. The anomalous behaviors of these properties, especially the negative pressure dependence of thermal conductivity, have been observed in the higher-pressure region. PMID:26729101

Methods of making monolayers

DOEpatents

Alford, Kentin L [Pasco, WA; Simmons, Kevin L [Kennewick, WA; Samuels, William D [Richland, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [Albuquerque, NM; Shin, Yongsoon [Richland, WA; Fryxell, Glen E [Kennewick, WA

2009-12-08

The invention pertains to methods of forming monolayers on various surfaces. The surfaces can be selected from a wide array of materials, including, for example, aluminum dioxide, silicon dioxide, carbon and SiC. The substrates can be planar or porous. The monolayer is formed under enhanced pressure conditions. The monolayer contains functionalized molecules, and accordingly functionalizes a surface of the substrate. The properties of the functionalized substrate can enhance the substrate's applicability for numerous purposes including, for example, utilization in extracting contaminants, or incorporation into a polymeric matrix.

Methods of making monolayers

DOEpatents

Alford, Kentin L [Pasco, WA; Simmons, Kevin L [Kennewick, WA; Samuels, William D [Richland, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [Albuquerque, NM; Shin, Yongsoon [Richland, WA; Fryxell, Glen E [Kennewick, WA

2009-09-15

The invention pertains to methods of forming monolayers on various surfaces. The surfaces can be selected from a wide array of materials, including, for example, aluminum dioxide, silicon dioxide, carbon and SiC. The substrates can be planar or porous. The monolayer is formed under enhanced pressure conditions. The monolayer contains functionalized molecules, and accordingly functionalizes a surface of the substrate. The properties of the functionalized substrate can enhance the substrate's applicability for numerous purposes including, for example, utilization in extracting contaminants, or incorporation into a polymeric matrix.

A Cu-Zn nanoparticle promoter for selective carbon dioxide reduction and its application in visible-light-active Z-scheme systems using water as an electron donor.

PubMed

Yin, Ge; Sako, Hiroshi; Gubbala, Ramesh V; Ueda, Shigenori; Yamaguchi, Akira; Abe, Hideki; Miyauchi, Masahiro

2018-04-17

Selective carbon dioxide photoreduction to produce formic acid was achieved under visible light irradiation using water molecules as electron donors, similar to natural plants, based on the construction of a Z-scheme light harvesting system modified with a Cu-Zn alloy nanoparticle co-catalyst. The faradaic efficiency of our Z-scheme system for HCOOH generation was over 50% under visible light irradiation.

Adsorption and Gas Separation of Molecules by Carbon Nanohorns.

PubMed

Gatica, Silvina M; Nekhai, Anton; Scrivener, Adam

2016-05-19

In this paper, we report the results of Monte Carlo simulations of the adsorption of neon, argon, methane and carbon dioxide in carbon nanohorns. We model the nanohorns as an array of carbon cones and obtained adsorption isotherms and isosteric heats. The main sites of adsorption are inside the cones and in the interstices between three cones. We also calculated the selectivity of carbon dioxide/methane, finding that nanohorns are a suitable substrate for gas separation. Our simulations are compared to available experimental data.

Effect of Greenhouse Gases Dissolved in Seawater.

PubMed

Matsunaga, Shigeki

2015-12-30

A molecular dynamics simulation has been performed on the greenhouse gases carbon dioxide and methane dissolved in a sodium chloride aqueous solution, as a simple model of seawater. A carbon dioxide molecule is also treated as a hydrogen carbonate ion. The structure, coordination number, diffusion coefficient, shear viscosity, specific heat, and thermal conductivity of the solutions have been discussed. The anomalous behaviors of these properties, especially the negative pressure dependence of thermal conductivity, have been observed in the higher-pressure region.

Formation of grafted surface layers on silicon dioxide particles and their investigation by means of thermoprogrammed oxidation

NASA Astrophysics Data System (ADS)

Aleksandrova, E. O.; Novichkov, R. V.; Olenin, A. Yu.; Zuev, B. K.

2017-03-01

Silica nanoparticles are obtained according to the Stober-Fink-Bohn method, and their surfaces are chemically modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. It is estimated that sols of porous silica nanoparticles (average sizes, 50-200 nm) form during primary chemical process; the average size of the particles can be increased to 400-500 nm by consecutive growth. Oxythermography (thermoprogrammed oxidation) measurements reveal a stepped dependence between the content of organic substance of nanoparticles and the duration of chemical modification reaction exists. It is concluded that this could be due to the formation of dense shell (or shells) as a result of sols aging between the cycles of growth; such shells impose diffusive restrictions when molecules penetrate into the pores of the internal volume of the particles.

The effect of catena position on greenhouse gas emissions from Dambo located termite (odontotermes transvaalensis) mounds from Central Zimbabwe

USDA-ARS?s Scientific Manuscript database

Nitrous oxide (N2O) is one of the most important greenhouse gases. The global warming potentials (GWP) of nitrous oxide (N2O) is 310 more, than that of carbon dioxide (CO2) during a 100 year time scale on molecule for molecule basis. Natural sources of N2O include wetlands. Sub-Saharan Africa is occ...

BILP-19-An Ultramicroporous Organic Network with Exceptional Carbon Dioxide Uptake.

PubMed

Klumpen, Christoph; Radakovitsch, Florian; Jess, Andreas; Senker, Jürgen

2017-08-12

Porous benzimidazole-based polymers (BILPs) have proven to be promising for carbon dioxide capture and storage. The polarity of their chemical structure in combination with an inherent porosity allows for adsorbing large amounts of carbon dioxide in combination with high selectivities over unpolar guest molecules such as methane and nitrogen. For this reason, among purely organic polymers, BILPs contain some of the most effective networks to date. Nevertheless, they are still outperformed by competitive materials such as metal-organic frameworks (MOFs) or metal doped porous polymers. Here, we report the synthesis of BILP-19 and its exceptional carbon dioxide uptake of up to 6 mmol•g-1 at 273 K, making the network comparable to state-of-the-art materials. BILP-19 precipitates in a particulate structure with a strongly anisotropic growth into platelets, indicating a sheet-like structure for the network. It exhibits only a small microporous but a remarkable ultra-microporous surface area of 144 m2•g-1 and 1325 m2•g-1, respectively. We attribute the exceptional uptake of small guest molecules such as carbon dioxide and water to the distinct ultra-microporosity. Additionally, a pronounced hysteresis for both guests is observed, which in combination with the platelet character is probably caused by an expansion of the interparticle space, creating additional accessible ultra-microporous pore volume. For nitrogen and methane, this effect does not occur which explains their low affinity. In consequence, Henry selectivities of 123 for CO2/N2 at 298 K and 12 for CO2/CH4 at 273 K were determined. The network was carefully characterized with solid-state nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, thermal gravimetry (TG) and elemental analyses as well as physisorption experiments with Ar, N2, CO2, CH4 and water.

Tunable top-down fabrication and functional surface coating of single-crystal titanium dioxide nanostructures and nanoparticles

NASA Astrophysics Data System (ADS)

Ha, Seungkyu; Janissen, Richard; Ussembayev, Yera Ye.; van Oene, Maarten M.; Solano, Belen; Dekker, Nynke H.

2016-05-01

Titanium dioxide (TiO2) is a key component of diverse optical and electronic applications that exploit its exceptional material properties. In particular, the use of TiO2 in its single-crystalline phase can offer substantial advantages over its amorphous and polycrystalline phases for existing and yet-to-be-developed applications. However, the implementation of single-crystal TiO2 has been hampered by challenges in its fabrication and subsequent surface functionalization. Here, we introduce a novel top-down approach that allows for batch fabrication of uniform high-aspect-ratio single-crystal TiO2 nanostructures with targeted sidewall profiles. We complement our fabrication approach with a functionalization strategy that achieves dense, uniform, and area-selective coating with a variety of biomolecules. This allows us to fabricate single-crystal rutile TiO2 nanocylinders tethered with individual DNA molecules for use as force- and torque-transducers in an optical torque wrench. These developments provide the means for increased exploitation of the superior material properties of single-crystal TiO2 at the nanoscale.Titanium dioxide (TiO2) is a key component of diverse optical and electronic applications that exploit its exceptional material properties. In particular, the use of TiO2 in its single-crystalline phase can offer substantial advantages over its amorphous and polycrystalline phases for existing and yet-to-be-developed applications. However, the implementation of single-crystal TiO2 has been hampered by challenges in its fabrication and subsequent surface functionalization. Here, we introduce a novel top-down approach that allows for batch fabrication of uniform high-aspect-ratio single-crystal TiO2 nanostructures with targeted sidewall profiles. We complement our fabrication approach with a functionalization strategy that achieves dense, uniform, and area-selective coating with a variety of biomolecules. This allows us to fabricate single-crystal rutile TiO2 nanocylinders tethered with individual DNA molecules for use as force- and torque-transducers in an optical torque wrench. These developments provide the means for increased exploitation of the superior material properties of single-crystal TiO2 at the nanoscale. Electronic supplementary information (ESI) available: Experimental details (ESI Methods) of the optic axis orientation of TiO2 nanocylinders, Cr etch mask fabrication, surface functionalization and its evaluation using fluorescence microscopy, preparation of DNA constructs, assembly of flow cells, bioconjugation of TiO2 nanocylinders, OTW instrumentation and measurements; TiO2 dry etching optimization and the etching parameters employed (Tables S1 and S2); dimensional analysis of TiO2 nanocylinders (Table S3); diverse applications of TiO2 at the nanoscale (Fig. S1); selection of etch mask material (Fig. S2); control of sidewall profiles in TiO2 etching (Fig. S3); size distributions of TiO2 nanocylinders (Fig. S4); quantitative comparisons of different surface linker molecules (Fig. S5); DLS measurements on TiO2 nanocylinders (Fig. S6); optical trap calibration (Fig. S7); and supplementary references. See DOI: 10.1039/c6nr00898d

Single Molecule Conductance of Oligothiophene Derivatives

NASA Astrophysics Data System (ADS)

Dell, Emma J.

This thesis studies the electronic properties of small organic molecules based on the thiophene motif. If we are to build next-generation devices, advanced materials must be designed which possess requisite electronic functionality. Molecules present attractive candidates for these ad- vanced materials since nanoscale devices are particularly sought after. However, selecting a molecule that is suited to a certain electronic function remains a challenge, and characterization of electronic behavior is therefore critical. Single molecule conductance measurements are a powerful tool to determine properties on the nanoscale and, as such, can be used to investigate novel building blocks that may fulfill the design requirements of next-generation devices. Combining these conductance results with strategic chemical synthesis allows for the development of new families of molecules that show attractive properties for future electronic devices. Since thiophene rings are the fruitflies of organic semiconductors on the bulk scale, they present an intriguing starting point for building functional materials on the nanoscale, and therefore form the structural basis of all molecules studied herein. First, the single-molecule conductance of a family of bithiophene derivatives was measured. A broad distribution in the single-molecule conductance of bithiophene was found compared with that of a biphenyl. This increased breadth in the conductance distribution was shown to be explained by the difference in 5-fold symmetry of thiophene rings as compared to the 6-fold symmetry of benzene rings. The reduced symmetry of thiophene rings results in a restriction on the torsion angle space available to these molecules when bound between two metal electrodes in a junction, causing each molecular junction to sample a different set of conformers in the conductance measurements. By contrast, the rotations of biphenyl are essentially unimpeded by junction binding, allowing each molecular junction to sample similar conformers. This work demonstrates that the conductance of bithiophene displays a strong dependence on the conformational fluctuations accessible within a given junction configuration, and that the symmetry of such small molecules can significantly influence their conductance behavior. Next, the single-molecule conductance of a family of oligothiophenes comprising one to six thiophene units was measured. An anomalous behavior was found: the peak of the conductance histogram distribution did not follow a clear exponential decay with increasing number of thiophene units in the chain. The electronic properties of the materials were characterized by optical spectroscopy and electrochemistry to gain an understanding of the factors affecting the conductance of these molecules. Different conformers in the junction were postulated to be a contributing factor to the anomalous trend in the observed conductance as a function of molecule length. Then, the electronic properties of the thiophene-1,1-dioxide unit were investigated. These motifs have become synthetically accessible in the last decade, due to Rozen's unprecedentedly potent oxidizing reagent - HOF˙CH 3CN - which has been shown to be powerful yet selective enough to oxidize thiophenes in various environments. The resulting thiophene-1,1-dioxides show great promise for electronic devices. The oxidation chemistry of thiophenes was expanded and tuning of the frontier energy levels was demonstrated through combining electron poor and electron rich units. Finally, charge carriers in single-molecule junctions were shown to be tunable within a family of molecules containing these thiophene-1,1-dioxide (TDO) building blocks. Oligomers of TDO were designed in order to increase electron affinity, maintain delocalized frontier orbitals, while significantly decreasing the transport gap. Through thermopower measurements, the dominant charge carriers were shown to change from holes to electrons as the number of TDO units was increased. This resulted in a unique system in which the charge carrier depends on backbone length, providing a new means to tune p- and n-type transport in organic materials. Taken together, the results presented in this thesis offer an insight into how molecular symme- try and the accessible conformers within a junction have important consequences on conductance behavior. Additionally, thiophene-1,1-dioxide is shown to be an exciting unit for single molecule devices, especially when combined with electron rich thiophene flanking groups. By demon- strating, for the first time, a change in conductance pathway with molecular length, this work provides a framework for using frontier orbital levels to strategically design electronic building blocks.

Effects of low sulfur dioxide concentrations on bioactive compounds and antioxidant properties of Aglianico red wine.

PubMed

Gabriele, Morena; Gerardi, Chiara; Lucejko, Jeannette J; Longo, Vincenzo; Pucci, Laura; Domenici, Valentina

2018-04-15

This study analyzed the effect of low sulfur dioxide concentrations on the chromatic properties, phytochemical composition and antioxidant activity of Aglianico red wines with respect to wines produced from conventional winemaking. We determined the phytochemical composition by spectrophotometric methods and HPLC-DAD analysis and the in vitro antioxidant activity of different wine samples by the ORAC assay. The main important classes of fluorophore molecules in red wine were identified by Front-Face fluorescence spectroscopy, and the emission intensity trend was investigated at various sulfur dioxide concentrations. Lastly, we tested the effects of both conventional and low sulfite wines on ex vivo human erythrocytes under oxidative stimulus by the cellular antioxidant activity (CAA) assay and the hemolysis test. The addition of sulfur dioxide, which has well-known side effects, increased the content of certain bioactive components but did not raise the erythrocyte antioxidant capacity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Accelerating electrostatic pair methods on graphical processing units to study molecules in supercritical carbon dioxide.

PubMed

Baker, John A; Hirst, Jonathan D

2014-01-01

Traditionally, electrostatic interactions are modelled using Ewald techniques, which provide a good approximation, but are poorly suited to GPU architectures. We use the GPU versions of the LAMMPS MD package to implement and assess the Wolf summation method. We compute transport and structural properties of pure carbon dioxide and mixtures of carbon dioxide with either methane or difluoromethane. The diffusion of pure carbon dioxide is indistinguishable when using the Wolf summation method instead of PPPM on GPUs. The optimum value of the potential damping parameter, α, is 0.075. We observe a decrease in accuracy when the system polarity increases, yet the method is robust for mildly polar systems. We anticipate the method can be used for a number of techniques, and applied to a variety of systems. Substitution of PPPM can yield a two-fold decrease in the wall-clock time.

Apparatus to recover tritium from tritiated molecules

DOEpatents

Swansiger, William A.

1988-01-01

An apparatus for recovering tritium from tritiated compounds is provided, including a preheater for heating tritiated water and other co-injected tritiated compounds to temperatures of about 600.degree. C. and a reactor charged with a mixture of uranium and uranium dioxide for receiving the preheated mixture. The reactor vessel is preferably stainless steel of sufficient mass so as to function as a heat sink preventing the reactor side walls from approaching high temperatures. A disposable copper liner extends between the reaction chamber and stainless steel outer vessel to prevent alloying of the uranium with the outer vessel. The uranium dioxide functions as an insulating material and heat sink preventing the reactor side walls from attaining reaction temperatures to thereby minimize tritium permeation rates. The uranium dioxide also functions as a diluent to allow for volumetric expansion of the uranium as it is converted to uranium dioxide.

Investigation of industrial-scale carbon dioxide reduction using pulsed electron beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrov, G. M.; Apruzese, J. P.; Petrova, Tz. B.

Carbon dioxide is the most important greenhouse gas contributing to global warming. To help mitigate increasing CO{sub 2} concentrations, we investigate a method of carbon dioxide reduction using high-power electron beams, which can be used on an industrial scale. A series of experiments are conducted in which the reduction of CO{sub 2} is measured for different gas compositions and power deposition rates. An electron beam deposition model is applied to compute reduction rates of CO{sub 2} and energy cost for breaking a CO{sub 2} molecule in flue gas and pure carbon dioxide at atmospheric pressure. For flue gas consisting ofmore » 82% N{sub 2}, 6% O{sub 2}, and 12% CO{sub 2}, the calculated energy cost is 85 eV per molecule. In order to dissociate 50% of the CO{sub 2} molecules, beam energy density deposition on the order of 20 J/cm{sup 3} is required. Electron beam irradiation of 12.6 liter gas volume containing 90% CO{sub 2} and 10% CH{sub 4} at beam energy density deposition of 4.2 J/cm{sup 3}, accumulated over 43 shots in a 20 min interval, reduced the CO{sub 2} concentration to 78%. Analogous experiments with a gas mixture containing 11.5% CO{sub 2}, 11.5% CH{sub 4}, and balance of Ar, reduced the CO{sub 2} concentration to below 11% with energy deposition 0.71 J/cm{sup 3}, accumulated over 10 shots in a 5 min interval. The experimental data and the theoretical predictions of CO{sub 2} reduction using pulsed electron beams are in agreement within the experimental error. Other techniques to enhance the removal of CO{sub 2} with pulsed electron beams are also explored, yielding new possible avenues of research.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hur, Tae-Bong; Fazio, James; Romanov, Vyacheslav

Due to increasing atmospheric CO2 concentrations causing the global energy and environmental crises, geological sequestration of carbon dioxide is now being actively considered as an attractive option to mitigate greenhouse gas emissions. One of the important strategies is to use deep unminable coal seams, for those generally contain significant quantities of coal bed methane that can be recovered by CO2 injection through enhanced coal bed natural gas production, as a method to safely store CO2. It has been well known that the adsorbing CO2 molecules introduce structural deformation, such as distortion, shrinkage, or swelling, of the adsorbent of coal organicmore » matrix. The accurate investigations of CO2 sorption capacity as well as of adsorption behavior need to be performed under the conditions that coals deform. The U.S. Department of Energy-National Energy Technology Laboratory and Regional University Alliance are conducting carbon dioxide sorption isotherm experiments by using manometric analysis method for estimation of CO2 sorption capacity of various coal samples and are constructing a gravimetric apparatus which has a visual window cell. The gravimetric apparatus improves the accuracy of carbon dioxide sorption capacity and provides feasibility for the observation of structural deformation of coal sample while carbon dioxide molecules interact with coal organic matrix. The CO2 sorption isotherm measurements have been conducted for moist and dried samples of the Central Appalachian Basin (Russell County, VA) coal seam, received from the SECARB partnership, at the temperature of 55 C.« less

W.A. Parish Post Combustion CO 2 Capture and Sequestration Project Final Public Design Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Armpriester, Anthony

The Petra Nova Project is a commercial scale post-combustion carbon dioxide capture project that is being developed by a joint venture between NRG Energy (NRG) and JX Nippon Oil and Gas Exploration (JX). The project is designed to separate and capture carbon dioxide from an existing coal-fired unit's flue gas slipstream at NRG's W.A. Parish Generation Station located southwest of Houston, Texas. The captured carbon dioxide will be transported by pipeline and injected into the West Ranch oil field to boost oil production. The project, which is partially funded by financial assistance from the U.S. Department of Energy will usemore » Mitsubishi Heavy Industries of America, Inc.'s Kansai Mitsubishi Carbon Dioxide Recovery (KM-CDR(R)) advanced amine-based carbon dioxide absorption technology to treat and capture at least 90% of the carbon dioxide from a 240 megawatt equivalent flue gas slipstream off of Unit 8 at W.A. Parish. The project will capture approximately 5,000 tons of carbon dioxide per day or 1.5 million tons per year that Unit 8 would otherwise emit, representing the largest commercial scale deployment of post-combustion carbon dioxide capture at a coal power plant to date. The joint venture issued full notice to proceed in July 2014 and when complete, the project is expected to be the world's largest post-combustion carbon dioxide capture facility on an existing coal plant. The detailed engineering is sufficiently complete to prepare and issue the Final Public Design Report.« less

Infrared Lasers in Chemistry.

ERIC Educational Resources Information Center

John, Phillip

1982-01-01

Selected infrared laser chemistry topics are discussed including carbon dioxide lasers, infrared quanta and molecules, laser-induced chemistry, structural isomerization (laser purification, sensitized reactions, and dielectric breakdown), and fundamental principles of laser isotope separation, focusing on uranium isotope separation. (JN)

[Hygienic evaluation of direct heating of the air delivered to the shaft].

PubMed

Velichkovskiĭ, B T; Malikov, Iu K; Troitskaia, N A; Belen'kaia, M A; Sergeeva, N V; Shirokova, O V; Kashanskiĭ, S V; Slyshkina, T V; Simonova, O V; Zykova, V A

2011-01-01

The paper gives the results of exploring a test pre-heating system for the air (APHS) delivered to the shaft. The system has been first used in the Urals. The supply air is heated by burning natural gas in the air current. The APHS system with a RG air heater (000 "Gas-Engineering") is equipped in addition to the existing heaters to enhance heat supply reliability in northern conditions. The data of the studies show that in all periods of the heating season (interseason, moderate frosts, the coldest month), the concentrations of hazardous substances, such as nitric oxides, nitric dioxide, sulfur dioxide, carbon dioxide, benz(a)pyrene, solid aerosol in the shaft-delivered air, do not exceed those given in the existing regulation provided that the design operating conditions are met. With the maximum gas consumption, the coldest month only was marked by the nitric dioxide content being greater than the standard values, causing the maximum projected natural gas consumption to be lower in the APHS system. The air level of nitric dioxide proved to be a major hygiene indicator while using this air heater.

Distribution of Sulfur Dioxide Frost on Io

NASA Image and Video Library

1998-03-26

Sulfur dioxide, normally a gas at room temperatures, is known to exist on Io surface as a frost, condensing there from the hot gases emanating from the Io volcanoes. This image was taken in 1996 by NASA Galileo spacecraft.

Climate change reference guide

DOT National Transportation Integrated Search

2009-01-01

At the heart of climate change is the greenhouse effect, in which molecules of various gases trap heat in Earths atmosphere and keep it warm enough to support life. Carbon dioxide and other greenhouse gases (GHGs) are an important part of Ea...

Early Detection of Autism (ASD) by a Non-invasive Quick Measurement of Markedly Reduced Acetylcholine & DHEA and Increased β-Amyloid (1-42), Asbestos (Chrysotile), Titanium Dioxide, Al, Hg & often Coexisting Virus Infections (CMV, HPV 16 and 18), Bacterial Infections etc. in the Brain and Corresponding Safe Individualized Effective Treatment.

PubMed

Omura, Yoshiaki; Lu, Dominic; Jones, Marilyn K; Nihrane, Ahdallah; Duvvi, Harsha; Shimotsuura, Yasuhiro; Ohki, Motomu

2015-01-01

A brief historical background on Autism & some of the important symptoms associated with Autism are summarized. Using strong Electro Magnetic Field Resonance Phenomenon between 2 identical molecules with identical weight (which received U.S. Patent) non-invasively & rapidly we can detect various molecules including neurotransmitters, bacteria, virus, fungus, metals & abnormal molecules. Simple non- invasive measurement of various molecules through pupils & head of diagnosed or suspected Autism patients indicated that in Autism patients following changes were often found: 1) Acetylcholine is markedly reduced; 2) Alzheimer's disease markers (i.e. β-Amyloid (1-42), Tau Protein, Apolipoprotein (Apo E4)) are markedly increased; 3) Chrysotile Asbestos is increased; 4) Titanium Dioxide (TiO2) is moderately increased; 5) Al is moderately increased; 6) Hg is moderately increased; 7) Dopamine, Serotonin & GABA are significantly reduced (up to about 1/10 of normal); 8) Often viral infections (such as CMV, HHV-6, HPV-16, HPV-18, etc.), and Bacterial infections (such as Chlamydia trachomatis, Mycobacterium TB, Borrelia Burgdorferi, etc.) coexist. Research by others on Autism spectrum disorder (ASD) shows that it is a group of complex neurodevelopmental disorders, with about 70% of ASD patients also suffering from gastro-intestinal problems. While Alzheimer disease (AD) is characterized by formation of 1) Amyloid plaques, 2) Neurofibrillary tangles inside of neurons, and 3) Loss of connections between neurons. More than 90% of AD develops in people over the age of 65. These 3 characteristics often progressively worsen over time. Although Autism Spectrum Disorder and Alzheimer's disease are completely different diseases they have some similar biochemical changes. Eight examples of such measurement & analysis are shown for comparison. Most of Autism patients improved significantly by removing the source or preventing intake of Asbestos, TiO2, Al & Hg or enhancing urinary output of above abnormal substances & coexisting infections, if treatment is given early. When HPV-16 & HPV-18 coexist, at triangular central area of the top of head, in addition to inability to talk, severe neuromuscular problems of lower extremity were found to also exist. However, if treatment is given 3-4 years after onset of Autism symptoms, even when successful biochemical reduction of above abnormal substances occurs, clinical improvement is less significant, since permanent damage in brain tissue seems to already exist. Therefore, early diagnosis & early treatment is very important for both Autism & Alzheimer's disease. In addition the optimal doses of Vitamin D3 and Taurine may play an important role in the future treatment of Autism, Alzheimer's Disease and memory disturbances by significantly increasing Acetylcholine and DHEA levels, enhancing the excretion of toxic substances in the urine, as well as having an anticancer effect.

Ultrafast measurements of chlorine dioxide photochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ludowise, P.D.

Time-resolved mass spectrometry and time-resolved photoelectron spectroscopy are used to study the ultrafast photodissociation dynamics of chlorine dioxide, an important constituent in stratospheric ozone depletion. Chapter 1 introduces these pump/probe techniques, in which a femtosecond pump pulse excites a molecule to a dissociative state. At a later time, a second femtosecond probe pulse ionizes the molecule. The resulting mass and photoelectron spectra are acquired as a function of the delay between the pump and probe pulses, which follows the evolution of the molecule on the excited state. A comparison to other techniques used to study reaction dynamics is discussed. Chaptermore » 2 includes a detailed description of the design and construction of the experimental apparatus, which consists of a femtosecond laser system, a molecular beam time-of-flight spectrometer, and a data acquisition system. The time-of-flight spectrometer is specifically designed to have a short flight distance to maximize the photoelectron collection efficiency without degrading the resolution, which is limited by the bandwidth of the femtosecond laser system. Typical performance of the apparatus is demonstrated in a study of the time-resolved photoelectron spectroscopy of nitric oxide. The results of the time-resolved mass spectrometry experiments of chlorine dioxide are presented in Chapter 3. Upon excitation to the A {sup 2}A{sub 2} state near 3.2 eV, the molecule dissociates through an indirect two-step mechanism. The direct dissociation channel has been predicted to be open, but is not observed. A quantum beat is observed in the OClO{sup +} species, which is described as a vibrational coherence of the optically prepared A {sup 2}A{sub 2} state. Chapter 4 presents the results of the time-resolved photoelectron experiments of chlorine dioxide. At short delay time, the quantum beat of the OClO{sup +} species is observed in the X {sup 1}A{sub 1} state of the ion. At infinite delay, the signal is dominated by the ClO{sup +} ion, observed in a variety of electronic states. The photoelectron data is shown to support the indirect two-step dissociation mechanism derived from the mass results. Conclusions of the mass and photoelectron results are discussed in context of the stratospheric ozone depletion problem.« less

Visual and reversible carbon dioxide sensing enabled by doctor blade coated macroporous photonic crystals.

PubMed

Lin, Yi-Han; Suen, Shing-Yi; Yang, Hongta

2017-11-15

With significant impacts of carbon dioxide on global climate change, carbon dioxide sensing is of great importance. However, most of the existing sensing technologies are prone to interferences from carbon monoxide, or suffer from the use of sophisticated instruments. This research reports the development of reproducible carbon dioxide sensor using roll-to-roll compatible doctor blade coated three-dimensional macroporous photonic crystals. The pores are functionalized with amine groups to allow the reaction with carbon dioxide in the presence of humidity. The adsorption of carbon dioxide leads to red-shift and amplitude reduction of the optical stop bands, resulting in carbon dioxide detection with visible readout. The dependences of the diffraction wavelength on carbon dioxide partial pressure for various amine-functionalized photonic crystals and different humidities in the environment are systematically investigated. In addition, the reproducibility of carbon dioxide sensing has also been demonstrated in this research. Copyright © 2017 Elsevier Inc. All rights reserved.

Chemical reaction CO+OH • → CO 2+H • autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces

DOE PAGES

Masunov, Artem E.; Wait, Elizabeth; Vasu, Subith S.

2016-06-28

The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO 2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO 2 to OH radical and CO molecule, hydrogen transfer frommore » oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO 2 medium. Furthermore, tt may open a new venue for controlling reaction rates for chemical manufacturing.« less

Engineers Clean Mirror with Carbon Dioxide Snow

NASA Image and Video Library

2015-01-22

Just like drivers sometimes use snow to clean their car mirrors in winter, two Exelis Inc. engineers are practicing "snow cleaning'" on a test telescope mirror for the James Webb Space Telescope at NASA's Goddard Space Flight Center in Greenbelt, Maryland. By shooting carbon dioxide snow at the surface, engineers are able to clean large telescope mirrors without scratching them. "The snow-like crystals (carbon dioxide snow) knock contaminate particulates and molecules off the mirror," said Lee Feinberg, NASA optical telescope element manager. This technique will only be used if the James Webb Space Telescope's mirror is contaminated during integration and testing. The Webb telescope is the scientific successor to NASA's Hubble Space Telescope. It will be the most powerful space telescope ever built. With a mirror seven times as large as Hubble's and infrared capability, Webb will be capturing light from 13.5 billion light years away. To do this, its mirror must be kept super clean. "Small dust particles or molecules can impact the science that can be done with the Webb," said Feinberg. "So cleanliness especially on the mirrors is critical." Webb is an international project led by NASA with its partners, the European Space Agency and the Canadian Space Agency. Image credit: NASA/Goddard/Chris Gunn

Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide.

PubMed

Rochette, Étienne; Courtemanche, Marc-André; Pulis, Alexander P; Bi, Wenhua; Fontaine, Frédéric-Georges

2015-06-29

The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6‑tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robust, showing little sign of degradation after heating at 80 °C in benzene with 10 equiv. of formic acid for 24 h. The robustness of the system could be exploited in the design of metal-free catalysts for the hydrogenation of carbon dioxide.

Primitive control of cellular metabolism

NASA Technical Reports Server (NTRS)

Mitz, M. A.

1974-01-01

It is pointed out that control substances must have existed from the earliest times in the evolution of life and that the same control mechanisms must exist today. The investigation reported is concerned with the concept that carbon dioxide is a primitive regulator of cell function. The effects of carbon dioxide on cellular materials are examined, taking into account questions of solubilization, dissociation, changes of charge, stabilization, structural changes, wettability, the exclusion of other gases, the activation of compounds, changes in plasticity, and changes in membrane permeability.

The vibrational excitation of hot molecules by low energy electron impact

NASA Astrophysics Data System (ADS)

Kato, H.; Ohkawa, M.; Hoshino, M.; Campbell, L.; Brunger, M. J.; Tanaka, H.

2010-01-01

We report vibrational excitation functions and angular distributions for electron scattering from the ground vibrational quantum (000), the bending vibrational quantum (010) and the unresolved first bending overtone (020) and symmetric stretch (100) modes of the ground-electronic state in hot (750 K) carbon dioxide (CO2) molecules. The excitation function measurements were carried out at incident electron energies in the range of 1-9 eV, and at the electron scattering angles of 30°, 60°, 90° and 120°.

Idiosyncrasies of Physical Vapor Deposition Processes from Various Knudsen Cells for Quinacridone Thin Film Growth on Silicon Dioxide

PubMed Central

2015-01-01

Thin films of quinacridone deposited by physical vapor deposition on silicon dioxide were investigated by thermal desorption spectroscopy (TDS), mass spectrometry (MS), atomic force microscopy (AFM), specular and grazing incidence X-ray diffraction (XRD, GIXD), and Raman spectroscopy. Using a stainless steel Knudsen cell did not allow the preparation of a pure quinacridone film. TDS and MS unambiguously showed that in addition to quinacridone, desorbing at about 500 K (γ-peak), significant amounts of indigo desorbed at about 420 K (β-peak). The existence of these two species on the surface was verified by XRD, GIXD, and Raman spectroscopy. The latter spectroscopies revealed that additional species are contained in the films, not detected by TDS. In the film mainly composed of indigo a species was identified which we tentatively attribute to carbazole. The film consisting of mainly quinacridone contained in addition p-sexiphenyl. The reason for the various decomposition species effusing from the metal Knudsen cell is the comparably high sublimation temperature of the hydrogen bonded quinacridone. With special experimental methods and by using glass Knudsen-type cells we were able to prepare films which exclusively consist of molecules either corresponding to the β-peak or the γ-peak. These findings are of relevance for choosing the proper deposition techniques in the preparation of quinacridone films in the context of organic electronic devices. PMID:26401189

Phenolic Wastewater Treatment Alternatives.

DTIC Science & Technology

1980-06-01

15 Potassium Permanganate ................ 19 Iron (VI) Ferrate ..................... 22 Catalytic Oxidation ..................... 22...carbon dioxide, potassium hydroxide, and manganese dioxide which were readily handled by the existing system. d. Iron (VI) Ferrate Ferrate is iron in...the following systems/processes: Granular Activated Carbon (GAC) adsorption, ozone oxidation, hydrogen peroxide oxidation, potassium permanganate

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

Sharp, Donald J.; Armstrong, Pamela S.; Panitz, Janda Kirk G.

1998-01-01

A solid electrolytic capacitor having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

Sharp, D.J.; Armstrong, P.S.; Panitz, J.K.G.

1998-03-17

A solid electrolytic capacitor is described having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects. 2 figs.

Appreciating Oxygen

ERIC Educational Resources Information Center

Weiss, Hilton M.

2008-01-01

Photosynthetic flora and microfauna utilize light from the sun to convert carbon dioxide and water into carbohydrates and oxygen. While these carbohydrates and their derivative hydrocarbons are generally considered to be fuels, it is the thermodynamically energetic oxygen molecule that traps, stores, and provides almost all of the energy that…

Photoinitated charge separation in a hybrid titanium dioxide metalloporphyrin peptide material

NASA Astrophysics Data System (ADS)

Fry, H. Christopher; Liu, Yuzi; Dimitrijevic, Nada M.; Rajh, Tijana

2014-08-01

In natural systems, electron flow is mediated by proteins that spatially organize donor and acceptor molecules with great precision. Achieving this guided, directional flow of information is a desirable feature in photovoltaic media. Here, we design self-assembled peptide materials that organize multiple electronic components capable of performing photoinduced charge separation. Two peptides, c16-AHL3K3-CO2H and c16-AHL3K9-CO2H, self-assemble into fibres and provide a scaffold capable of binding a metalloporphyrin via histidine axial ligation and mineralize titanium dioxide (TiO2) on the lysine-rich surface of the resulting fibrous structures. Electron paramagnetic resonance studies of this self-assembled material under continuous light excitation demonstrate charge separation induced by excitation of the metalloporphyrin and mediated by the peptide assembly structure. This approach to dye-sensitized semiconducting materials offers a means to spatially control the dye molecule with respect to the semiconducting material through careful, strategic peptide design.

Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis.

PubMed

Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans-Hermann

2017-05-01

In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS 18 O/ 16 O monitoring for future method development is proposed.

Influence of Water Vapors and Hydrogen on the Energy Band Bending in the SnO2 Microcrystals of Polycrystalline Tin Dioxide Films

NASA Astrophysics Data System (ADS)

Gaman, V. I.; Almaev, A. V.; Sevast'yanov, E. Yu.; Maksimova, N. K.

2015-06-01

The results of studying the dependence of the energy band bending at the interface of contacting SnO2 microcrystals in the polycrystalline tin dioxide film on the humidity level of clean air and hydrogen concentration in the gas mixture of clean air + H2 are presented. The experimental results showed that the bending of energy bands in SnO2 is decreased under exposure to the water vapors and molecular hydrogen. The presence of two types of the adsorption centers for water molecules on the surface of SnO2 is found. It is shown that at the absolute humidity of the gas mixture above 12 g/m3, the H2O and H2 molecules are adsorbed on the same centers, whose surface density is of 1012 сm-2 at a concentration of donor impurity in SnO2 equal to 1018 сm-3.

Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures

PubMed Central

Zhang, Xing; Wu, Zishan; Zhang, Xiao; Li, Liewu; Li, Yanyan; Xu, Haomin; Li, Xiaoxiao; Yu, Xiaolu; Zhang, Zisheng; Liang, Yongye; Wang, Hailiang

2017-01-01

Electrochemical reduction of carbon dioxide with renewable energy is a sustainable way of producing carbon-neutral fuels. However, developing active, selective and stable electrocatalysts is challenging and entails material structure design and tailoring across a range of length scales. Here we report a cobalt-phthalocyanine-based high-performance carbon dioxide reduction electrocatalyst material developed with a combined nanoscale and molecular approach. On the nanoscale, cobalt phthalocyanine (CoPc) molecules are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for carbon monoxide, and enhanced durability. On the molecular level, the catalytic performance is further enhanced by introducing cyano groups to the CoPc molecule. The resulting hybrid catalyst exhibits >95% Faradaic efficiency for carbon monoxide production in a wide potential range and extraordinary catalytic activity with a current density of 15.0 mA cm−2 and a turnover frequency of 4.1 s−1 at the overpotential of 0.52 V in a near-neutral aqueous solution. PMID:28272403

A 3-hydroxypropionate/4-hydroxybutyrate autotrophic carbon dioxide assimilation pathway in Archaea.

PubMed

Berg, Ivan A; Kockelkorn, Daniel; Buckel, Wolfgang; Fuchs, Georg

2007-12-14

The assimilation of carbon dioxide (CO2) into organic material is quantitatively the most important biosynthetic process. We discovered that an autotrophic member of the archaeal order Sulfolobales, Metallosphaera sedula, fixed CO2 with acetyl-coenzyme A (acetyl-CoA)/propionyl-CoA carboxylase as the key carboxylating enzyme. In this system, one acetyl-CoA and two bicarbonate molecules were reductively converted via 3-hydroxypropionate to succinyl-CoA. This intermediate was reduced to 4-hydroxybutyrate and converted into two acetyl-CoA molecules via 4-hydroxybutyryl-CoA dehydratase. The key genes of this pathway were found not only in Metallosphaera but also in Sulfolobus, Archaeoglobus, and Cenarchaeum species. Moreover, the Global Ocean Sampling database contains half as many 4-hydroxybutyryl-CoA dehydratase sequences as compared with those found for another key photosynthetic CO2-fixing enzyme, ribulose-1,5-bisphosphate carboxylase-oxygenase. This indicates the importance of this enzyme in global carbon cycling.

7-Phenoxy-Substituted 3,4-Dihydro-2H-1,2,4-benzothiadiazine 1,1-Dioxides as Positive Allosteric Modulators of α-Amino-3-hydroxy-5-methyl-4-isoxazolepropionic Acid (AMPA) Receptors with Nanomolar Potency.

PubMed

Goffin, Eric; Drapier, Thomas; Larsen, Anja Probst; Geubelle, Pierre; Ptak, Christopher P; Laulumaa, Saara; Rovinskaja, Karoline; Gilissen, Julie; Tullio, Pascal de; Olsen, Lars; Frydenvang, Karla; Pirotte, Bernard; Hanson, Julien; Oswald, Robert E; Kastrup, Jette Sandholm; Francotte, Pierre

2018-01-11

We report here the synthesis of 7-phenoxy-substituted 3,4-dihydro-2H-1,2,4-benzothiadiazine 1,1-dioxides and their evaluation as AMPA receptor positive allosteric modulators (AMPApams). The impact of substitution on the phenoxy ring and on the nitrogen atom at the 4-position was examined. At GluA2(Q) expressed in HEK293 cells (calcium flux experiment), the most potent compound was 11m (4-cyclopropyl-7-(3-methoxyphenoxy)-3,4-dihydro-2H-1,2,4-benzothiadiazine 1,1-dioxide, EC 50 = 2.0 nM). The Hill coefficient in the screening and the shape of the dimerization curve in small-angle X-ray scattering (SAXS) experiments using isolated GluA2 ligand-binding domain (GluA2-LBD) are consistent with binding of one molecule of 11m per dimer interface, contrary to most benzothiadiazine dioxides developed to date. This observation was confirmed by the X-ray structure of 11m bound to GluA2-LBD and by NMR. This is the first benzothiadiazine dioxide AMPApam to reach the nanomolar range.

14 CFR 23.1197 - Fire extinguishing agents.

Code of Federal Regulations, 2012 CFR

2012-01-01

... materials in the area protected by the fire extinguishing system; and (2) Have thermal stability over the... exist in the extinguishing system. This must be shown by test except for built-in carbon dioxide fuselage compartment fire extinguishing systems for which— (1) Five pounds or less of carbon dioxide will...

Synergism of Saturn, Enceladus and Titan and Formation of HCNO Prebiotic Molecules

NASA Technical Reports Server (NTRS)

Sittler, Edward C.; Cooper, John F.

2011-01-01

Saturn as a system has two very exotic moons Titan and Enceladus. Titan, taking in energy from Saturn's magnetosphere, solar UV irradiation, and cosmic rays, can make HCN based molecules as discussed in earlier paper by Raulin and Owen. Space radiation effects at both moons, and as coupled by the Saturn magnetosphere, could cause an unexpected series of events potentially leading to prebiotic chemical evolution at Titan with HCNO from magnetospheric oxygen as the new ingredient. The "Old Faithful" model suggests that Enceladus, highly irradiated by Saturn magnetospheric electrons and thus having a source of chemical energy from radiolytic gas production, has episodic ejections of water vapor, carbon dioxide, and various hydrocarbons into Saturn's magnetosphere. The hydrocarbons do not survive transport through the plasma environment, but oxygen ions from Enceladus water molecules become the dominant ion species in the outer magnetosphere. At Titan, Cassini discovered that 1) keV oxygen ions, evidently from Enceladus, are bombarding Titan's upper atmosphere and 2) heavy positive and negative ions exist in significant abundances within Titan's upper atmosphere. Initial models of heavy ion formation in Titan's upper atmosphere invoked polymerization of aromatics such as benzenes and their radicals to make polycyclic aromatic hydrocarbons (PAH) , while a more recent model by Sittler et al., has raised the possibility of carbon chains forming from the polymerization of acetylene and its radicals to make fullerenes. Laboratory measurements indicate that fullerenes, which are hollow carbon shells, can trap keV oxygen ions. Clustering of the fullerenes with aerosol mixtures from PAHs and the dominant nitrogen molecules could form larger aerosols enriched in trapped oxygen. Aerosol precipitation could then convey these chemically complex structures deeper into the atmosphere and to the moon surface. Ionizing solar UV, magnetospheric electron, and galactic cosmic ray irradiation would provide further energy for processing into more complex organic forms. Further ionizing irradiation from cosmic rays deep in the atmosphere "tho lin" molecules are produced with all the molecular components present from which prebiotic organic molecules can form. This synergy of Saturn system, exogenic irradiation, and molecular processes provides a potential pathway for accumulation of prebiotic chemistry on the surface of Titan. Since fullerenes are also thought to exist in interstellar space, similar processes may also occur there to seed molecular clouds with prebiotic chemical species. We will also discuss possible future laboratory experiments that could be done to investigate fullerene formation at Titan and the trapping of oxygen in fullerenes.

Reduction of Carbon Dioxide by a Molybdenum-Containing Formate Dehydrogenase: A Kinetic and Mechanistic Study.

PubMed

Maia, Luisa B; Fonseca, Luis; Moura, Isabel; Moura, José J G

2016-07-20

Carbon dioxide accumulation is a major concern for the ecosystems, but its abundance and low cost make it an interesting source for the production of chemical feedstocks and fuels. However, the thermodynamic and kinetic stability of the carbon dioxide molecule makes its activation a challenging task. Studying the chemistry used by nature to functionalize carbon dioxide should be helpful for the development of new efficient (bio)catalysts for atmospheric carbon dioxide utilization. In this work, the ability of Desulfovibrio desulfuricans formate dehydrogenase (Dd FDH) to reduce carbon dioxide was kinetically and mechanistically characterized. The Dd FDH is suggested to be purified in an inactive form that has to be activated through a reduction-dependent mechanism. A kinetic model of a hysteretic enzyme is proposed to interpret and predict the progress curves of the Dd FDH-catalyzed reactions (initial lag phase and subsequent faster phase). Once activated, Dd FDH is able to efficiently catalyze, not only the formate oxidation (kcat of 543 s(-1), Km of 57.1 μM), but also the carbon dioxide reduction (kcat of 46.6 s(-1), Km of 15.7 μM), in an overall reaction that is thermodynamically and kinetically reversible. Noteworthy, both Dd FDH-catalyzed formate oxidation and carbon dioxide reduction are completely inactivated by cyanide. Current FDH reaction mechanistic proposals are discussed and a different mechanism is here suggested: formate oxidation and carbon dioxide reduction are proposed to proceed through hydride transfer and the sulfo group of the oxidized and reduced molybdenum center, Mo(6+)═S and Mo(4+)-SH, are suggested to be the direct hydride acceptor and donor, respectively.

A first-principles study on the interaction of biogas with noble metal (Rh, Pt, Pd) decorated nitrogen doped graphene as a gas sensor: A DFT study

NASA Astrophysics Data System (ADS)

Zhao, Chunjiang; Wu, Huarui

2018-03-01

Density functional theory calculations are carried out to investigate the adsorption characteristics of methane (CH4), carbon dioxide (CO2), hydrogen (H2), hydrogen sulfide (H2S), nitrogen (N2), and oxygen (O2) on the surface of pyridine-like nitrogen doped graphene (PNG) as well as noble metal (Rh, Pt, Pd) decorated PNG to elaborate their potentials as gas sensors. The adsorption intensities of biogas on noble metal (Rh, Pt, Pd) decorated PNG are in the order of O2> H2S> N2> CH4> CO2> H2, which are corresponded to the order of their sensitivity on surface. Compared with biogas adsorption on pristine PNG, there exist higher adsorption ability, higher charge transfer and higher orbital hybridization upon adsorption on noble metal (Rh, Pt, Pd) decorated PNG. Consequently, the noble metal (Rh, Pt, Pd) decorated PNG can transform the existence of CH4, CO2, H2, H2S, N2, and O2 molecules into electrical signal and they could potentially be used as ideal sensors for detection of biogas in ambient situation.

Penetration of Solar Radiation into Solid Carbon Dioxide

NASA Astrophysics Data System (ADS)

Chinnery, H. E.; Hagermann, A.; Kaufmann, E.; Lewis, S. R.; Grady, M. M.

2017-09-01

Carbon dioxide ice exists naturally on the surface of Mars. This is a unique environment, with no Earth analogues, and so determining the properties of such a surface is important to further our understanding of the Martian environment. Laboratory experiments have determined the e-folding scale, or absorption scale length, for carbon dioxide slab ice, granular ice and snow. This is a universal measure of how transparent a material is to visible light, and so has implications for the radiative budget of carbon dioxide ice covered surfaces, as well as physical processes, such as the so-called spider formations in the cryptic region near the Martian south pole.

Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Bonding in O3 and SO2.

PubMed

Takeshita, Tyler Y; Lindquist, Beth A; Dunning, Thom H

2015-07-16

There are many well-known differences in the physical and chemical properties of ozone (O3) and sulfur dioxide (SO2). O3 has longer and weaker bonds than O2, whereas SO2 has shorter and stronger bonds than SO. The O-O2 bond is dramatically weaker than the O-SO bond, and the singlet-triplet gap in SO2 is more than double that in O3. In addition, O3 is a very reactive species, while SO2 is far less so. These disparities have been attributed to variations in the amount of diradical character in the two molecules. In this work, we use generalized valence bond (GVB) theory to characterize the electronic structure of ozone and sulfur dioxide, showing O3 does indeed possess significant diradical character, whereas SO2 is effectively a closed shell molecule. The GVB results provide critical insights into the genesis of the observed difference in these two isoelectronic species. SO2 possesses a recoupled pair bond dyad in the a"(π) system, resulting in SO double bonds. The π system of O3, on the other hand, has a lone pair on the central oxygen atom plus a pair of electrons in orbitals on the terminal oxygen atoms that give rise to a relatively weak π interaction.

Advanced air revitalization system modeling and testing

NASA Technical Reports Server (NTRS)

Dall-Baumann, Liese; Jeng, Frank; Christian, Steve; Edeer, Marybeth; Lin, Chin

1990-01-01

To support manned lunar and Martian exploration, an extensive evaluation of air revitalization subsystems (ARS) is being conducted. The major operations under study include carbon dioxide removal and reduction; oxygen and nitrogen production, storage, and distribution; humidity and temperature control; and trace contaminant control. A comprehensive analysis program based on a generalized block flow model was developed to facilitate the evaluation of various processes and their interaction. ASPEN PLUS was used in modelling carbon dioxide removal and reduction. Several life support test stands were developed to test new and existing technologies for their potential applicability in space. The goal was to identify processes which use compact, lightweight equipment and maximize the recovery of oxygen and water. The carbon dioxide removal test stands include solid amine/vacuum desorption (SAVD), regenerative silver oxide chemisorption, and electrochemical carbon dioxide concentration (EDC). Membrane-based carbon dioxide removal and humidity control, catalytic reduction of carbon dioxide, and catalytic oxidation of trace contaminants were also investigated.

Film growth, adsorption and desorption kinetics of indigo on SiO2

PubMed Central

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2015-01-01

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer des orption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption. PMID:24832297

Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherwitzl, Boris, E-mail: b.scherwitzl@tugraz.at; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation ofmore » dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.« less

Film growth, adsorption and desorption kinetics of indigo on SiO2.

PubMed

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

Multivariate co-integration analysis of the Kaya factors in Ghana.

PubMed

Asumadu-Sarkodie, Samuel; Owusu, Phebe Asantewaa

2016-05-01

The fundamental goal of the Government of Ghana's development agenda as enshrined in the Growth and Poverty Reduction Strategy to grow the economy to a middle income status of US$1000 per capita by the end of 2015 could be met by increasing the labour force, increasing energy supplies and expanding the energy infrastructure in order to achieve the sustainable development targets. In this study, a multivariate co-integration analysis of the Kaya factors namely carbon dioxide, total primary energy consumption, population and GDP was investigated in Ghana using vector error correction model with data spanning from 1980 to 2012. Our research results show an existence of long-run causality running from population, GDP and total primary energy consumption to carbon dioxide emissions. However, there is evidence of short-run causality running from population to carbon dioxide emissions. There was a bi-directional causality running from carbon dioxide emissions to energy consumption and vice versa. In other words, decreasing the primary energy consumption in Ghana will directly reduce carbon dioxide emissions. In addition, a bi-directional causality running from GDP to energy consumption and vice versa exists in the multivariate model. It is plausible that access to energy has a relationship with increasing economic growth and productivity in Ghana.

Organic synthesis in experimental impact shocks

NASA Technical Reports Server (NTRS)

McKay, C. P.; Borucki, W. J.

1997-01-01

Laboratory simulations of shocks created with a high-energy laser demonstrate that the efficacy of organic production depends on the molecular, not just the elemental composition of the shocked gas. In a methane-rich mixture that simulates a low-temperature equilibrium mixture of cometary material, hydrogen cyanide and acetylene were produced with yields of 5 x 10(17) molecules per joule. Repeated shocking of the methane-rich mixture produced amine groups, suggesting the possible synthesis of amino acids. No organic molecules were produced in a carbon dioxide-rich mixture, which is at odds with thermodynamic equilibrium approaches to shock chemistry and has implications for the modeling of shock-produced organic molecules on early Earth.

CONSIDERATIONS FOR A REGULATORY FRAMEWORK FOR LARGE-SCALE GEOLOGIC SEQUESTRATION OF CARBON DIOXIDE: A NORTH AMERICAN PERSPECTIVE

EPA Science Inventory

Large scale geologic sequestration (GS) of carbon dioxide poses a novel set of challenges for regulators. This paper focuses on the unique needs of large scale GS projects in light of the existing regulatory regimes in the United States and Canada and identifies several differen...

Ultraviolet Pretreatment of Titanium Dioxide and Tin-Doped Indium Oxide Surfaces as a Promoter of the Adsorption of Organic Molecules in Dry Deposition Processes: Light Patterning of Organic Nanowires.

PubMed

Oulad-Zian, Youssef; Sanchez-Valencia, Juan R; Parra-Barranco, Julian; Hamad, Said; Espinos, Juan P; Barranco, Angel; Ferrer, Javier; Coll, Mariona; Borras, Ana

2015-08-04

In this article we present the preactivation of TiO2 and ITO by UV irradiation under ambient conditions as a tool to enhance the incorporation of organic molecules on these oxides by evaporation at low pressures. The deposition of π-stacked molecules on TiO2 and ITO at controlled substrate temperature and in the presence of Ar is thoroughly followed by SEM, UV-vis, XRD, RBS, and photoluminescence spectroscopy, and the effect is exploited for the patterning formation of small-molecule organic nanowires (ONWs). X-ray photoelectron spectroscopy (XPS) in situ experiments and molecular dynamics simulations add critical information to fully elucidate the mechanism behind the increase in the number of adsorption centers for the organic molecules. Finally, the formation of hybrid organic/inorganic semiconductors is also explored as a result of the controlled vacuum sublimation of organic molecules on the open thin film microstructure of mesoporous TiO2.

Atlas of high resolution infrared spectra of carbon dioxide

NASA Technical Reports Server (NTRS)

Rinsland, C. P.; Benner, D. C.; Devi, V. M.; Ferry, P. S.; Sutton, C. H.; Richardson, D. J.

1984-01-01

An atlas of long-path room-temperature absorption spectra of carbon dioxide is presented for the spectral intervals 1830-2100 cm, 2395-2680 cm, and 3140-3235 cm. The spectral data were recorded at high signal to noise with the 0.01 cm resolution Fourier transform interferometer. The spectra were obtained with pressures between 1 and 10 Torr of CO2 and with total paths between 24 and 384 meters. A compilation of the measured line positions and the assignments derived from the analysis are presented. Of the 3336 lines in the atlas, 94 percent were identified as CO2 lines or as residual lines H2O and CO. Calculated positions are presented for the carbon dioxide lines; a total of 52 bands of C-12O2-16, C-13O2-16, C-12O-16O-18, C-12O-16O-17, and C-13O-16O18 were identified. The weakest carbon dioxide lines marked in the atlas have intensities of approximately 0.5 x 10 to the negative 26th power cm/molecule at room temperature.

Importance of network density of nanotube: Effect on nitrogen dioxide gas sensing by solid state resistive sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishra, Prabhash; Grachyova, D. V.; Moskalenko, A. S.

2016-04-13

Dispersion of single-walled carbon nanotubes (SWCNTs) is an established fact, however, its effect on toxic gas sensing for the development of solid state resistive sensor was not well reported. In this report, the dispersion quality of SWCNTs has been investigated and improved, and this well-dispersed SWCNTs network was used for sensor fabrication to monitor nitrogen dioxide gas. Ultraviolet (UV)-visible spectroscopic studies shows the strength of SWNTs dispersion and scanning electron microscopy (SEM) imaging provides the morphological properties of the sensor device. In this gas sensor device, two sets of resistive type sensors were fabricated that consisting of a pair ofmore » interdigitated electrodes (IDEs) using dielectrophoresis technique with different SWCNTs network density. With low-density SWCNTs networks, this fabricated sensor exhibits a high response for nitrogen dioxide sensing. The sensing of nitrogen dioxide is mainly due to charge transfer from absorbed molecules to sidewalls of nanotube and tube-tube screening acting a major role for the transport properties of charge carriers.« less

Metal-organic framework thin films on a surface of optical fibre long period grating for chemical sensing

NASA Astrophysics Data System (ADS)

Hromadka, J.; Tokay, B.; James, S.; Korposh, S.

2017-04-01

An optical fibre long period grating (LPG) modified with a thin film of HKUST-1, a material from metal organic framework (MOF) family, was employed for the detection of carbon dioxide. The sensing mechanism is based on the measurement of the change of the refractive index (RI) of the coating that is induced by the penetration of CO2 molecules into the HKUST-1 pores. The responses of the resonance bands in the transmission spectrum of an LPG modified with 40 layers of HKUST-1 upon exposure to carbon dioxide in mixture with nitrogen were investigated.

Curcumin inhibits activation induced by urban particulate material or titanium dioxide nanoparticles in primary human endothelial cells

PubMed Central

Montiel-Dávalos, Angélica; Silva Sánchez, Guadalupe Jazmin; Huerta-García, Elizabeth; Rueda-Romero, Cristhiam; Soca Chafre, Giovanny; Mitre-Aguilar, Irma B.; Alfaro-Moreno, Ernesto; Pedraza-Chaverri, José

2017-01-01

Curcumin has protective effects against toxic agents and shows preventive properties for various diseases. Particulate material with an aerodynamic diameter of ≤10 μm (PM10) and titanium dioxide nanoparticles (TiO2-NPs) induce endothelial dysfunction and activation. We explored whether curcumin is able to attenuate different events related to endothelial activation. This includes adhesion, expression of adhesion molecules and oxidative stress induced by PM10 and TiO2-NPs. Human umbilical vein endothelial cells (HUVEC) were treated with 1, 10 and 100 μM curcumin for 1 h and then exposed to PM10 at 3 μg/cm2 or TiO2-NPs at 10 μg/cm2. Cell adhesion was evaluated by co-culture with U937 human myelomonocytic cells. Adhesion molecules expression was measured by flow cytometry after 3 or 24 h of exposure. Oxidative stress was determined by 2,7-dichlorodihydrofluorescein (H2DCF) oxidation. PM10 and TiO2-NPs induced the adhesion of U937 cells and the expression of E- and P-selectins, intercellular adhesion molecule-1 (ICAM-1), vascular cell adhesion molecule-1 (VCAM-1) and platelet-endothelial cell adhesion molecule-1 (PECAM-1). The expression of E- and P-selectins matched the adhesion of monocytes to HUVEC after 3 h. In HUVEC treated with 1 or 10 μM curcumin, the expression of adhesion molecules and monocytes adhesion was significantly diminished. Curcumin also partially reduced the H2DCF oxidation induced by PM10 and TiO2-NPs. Our results suggest an anti-inflammatory and antioxidant role by curcumin attenuating the activation caused on endothelial cells by exposure to particles. Therefore, curcumin could be useful in the treatment of diseases where an inflammatory process and endothelial activation are involved. PMID:29244817

Structural Evolution of Supercritical CO2 across the Frenkel Line.

PubMed

Bolmatov, Dima; Zav'yalov, D; Gao, M; Zhernenkov, Mikhail

2014-08-21

Here, we study structural properties of the supercritical carbon dioxide and discover the existence of persistent medium-range order correlations, which make supercritical carbon dioxide nonuniform and heterogeneous on an intermediate length scale. We report on the CO2 heterogeneity shell structure where, in the first shell, both carbon and oxygen atoms experience gas-like-type interactions with short-range order correlations while within the second shell, oxygen atoms essentially exhibit a liquid-like type of interactions due to localization of transverse-like phonon packets. Importantly, we highlight a catalytic role of atoms inside of the nearest-neighbor heterogeneity shell in providing a mechanism for diffusion and proving the existence of an additional thermodynamic boundary in the supercritical carbon dioxide on an intermediate length scale. Finally, we discuss important implications for answering the intriguing question whether Venus may have had CO2 oceans and urge for an experimental detection of this persistent local-order heterogeneity.

Molecular dynamics studies of water deposition on hematite surfaces

NASA Astrophysics Data System (ADS)

Kvamme, Bjørn; Kuznetsova, Tatiana; Haynes, Martin

2012-12-01

The interest in carbon dioxide for enhanced oil recovery is increasing proportional to the decrease in naturally driven oil production and also due to the increasing demand for reduced emission of carbon dioxide to the atmosphere. Transport of carbon dioxide in offshore pipelines involves high pressure and low temperatures which may lead to the formation of hydrate between residual water dissolved in carbon dioxide. The critical question is whether the water at some condition of temperature and pressure will drop out as liquid droplets or as water adsorbed on the surfaces of the pipeline and then subsequently form hydrates heterogeneously. In this work we have used the 6-311G basis set with B3LYP to estimate the charge distribution of different sizes of hematite crystals. The obtained surface charge distribution were kept unchanged while the inner charge distribution where scaled so as to result in an overall neutral crystal. These rust particles were embedded in water and chemical potential for adsorbed water molecules were estimated through thermodynamic integration and compared to similar estimates for same size water cluster. Estimated values of water chemical potentials indicate that it is thermodynamically favorable for water to adsorb on hematite, and that evaluation of potential carbon dioxide hydrate formation conditions and kinetics should be based this sequence of processes.

TRPs as chemosensors (ROS, RNS, RCS, gasotransmitters).

PubMed

Shimizu, Shunichi; Takahashi, Nobuaki; Mori, Yasuo

2014-01-01

The transient receptor potential (trp) gene superfamily encodes TRP proteins that act as multimodal sensor cation channels for a wide variety of stimuli from outside and inside the cell. Upon chemical or physical stimulation of cells, TRP channels transduce electrical and/or Ca(2+) signals via their cation channel activities. These functional features of TRP channels allow the body to react and adapt to different forms of environmental changes. Indeed, members of one class of TRP channels have emerged as sensors of reactive oxygen species (ROS), reactive nitrogen species (RNS), reactive carbonyl species (RCS), and gaseous messenger molecules including molecular oxygen (O2), hydrogen sulfide (H2S), and carbon dioxide (CO2). Hydrogen peroxide (H2O2), an ROS, triggers the production of ADP-ribose, which binds and activates TRPM2. In addition to TRPM2, TRPC5, TRPV1, and TRPA1 are also activated by H2O2 via modification of cysteine (Cys) free sulfhydryl groups. Nitric oxide (NO), a vasoactive gaseous molecule, regulates TRP channels directly via Cys S-nitrosylation or indirectly via cyclic GMP (cGMP)/protein kinase G (PKG)-dependent phosphorylation. Anoxia induced by O2-glucose deprivation and severe hypoxia activates TRPM7 and TRPC6, respectively, whereas TRPA1 serves as a sensor of mild hypoxia and hyperoxia in vagal and sensory neurons. TRPA1 also detects other gaseous molecules, such as hydrogen sulfide (H2S) and carbon dioxide (CO2). In this review, we highlight our current knowledge of TRP channels as chemosensors for ROS, RNS, RCS, and gaseous molecules and discuss their functional impacts on physiological and pathological events.

Interactions of carbon dioxide with model organic molecules: A comparative theoretical study

NASA Astrophysics Data System (ADS)

Trung, Nguyen Tien; Nguyen, Minh Tho

2013-08-01

Interaction energies obtained using CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ computations including both ZPE and BSSE corrections range from -2.9 to -14.2 kJ mol-1. While formic acid forms the most stable complex with CO2, formaldehyde yields the least stable complex. Lewis acid-base interaction such as C-N⋯C(CO2), Cdbnd O⋯C(CO2), which overcomes C-H⋯O blue-shifting hydrogen bond, plays a significant role in stabilizing most complexes. However, the strength of (HCOOH, CO2) is mainly determined by O-H⋯O red-shifting hydrogen bond. The C-H⋯O blue-shifting hydrogen bond is revealed upon complexation of CH3OH, HCHO, HCOOH, CH3COCH3 and HCOOCH3 with CO2. Remarkably, existence of weak hydrogen bonded C-H⋯O interaction is not found in the (CH3OCH3, CO2) and (CH3NH2, CO2) pairs.

Three-dimensional iron(ii) porous coordination polymer exhibiting carbon dioxide-dependent spin crossover.

PubMed

Shin, Jong Won; Jeong, Ah Rim; Jeoung, Sungeun; Moon, Hoi Ri; Komatsumaru, Yuki; Hayami, Shinya; Moon, Dohyun; Min, Kil Sik

2018-04-24

We report a three-dimensional Fe(ii) porous coordination polymer that exhibits a spin crossover temperature change following CO2 sorption (though not N2 sorption). Furthermore, single crystals of the desolvated polymer with CO2 molecules at three different temperatures were characterised by X-ray crystallography.

Recent progress in [11 C]carbon dioxide ([11 C]CO2 ) and [11 C]carbon monoxide ([11 C]CO) chemistry.

PubMed

Taddei, Carlotta; Gee, Antony D

2018-03-01

[ 11 C]Carbon dioxide ([ 11 C]CO 2 ) and [ 11 C]carbon monoxide ([ 11 C]CO) are 2 attractive precursors for labelling the carbonyl position (C═O) in a vast range of functionalised molecules (eg, ureas, amides, and carboxylic acids). The development of radiosynthetic methods to produce functionalised 11 C-labelled compounds is required to enhance the radiotracers available for positron emission tomography, molecular, and medical imaging applications. Following a brief summary of secondary 11 C-precursor production and uses, the review focuses on recent progress with direct 11 C-carboxylation routes with [ 11 C]CO 2 and 11 C-carbonylation with [ 11 C]CO. Novel approaches to generate [ 11 C]CO using CO-releasing molecules (CO-RMs), such as silacarboxylic acids and disilanes, applied to radiochemistry are described and compared with standard [ 11 C]CO production methods. These innovative [ 11 C]CO synthesis strategies represent efficient and reliable [ 11 C]CO production processes, enabling the widespread use of [ 11 C]CO chemistry within the wider radiochemistry community. Copyright © 2017 John Wiley & Sons, Ltd.

Single molecule magnets with protective ligand shells on gold and titanium dioxide surfaces: In situ electrospray deposition and x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Handrup, Karsten; Richards, Victoria J.; Weston, Matthew; Champness, Neil R.; O'Shea, James N.

2013-10-01

Two single molecule magnets based on the dodecamanganese (III, IV) cluster with either benzoate or terphenyl-4-carboxylate ligands, have been studied on the Au(111) and rutile TiO2(110) surfaces. We have used in situ electrospray deposition to produce a series of surface coverages from a fraction of a monolayer to multilayer films in both cases. X-ray absorption spectroscopy measured at the Mn L-edge (Mn 2p) has been used to study the effect of adsorption on the oxidation states of the manganese atoms in the core. In the case of the benzoate-functionalised complex reduction of the manganese metal centres is observed due to the interaction of the manganese core with the underlying surface. In the case of terphenyl-4-carboxylate, the presence of this much larger ligand prevents the magnetic core from interacting with either the gold or the titanium dioxide surfaces and the characteristic Mn3+ and Mn4+ oxidation states necessary for magnetic behaviour are preserved.

Remote carboxylation of halogenated aliphatic hydrocarbons with carbon dioxide

NASA Astrophysics Data System (ADS)

Juliá-Hernández, Francisco; Moragas, Toni; Cornella, Josep; Martin, Ruben

2017-05-01

Catalytic carbon-carbon bond formation has enabled the streamlining of synthetic routes when assembling complex molecules. It is particularly important when incorporating saturated hydrocarbons, which are common motifs in petrochemicals and biologically relevant molecules. However, cross-coupling methods that involve alkyl electrophiles result in catalytic bond formation only at specific and previously functionalized sites. Here we describe a catalytic method that is capable of promoting carboxylation reactions at remote and unfunctionalized aliphatic sites with carbon dioxide at atmospheric pressure. The reaction occurs via selective migration of the catalyst along the hydrocarbon side-chain with excellent regio- and chemoselectivity, representing a remarkable reactivity relay when compared with classical cross-coupling reactions. Our results demonstrate that site-selectivity can be switched and controlled, enabling the functionalization of less-reactive positions in the presence of a priori more reactive ones. Furthermore, we show that raw materials obtained in bulk from petroleum processing, such as alkanes and unrefined mixtures of olefins, can be used as substrates. This offers an opportunity to integrate a catalytic platform en route to valuable fatty acids by transforming petroleum-derived feedstocks directly.

Ab initio intermolecular potential energy surface for the CO2—N2 system and related thermophysical properties

NASA Astrophysics Data System (ADS)

Crusius, Johann-Philipp; Hellmann, Robert; Castro-Palacio, Juan Carlos; Vesovic, Velisa

2018-06-01

A four-dimensional potential energy surface (PES) for the interaction between a rigid carbon dioxide molecule and a rigid nitrogen molecule was constructed based on quantum-chemical ab initio calculations up to the coupled-cluster level with single, double, and perturbative triple excitations. Interaction energies for a total of 1893 points on the PES were calculated using the counterpoise-corrected supermolecular approach and basis sets of up to quintuple-zeta quality with bond functions. The interaction energies were extrapolated to the complete basis set limit, and an analytical site-site potential function with seven sites for carbon dioxide and five sites for nitrogen was fitted to the interaction energies. The CO2—N2 cross second virial coefficient as well as the dilute gas shear viscosity, thermal conductivity, and binary diffusion coefficient of CO2—N2 mixtures were calculated for temperatures up to 2000 K to validate the PES and to provide reliable reference values for these important properties. The calculated values are in very good agreement with the best experimental data.

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Coutts, Janelle; Hintze, Paul E.; Muscatello, Anthony C.; Gibson, Tracy L.; Captain, James G.; Lunn, Griffin M.; Devor, Robert W.; Bauer, Brint; Parks, Steve

2016-01-01

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50 because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Hintze, Paul E.; Muscatello, Anthony C.; Meier, Anne J.; Gibson, Tracy L.; Captain, James G.; Lunn, Griffin M.; Devor, Robert W.

2016-01-01

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Hintze, Paul E.; Muscatello, Anthony C.; Gibson, Tracy L.; Captain, James G.; Lunn, Griffin M.; Devor, Robert W.; Bauer, Brint; Parks, Steve

2016-01-01

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon, is capable of recovering all the oxygen from carbon dioxide, and it is a promising alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon, and the resulting carbon buildup eventually fouls the catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Effects of Elevated Carbon Dioxide on Photosynthesis and Carbon Partitioning: A Perspective on Root Sugar Sensing and Hormonal Crosstalk

PubMed Central

Thompson, Michael; Gamage, Dananjali; Hirotsu, Naoki; Martin, Anke; Seneweera, Saman

2017-01-01

Plant responses to atmospheric carbon dioxide will be of great concern in the future, as carbon dioxide concentrations ([CO2]) are predicted to continue to rise. Elevated [CO2] causes increased photosynthesis in plants, which leads to greater production of carbohydrates and biomass. Which organ the extra carbohydrates are allocated to varies between species, but also within species. These carbohydrates are a major energy source for plant growth, but they also act as signaling molecules and have a range of uses beyond being a source of carbon and energy. Currently, there is a lack of information on how the sugar sensing and signaling pathways of plants are affected by the higher content of carbohydrates produced under elevated [CO2]. Particularly, the sugar signaling pathways of roots are not well understood, along with how they are affected by elevated [CO2]. At elevated [CO2], some plants allocate greater amounts of sugars to roots where they are likely to act on gene regulation and therefore modify nutrient uptake and transport. Glucose and sucrose also promote root growth, an effect similar to what occurs under elevated [CO2]. Sugars also crosstalk with hormones to regulate root growth, but also affect hormone biosynthesis. This review provides an update on the role of sugars as signaling molecules in plant roots and thus explores the currently known functions that may be affected by elevated [CO2]. PMID:28848452

Effects of Elevated Carbon Dioxide on Photosynthesis and Carbon Partitioning: A Perspective on Root Sugar Sensing and Hormonal Crosstalk.

PubMed

Thompson, Michael; Gamage, Dananjali; Hirotsu, Naoki; Martin, Anke; Seneweera, Saman

2017-01-01

Plant responses to atmospheric carbon dioxide will be of great concern in the future, as carbon dioxide concentrations ([CO 2 ]) are predicted to continue to rise. Elevated [CO 2 ] causes increased photosynthesis in plants, which leads to greater production of carbohydrates and biomass. Which organ the extra carbohydrates are allocated to varies between species, but also within species. These carbohydrates are a major energy source for plant growth, but they also act as signaling molecules and have a range of uses beyond being a source of carbon and energy. Currently, there is a lack of information on how the sugar sensing and signaling pathways of plants are affected by the higher content of carbohydrates produced under elevated [CO 2 ]. Particularly, the sugar signaling pathways of roots are not well understood, along with how they are affected by elevated [CO 2 ]. At elevated [CO 2 ], some plants allocate greater amounts of sugars to roots where they are likely to act on gene regulation and therefore modify nutrient uptake and transport. Glucose and sucrose also promote root growth, an effect similar to what occurs under elevated [CO 2 ]. Sugars also crosstalk with hormones to regulate root growth, but also affect hormone biosynthesis. This review provides an update on the role of sugars as signaling molecules in plant roots and thus explores the currently known functions that may be affected by elevated [CO 2 ].

Study of carbon dioxide adsorption on a Cu-nitroprusside polymorph

DOE PAGES

Roque-Malherbe, R.; Lozano, C.; Polanco, R.; ...

2011-03-26

A careful structural characterization was carried out to unequivocally determine the structure of the synthesized material. The TGA, DRIFTS and a Pawley fitting of the XRD powder profiles indicate that the hydrated and in situ dehydrated polymorph crystallizes in the orthorhombic space group Pnma. Meanwhile, the CO 2 isosteric heat of adsorption appears to be independent of loading with an average value of 30 kJ/mol. This translates to a physisorption type interaction, where the adsorption energy corresponding to wall and lateral interactions are mutually compensated to produce, an apparently, homogeneous adsorption energy. The somewhat high adsorption energy is probably duemore » to the confinement of the CO 2 molecules in the nitroprusside pores. Statistical Physics and the Dubinin theory for pore volume filling allowed model the CO 2 equilibrium adsorption process in Cu-nitroprusside. A DRIFTS test for the adsorbed CO 2 displayed a peak at about 2338 cm -1 that was assigned to a contribution due to physical adsorption of the molecule. Another peak found at 2362 cm -1 evidenced that this molecule interacts with the Cu 2+, which appears to act as an electron accepting Lewis acid site. In conclusion, the aim of the present paper is to report a Pnma stable Cu-nitroprusside polymorph obtained by the precipitation method that can adsorb carbon dioxide.« less

The Successful Treatment of Elephantiasis Nostras Verrucosa With Ablative Carbon Dioxide Laser.

PubMed

Robinson, Caitlin G; Lee, Kory R; Thomas, Valencia D

2018-03-01

Elephantiasis nostras verrucosa (ENV) is a disfiguring skin condition that is difficult to treat. Existing treatment modalities serve to improve cosmesis or treat symptoms. Herein, we report a case of ENV with lymphocutaneous fistula successfully treated with ablative carbon dioxide laser. A 57-year-old woman with biopsy-proven ENV with lymphocutaneous fistula was treated with ablative carbon dioxide laser to the symptomatic area of her right thigh in 3 treatment sessions over 6 months. The patient had resolution of lymphocutaneous drainage as well as 90% improvement in the appearance of ENV lesions at the 1-month follow-up visit. Ablative carbon dioxide laser may provide cosmetic, symptomatic, and medical benefit for patients with localized ENV.

An evaluation of possible mechanisms for conversion of sulfur dioxide to sulfuric acid and sulfate aerosols in the troposphere

Treesearch

Jack G. Calvert

1976-01-01

The mechanisms and rates of conversion of sulfur dioxide to sulfur trioxide, sulfuric acid, and other "sulfate" aerosol precursors are considered in view of current knowledge related to atmospheric reactions and chemical kinetics. Several heterogeneous pathways exist for SO2 oxidation promoted on solid catalyst particles and in aqueous...

Investigating molecule-semiconductor interfaces with nonlinear spectroscopies

NASA Astrophysics Data System (ADS)

Giokas, Paul George

Knowledge of electronic structures and transport mechanisms at molecule-semiconductor interfaces is motivated by their ubiquity in photoelectrochemical cells. In this dissertation, optical spectroscopies are used uncover the influence of electronic coupling, coherent vibrational motion, and molecular geometry, and other factors on dynamics initiated by light absorption at such interfaces. These are explored for a family of ruthenium bipyridyl chromophores bound to titanium dioxide. Transient absorption measurements show molecular singlet state electron injection in 100 fs or less. Resonance Raman intensity analysis suggests the electronic excitations possess very little charge transfer character. The connections drawn in this work between molecular structure and photophysical behavior contribute to the general understanding of photoelectrochemical cells. Knowledge of binding geometry in nanocrystalline films is challenged by heterogeneity of semiconductor surfaces. Polarized resonance Raman spectroscopy is used to characterize the ruthenium chromophore family on single crystal titanium dioxide . Chromophores display a broad distribution of molecular geometries at the interface, with increased variation in binding angle due to the presence of a methylene bridge, as well as additional phosphonate anchors. This result implies multiple binding configurations for chromophores which incorporate multiple phosphonate ligands, and indicates the need for careful consideration when developing surface-assembled chromophore-catalyst cells. Electron transfer transitions occurring on the 100 fs time scale challenge conventional second-order approximations made when modeling these reactions. A fourth-order perturbative model which includes the relationship between coincident electron transfer and nuclear relaxation processes is presented. Insights provided by the model are illustrated for a two-level donor molecule. The presented fourth-order rate formula constitutes a rigorous and intuitive framework for understanding sub-picosecond photoinduced electron transfer dynamics. Charge transfer systems fit by this model include catechol-sensitized titanium dioxide nanoparticles and a closely-related molecular complex. These systems exhibit vibrational coherence coincident with back-electron transfer in the first picosecond after excitation, which suggests that intramolecular nuclear motion strongly influences the electronic transfer process and plays an important role in the dynamics of interfacial systems following light absorption.

Loading amorphous Asarone in mesoporous silica SBA-15 through supercritical carbon dioxide technology to enhance dissolution and bioavailability.

PubMed

Zhang, Zhengzan; Quan, Guilan; Wu, Qiaoli; Zhou, Chan; Li, Feng; Bai, Xuequn; Li, Ge; Pan, Xin; Wu, Chuanbin

2015-05-01

The aim of this study was to load amorphous hydrophobic drug into ordered mesoporous silica (SBA-15) by supercritical carbon dioxide technology in order to improve the dissolution and bioavailability of the drug. Asarone was selected as a model drug due to its lipophilic character and poor bioavailability. In vitro dissolution and in vivo bioavailability of the obtained Asarone-SBA-15 were significantly improved as compared to the micronized crystalline drug. This study offers an effective, safe, and environmentally benign means of solving the problems relating to the solubility and bioavailability of hydrophobic molecules. Copyright © 2015 Elsevier B.V. All rights reserved.

Carbon dioxide-assisted fabrication of highly uniform submicron-sized colloidal carbon spheres via hydrothermal carbonization using soft drink

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moon, Gun-Hee; Shin, Yongsoon; Arey, Bruce W.

An eco-friendly and economical method for the formation of uniform-sized carbon spheres by hydrothermal dehydration/condensation of a commercial carbonated beverage at 200 oC is reported. CO2 dissolved in the beverage accelerates the dehydration kinetics of the dissolved sugar molecules leading to production of homogeneous carbon spheres having a diameter less than 850 nm. In the presence of CO2, the rough surface of these carbon spheres likely results from continuous Ostwald ripening of constituent microscopic carbon-containing spheres that are formed by subsequent polymerization of intermediate HMF molecules.

On the existence of Rydberg nuclear molecules

NASA Astrophysics Data System (ADS)

Bertulani, C. A.; Frederico, T.; Hussein, M. S.

2017-11-01

Present nuclear detection techniques prevents us from determining if the analogue of a Rydberg molecule exists for the nuclear case. But nothing in nature disallows their existence. As in the atomic case, Rydberg nuclear molecules would be a laboratory for new aspects and applications of nuclear physics. We propose that Rydberg nuclear molecules, which represent the exotic, halo nuclei version, such as 11Be +11Be, of the well known quasimolecules observed in stable nuclei such as 12C +12C, might be common structures that could manifest their existence along the dripline. A study of possible candidates and the expected structure of such exotic clustering of two halo nuclei: the Rydberg nuclear molecules, is made on the basis of three different methods. It is shown that such cluster structures might be stable and unexpectedly common.

The physics, biology, and environmental ethics of making mars habitable.

PubMed

McKay, C P; Marinova, M M

2001-01-01

The considerable evidence that Mars once had a wetter, more clement, environment motivates the search for past or present life on that planet. This evidence also suggests the possibility of restoring habitable conditions on Mars. While the total amounts of the key molecules--carbon dioxide, water, and nitrogen--needed for creating a biosphere on Mars are unknown, estimates suggest that there may be enough in the subsurface. Super greenhouse gases, in particular, perfluorocarbons, are currently the most effective and practical way to warm Mars and thicken its atmosphere so that liquid water is stable on the surface. This process could take approximately 100 years. If enough carbon dioxide is frozen in the South Polar Cap and absorbed in the regolith, the resulting thick and warm carbon dioxide atmosphere could support many types of microorganisms, plants, and invertebrates. If a planet-wide martian biosphere converted carbon dioxide into oxygen with an average efficiency equal to that for Earth's biosphere, it would take > 100,000 years to create Earth-like oxygen levels. Ethical issues associated with bringing life to Mars center on the possibility of indigenous martian life and the relative value of a planet with or without a global biosphere.

Recovery of tritium from tritiated molecules

DOEpatents

Swansiger, William A.

1987-01-01

A method of recovering tritium from tritiated compounds comprises the steps of heating tritiated water and other co-injected tritiated compounds in a preheater to temperatures of about 600.degree. C. The mixture is injected into a reactor charged with a mixture of uranium and uranium dioxide. The injected mixture undergoes highly exothermic reactions with the uranium causing reaction temperatures to occur in excess of the melting point of uranium, and complete decomposition of the tritiated compounds to remove tritium therefrom. The uranium dioxide functions as an insulating material and heat sink preventing the reactor side walls from attaining reaction temperatures to thereby minimize tritium permeation rates. The uranium dioxide also functions as a diluent to allow for volumetric expansion of the uranium as it is converted to uranium dioxide. The reactor vessel is preferably stainless steel of sufficient mass so as to function as a heat sink preventing the reactor side walls from approaching high temperatures. A disposable copper liner extends between the reaction chamber and stainless steel outer vessel to prevent alloying of the uranium with the outer vessel. Apparatus used to carry out the method of the invention is also disclosed.

The physics, biology, and environmental ethics of making mars habitable

NASA Technical Reports Server (NTRS)

McKay, C. P.; Marinova, M. M.

2001-01-01

The considerable evidence that Mars once had a wetter, more clement, environment motivates the search for past or present life on that planet. This evidence also suggests the possibility of restoring habitable conditions on Mars. While the total amounts of the key molecules--carbon dioxide, water, and nitrogen--needed for creating a biosphere on Mars are unknown, estimates suggest that there may be enough in the subsurface. Super greenhouse gases, in particular, perfluorocarbons, are currently the most effective and practical way to warm Mars and thicken its atmosphere so that liquid water is stable on the surface. This process could take approximately 100 years. If enough carbon dioxide is frozen in the South Polar Cap and absorbed in the regolith, the resulting thick and warm carbon dioxide atmosphere could support many types of microorganisms, plants, and invertebrates. If a planet-wide martian biosphere converted carbon dioxide into oxygen with an average efficiency equal to that for Earth's biosphere, it would take > 100,000 years to create Earth-like oxygen levels. Ethical issues associated with bringing life to Mars center on the possibility of indigenous martian life and the relative value of a planet with or without a global biosphere.

Molecular simulation of gas adsorption and diffusion in a breathing MOF using a rigid force field.

PubMed

García-Pérez, E; Serra-Crespo, P; Hamad, S; Kapteijn, F; Gascon, J

2014-08-14

Simulation of gas adsorption in flexible porous materials is still limited by the slow progress in the development of flexible force fields. Moreover, the high computational cost of such flexible force fields may be a drawback even when they are fully developed. In this work, molecular simulations of gas adsorption and diffusion of carbon dioxide and methane in NH2-MIL-53(Al) are carried out using a linear combination of two crystallographic structures with rigid force fields. Once the interactions of carbon dioxide molecules and the bridging hydroxyls groups of the framework are optimized, an excellent match is found for simulations and experimental data for the adsorption of methane and carbon dioxide, including the stepwise uptake due to the breathing effect. In addition, diffusivities of pure components are calculated. The pore expansion by the breathing effect influences the self-diffusion mechanism and much higher diffusivities are observed at relatively high adsorbate loadings. This work demonstrates that using a rigid force field combined with a minimum number of experiments, reproduces adsorption and simulates diffusion of carbon dioxide and methane in the flexible metal-organic framework NH2-MIL-53(Al).

Carbon dioxide-expanded liquid substrate phase: an effective medium for selective hydrogenation of cinnamaldehyde to cinnamyl alcohol.

PubMed

Zhao, Fengyu; Fujita, Shin-ichio; Sun, Jianmin; Ikushima, Yutaka; Arai, Masahiko

2004-10-21

It has been shown that CO(2)-expanded cinnamaldehyde liquid phase is a unique and effective medium for cinnamaldehyde hydrogenation to cinnamyl alcohol, due to interactions between the C[double bond, length as m-dash]O group of the substrate and CO(2) molecules and increased solubility of H(2).

Induced Infiltration of Hole-Transporting Polymer into Photocatalyst for Staunch Polymer-Metal Oxide Hybrid Solar Cells.

PubMed

Park, Jong Hwan; Jung, Youngsuk; Yang, Yooseong; Shin, Hyun Suk; Kwon, Soonchul

2016-10-05

For efficient solar cells based on organic semiconductors, a good mixture of photoactive materials in the bulk heterojunction on the length scale of several tens of nanometers is an important requirement to prevent exciton recombination. Herein, we demonstrate that nanoporous titanium dioxide inverse opal structures fabricated using a self-assembled monolayer method and with enhanced infiltration of electron-donating polymers is an efficient electron-extracting layer, which enhances the photovoltaic performance. A calcination process generates an inverse opal structure of titanium dioxide (<70 nm of pore diameters) providing three-dimensional (3D) electron transport pathways. Hole-transporting polymers was successfully infiltrated into the pores of the surface-modified titanium dioxide under vacuum conditions at 200 °C. The resulting geometry expands the interfacial area between hole- and electron-transport materials, increasing the thickness of the active layer. The controlled polymer-coating process over titanium dioxide materials enhanced photocurrent of the solar cell device. Density functional theory calculations show improved interfacial adhesion between the self-assembled monolayer-modified surface and polymer molecules, supporting the experimental result of enhanced polymer infiltration into the voids. These results suggest that the 3D inverse opal structure of the surface-modified titanium dioxide can serve as a favorable electron-extracting layer in further enhancing optoelectronic performance based on organic or organic-inorganic hybrid solar cell.

Revisiting the emissions-energy-trade nexus: evidence from the newly industrializing countries.

PubMed

Ahmed, Khalid; Shahbaz, Muhammad; Kyophilavong, Phouphet

2016-04-01

This paper applies Pedroni's panel cointegration approach to explore the causal relationship between trade openness, carbon dioxide emissions, energy consumption, and economic growth for the panel of newly industrialized economies (i.e., Brazil, India, China, and South Africa) over the period of 1970-2013. Our panel cointegration estimation results found majority of the variables cointegrated and confirm the long-run association among the variables. The Granger causality test indicates bidirectional causality between carbon dioxide emissions and energy consumption. A unidirectional causality is found running from trade openness to carbon dioxide emission and energy consumption and economic growth to carbon dioxide emissions. The results of causality analysis suggest that the trade liberalization in newly industrialized economies induces higher energy consumption and carbon dioxide emissions. Furthermore, the causality results are checked using an innovative accounting approach which includes forecast-error variance decomposition test and impulse response function. The long-run coefficients are estimated using fully modified ordinary least square (FMOLS) method, and results conclude that the trade openness and economic growth reduce carbon dioxide emissions in the long run. The results of FMOLS test sound the existence of environmental Kuznets curve hypothesis. It means that trade liberalization induces carbon dioxide emission with increased national output, but it offsets that impact in the long run with reduced level of carbon dioxide emissions.

Life on Mars: chemical arguments and clues from Martian meteorites.

PubMed

Brack, A; Pillinger, C T

1998-08-01

Primitive terrestrial life-defined as a chemical system able to transfer its molecular information via self-replication and to evolve-probably originated from the evolution of reduced organic molecules in liquid water. Several sources have been proposed for the prebiotic organic molecules: terrestrial primitive atmosphere (methane or carbon dioxide), deep-sea hydrothermal systems, and extraterrestrial meteoritic and cometary dust grains. The study of carbonaceous chondrites, which contain up to 5% by weight of organic matter, has allowed close examination of the delivery of extraterrestrial organic material. Eight proteinaceous amino acids have been identified in the Murchison meteorite among more than 70 amino acids. Engel reported that L-alanine was surprisingly more abundant than D-alanine in the Murchison meteorite. Cronin also found excesses of L-enantiomers for nonprotein amino acids. A large collection of micrometeorites has been recently extracted from Antarctic old blue ice. In the 50- to 100-micron size range, carbonaceous micrometeorites represent 80% of the samples and contain 2% of carbon, on average. They might have brought more carbon than that involved in the present surficial biomass. The early histories of Mars and Earth clearly show similarities. Liquid water was once stable on the surface of Mars, attesting the presence of an atmosphere capable of deccelerating C-rich micrometeorites. Therefore, primitive life may have developed on Mars as well and fossilized microorganisms may still be present in the near subsurface. The Viking missions to Mars in 1976 did not find evidence of either contemporary or past life, but the mass spectrometer on the lander aeroshell determined the atmospheric composition, which has allowed a family of meteorites to be identified as Martian. Although these samples are essentially volcanic in origin, it has been recognized that some of them contain carbonate inclusions and even veins that have a carbon isotopic composition indicative of an origin from Martian atmospheric carbon dioxide. The oxygen isotopic composition of these carbonate deposits allows calculation of the temperature regime existing during formation from a fluid that dissolved the carbon dioxide. As the composition of the fluid is unknown, only a temperature range can be estimated, but this falls between 0 degree and 90 degrees C, which would seem entirely appropriate for life processes. It was such carbonate veins that were found to host putative microfossils. Irrespective of the existence of features that could be considered to be fossils, carbonate-rich portions of Martian meteorites tend to have material, at more than 1000 ppm, that combusts at a low temperature; i.e., it is an organic form of carbon. Unfortunately, this organic matter does not have a diagnostic isotopic signature so it cannot be unambiguously said to be indigenous to the samples. However, many circumstantial arguments can be made to the effect that it is cogenetic with the carbonate and hence Martian. If it could be proved that the organic matter was preterrestrial, then the isotopic fractionation between it and the carbon is in the right sense for a biological origin.

Surface area of montmorillonite from the dynamic sorption of nitrogen and carbon dioxide

USGS Publications Warehouse

Thomas, Josephus; Bohor, Bruce F.

1968-01-01

Surface area determinations were made on a montmorillonite with various cations emplaced on the exchangeable sites, utilizing nitrogen and carbon dioxide as adsorbates at 77°K and 195°K, respectively, in a dynamic system. From the fraction of a Mississippi montmorillonite less than about 1 μ in size, samples were prepared by replacing the original exchangeable cations with Li+, Na+, K+, Rb+, Cs+, Mg++, Ca++, Ba++, and NH4+, forming a series of homoionic montmorillonite species.Surface areas from 3-point B.E.T. plots (half-hour adsorption points), with nitrogen as the adsorbate, ranged from 61 m2/g for Li-montmorillonite to 138 m2/g for Cs-montmorillonite, thus reflecting a certain degree of nitrogen penetration between layers. Complete penetration should theoretically result in a surface area of over 300 m2/g for this clay with a nitrogen monolayer between each pair of platelets. The experimental data indicate that the extent of penetration is time-dependent and is also a function of the interlayer forces as governed by the size and charge of the replaceable cation. This finding negates the generally accepted concept that nitrogen at 77°K does not penetrate the layers and provides a measure only of the external surface of expandable clay minerals.A further measure of the variation of interlayer forces is provided by the adsorption of carbon dioxide at 195°K. Surface area values ranged from 99 m2/g for Li-montmorillonite to 315 m2/g for Csmontmorillonite. Although the carbon dioxide molecule is larger than the nitrogen molecule, its greater penetration apparently is a result of its being kinetically more energetic (with a larger diffusion coefficient) at its higher adsorption temperature. Similar differences have been found with both adsorbates in the study of microporous substances, such as coal, where activated diffusion is of considerable significance.

IR femtochemistry on the surface of wide-gap ionic crystals

NASA Astrophysics Data System (ADS)

Laptev, V. B.; Chekalin, S. V.; Dorofeyev, I. A.; Kompanets, V. O.; Pigulsky, S. V.; Ryabov, E. A.

2018-02-01

We have found and studied a phenomenon of the growth of films resulting from decomposition of some organic and silicon-containing molecules adsorbed on the surface of ionic crystals under the action of IR (1.4-5.4 µm) femtosecond radiation of a moderate intensity, ~1011 W cm-2. In the gas phase, these molecules do not decompose. Microstructured films consisting of amorphous carbon, graphite oxide, and silicon dioxide have been obtained. The formation of carbon films was accompanied by the appearance of different hydrocarbons in the gas phase. The extensive films of graphite oxide have been obtained. The decomposition of molecules on the surface is apparently caused by non-resonant ionization and subsequent deep fragmentation. The mechanisms of ionization at relatively low intensities of the femtosecond IR radiation have been discussed.

Radiation Synthesis of Carbon Dioxide in Ice-coated Carbon: Implications for Interstellar Grains and Icy Moons

NASA Astrophysics Data System (ADS)

Raut, U.; Fulvio, D.; Loeffler, M. J.; Baragiola, R. A.

2012-06-01

We report the synthesis of carbon dioxide on an amorphous carbon-13 substrate coated with amorphous water ice from irradiation with 100 keV protons at 20 K and 120 K. The quantitative studies show that the CO2 is dispersed in the ice; its column density increases with ion fluence to a maximum value (in 1015 molecules cm-2) of ~1 at 20 K and ~3 at 120 K. The initial yield is 0.05 (0.1) CO2 per incident H+ at 20 (120) K. The CO2 destruction process, which limits the maximum column density, occurs with an effective cross section of ~2.5 (4.1) × 10-17 cm2 at 20 (120) K. We discuss radiation-induced oxidation by reactions of radicals in water with the carbon surface and demonstrate that these reactions can be a significant source of condensed carbon dioxide in interstellar grains and in icy satellites in the outer solar system.

Separation of Acetylene from Carbon Dioxide and Ethylene by a Water-Stable Microporous Metal-Organic Framework with Aligned Imidazolium Groups inside the Channels.

PubMed

Lee, Jaechul; Chuah, Chong Yang; Kim, Jaheon; Kim, Youngsuk; Ko, Nakeun; Seo, Younggyu; Kim, Kimoon; Bae, Tae Hyun; Lee, Eunsung

2018-04-24

Separation of acetylene from carbon dioxide and ethylene is challenging in view of their similar sizes and physical properties. Metal-organic frameworks (MOFs) in general are strong candidates for these separations owing to the presence of functional pore surfaces that can selectively capture a specific target molecule. Here, we report a novel 3D microporous cationic framework named JCM-1. This structure possesses imidazolium functional groups on the pore surfaces and pyrazolate as a metal binding group, which is well known to form strong metal-to-ligand bonds. The selective sorption of acetylene over carbon dioxide and ethylene in JCM-1 was successfully demonstrated by equilibrium gas adsorption analysis as well as dynamic breakthrough measurement. Furthermore, its excellent hydrolytic stability makes the separation processes highly recyclable without a substantial loss in acetylene uptake capacity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of high-pressure CO 2 sorption isotherms on Eastern and Western US coals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romanov, V; Hur, T -B; Fazio, J

2013-10-01

Accurate estimation of carbon dioxide (CO 2) sorption capacity of coal is important for planning the CO 2 sequestration efforts. In this work, we investigated sorption and swelling behavior of several Eastern and Western US coal samples from the Central Appalachian Basin and from San Juan Basin. The CO 2 sorption isotherms have been completed at 55°C for as received and dried samples. The role of mineral components in coal, the coal swelling, the effects of temperature and moisture, and the error propagation have been analyzed. Changes in void volume due to dewatering and other factors such as temporary cagingmore » of carbon dioxide molecules in coal matrix were identified among the main factors affecting accuracy of the carbon dioxide sorption isotherms. The (helium) void volume in the sample cells was measured before and after the sorption isotherm experiments and was used to build the volume-corrected data plots.« less

Growth of methanogens on a Mars soil simulant.

PubMed

Kral, Timothy A; Bekkum, Curtis R; McKay, Christopher P

2004-12-01

Currently, the surface of Mars is probably too cold, too dry, and too oxidizing for life, as we know it, to exist. But the subsurface is another matter. Life forms that might exist below the surface could not obtain their energy from photosynthesis, but rather they would have to utilize chemical energy. Methanogens are one type of microorganism that might be able to survive below the surface of Mars. A potential habitat for existence of methanogens on Mars might be a geothermal source of hydrogen, possibly due to volcanic or hydrothermal activity, or the reaction of basalt and anaerobic water, carbon dioxide, which is abundant in the martian atmosphere, and of course, subsurface liquid water. We report here that certain methanogens can grow on a Mars soil simulant when supplied with carbon dioxide, molecular hydrogen, and varying amounts of water.

Membrane-micelle model for humus in soils and sediments and its relation to humification

USGS Publications Warehouse

Wershaw, Robert L.

1994-01-01

Humification, the process whereby biomass consisting of dead plant and animal remains is converted into soil organic matter (humus), is one of the basic processes of the carbon cycle. The organic compounds that make up plant and animal tissue are thermodynamically unstable in the oxidizing atmosphere at the surface of the Earth. After the organisms in which they are incorporated die, the compounds are converted back to carbon dioxide and water by degradation reactions catalyzed by enzymes secreted by micro-organisms. However, not all the organic compounds in the dead biomass are immediately converted; some of the material is only partially oxidized. The residue left after partial oxidative degradation of the dead biomass is the source of the organic compounds that accumulate in soils and sediments as humus. Previously, humification was thought to involve a conversion of degradation products by a series of polymerization reactions into new types of polymeric species that are different from the precursor molecular species in the original biomass. However, it is proposed here that the depolymerization and oxidation reactions that take place during the enzymatic degradation of biopolymers produce amphiphiles--molecules that have a polar (hydrophilic) part and a nonpolar (hydrophobic) part. These amphiphiles that result from the partial oxidative degradation of dead biomass assemble spontaneously into ordered aggregates in which the hydrophobic parts of the molecules form the interiors and the hydrophilic parts of the molecules make up the exterior surfaces of the aggregates. These ordered aggregates constitute the humus in soils and sediments. Humus ordered aggregates most likely exist as bilayer membranes coating mineral grains and as micelles in solution.

The millimeter-wavelength sulfur dioxide absorption spectra measured under simulated Venus conditions

NASA Astrophysics Data System (ADS)

Bellotti, Amadeo; Steffes, Paul G.

2015-07-01

Over 130 laboratory measurements of the 2-4 mm wavelength opacity of sulfur dioxide in a carbon dioxide atmosphere under simulated conditions for the upper Venus troposphere (temperatures between 308 and 343 K and pressures between 0.03 and 2 bar) have been made. These measurements along with the centimeter wavelength measurements by Steffes et al. (Steffes, P.G. et al. [2015]. Icarus 245, 153-161) have been used to empirically assess existing formalisms for sulfur dioxide opacity in a carbon dioxide atmosphere (Fahd, A.K., Steffes, P.G. [1992]. Icarus 97(2), 200-210; Suleiman, S.H. et al. [1996]. J. Geophys. Res.: Planets 101(E2), 4623-4635). The Van Vleck and Weisskopf Model (VVW) used by Fahd and Steffes with the JPL rotational line catalog (Pickett, H. et al. [1998]. J. Quant. Spectrosc. Radiat. Transfer 60(5), 499-890) was found to fit 85.88% of all 500 measurements within the 2-sigma uncertainty. This work will improve the confidence in retrievals of the atmospheric abundance of sulfur dioxide from millimeter-wavelength observations of the Venus atmosphere.

Hydrogen molecule defect in proton-conductive SrTiO3 Perovskite

NASA Astrophysics Data System (ADS)

Onishi, Taku

2017-11-01

In proton-conductive SrTiO3 perovskite, no hydrogen molecule defect ideally exists. However, the unforeseen chemical reaction is often observed after the use of fuel cell. From the viewpoint of battery safety, we have investigated the effect of hydrogen molecule defect by molecular orbital analysis. When counter cation vacancy exists, the activation energy for hydrogen molecule migration was 1.39 - 1.50 eV, which is much smaller than the dissociation energy of hydrogen molecule. It implies that hydrogen molecule may migrate without its dissociation.

Collision-induced dissociation processes of protonated benzoic acid and related compounds: competitive generation of protonated carbon dioxide or protonated benzene.

PubMed

Xu, Sihang; Pavlov, Julius; Attygalle, Athula B

2017-04-01

Upon activation in the gas phase, protonated benzoic acid (m/z 123) undergoes fragmentation by several mechanisms. In addition to the predictable water loss followed by a CO loss, the m/z 123 ion more intriguingly eliminates a molecule of benzene to generate protonated carbon dioxide (H - O +  ═ C ≡ O, m/z 45), or a molecule of carbon dioxide to yield protonated benzene (m/z 79). Experimental evidence shows that the incipient proton ambulates during the fragmentation processes. For the CO 2 or benzene loss, protonated benzoic acid transfers the charge-imparting proton initially to the ortho position and then to the ipso position to generate a transient species which dissociates to form an ion-neutral complex between benzene and protonated CO 2 . The formation of the m/z 45 ion is not a phenomenon unique to benzoic acid: spectra from protonated isophthalic acid, terephthalic acid, trans-cinnamic acid and some aliphatic acids also displayed a peak for m/z 45. However, the m/z 45 peak is structurally diagnostic only for certain benzene polycarboxylic acids because the spectra of compounds with two carboxyl groups on adjacent ring carbons do not produce a peak at m/z 45. For the m/z 79 ion to be formed, an intramolecular reaction should take place in which protonated CO 2 within the ion-neutral complex acts as the attacking electrophile to transfer a proton to benzene. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

H-implantation in SO 2 and CO 2 ices

NASA Astrophysics Data System (ADS)

Garozzo, M.; Fulvio, D.; Gomis, O.; Palumbo, M. E.; Strazzulla, G.

2008-07-01

Ices in the solar system are observed on the surface of planets, satellites, comets and asteroids where they are continuously subordinate at particle fluxes (cosmic ions, solar wind and charged particles caught in the magnetosphere of the planets) that deeply modify their physical and structural properties. Each incoming ion destroys molecular bonds producing fragments that, by recombination, form new molecules also different from the original ones. Moreover, if the incoming ion is reactive (H +, O n+ , S n+ , etc.), it can concur to the formation of new molecules. Those effects can be studied by laboratory experiments where, with some limitation, it is possible to reproduce the astrophysical environments of planetary ices. In this work, we describe some experiments of 15-100 keV H + and He + implantation in pure sulfur dioxide (SO 2) at 16 and 80 K and carbon dioxide (CO 2) at 16 K ices aimed to search for the formation of new molecules. Among other results we confirm that carbonic acid (H 2CO 3) is formed after H-implantation in CO 2, vice versa H-implantation in SO 2 at both temperatures does not produce measurable quantity of sulfurous acid (H 2SO 3). The results are discussed in the light of their relevance to the chemistry of some solar system objects, particularly of Io, the innermost of Jupiter's Galilean satellites, that exhibits a surface very rich in frost SO 2 and it is continuously bombarded with H + ions caught in Jupiter's magnetosphere.

BIOSYNTHESIS OF CHLORAMPHENICOL IV.

PubMed Central

Gottlieb, David; Carter, H. E.; Robbins, P. W.; Burg, R. W.

1962-01-01

Gottlieb, David (University of Illinois, Urbana), H. E. Carter, P. W. Robbins, and R. W. Burg. Biosynthesis of chloramphenicol. IV. Incorporation of carbon14-labeled precursors. J. Bacteriol. 84:888–895. 1962.—Metabolism of dl-phenylalanine stimulated antibiotic synthesis by Streptomyces venezuelae, and resulted in the fixation of carbons 1 and 2 into the carbonyl group of chloramphenicol. It probably occurs by the oxidation of these carbons to carbon dioxide, followed by incorporation. Carbon 3 and the adjacent ring carbon were found in the dichloromethyl and the carbonyl carbons, respectively, of the dichloroacetyl portion of the molecule. The phenyl group of the amino acid is not transferred to the ring in chloramphenicol. Another stimulatory amino acid, dl-norleucine, contributed carbon 2 only as the carbonyl carbon. dl-Leucine is metabolized so that two adjacent carbons appear as the carbons in the dichloroacetyl moiety of the antibiotic. From acetic acid, carbon 1 is found only in the carbonyl group of chloramphenicol; carbon 2 of the acid is more generally distributed among the ring and side chain of the p-nitrophenylserinol part of the antibiotic, but is in greatest concentration in the dichloroacetyl fraction. Formic acid and carbon dioxide also are transformed only to the carbonyl group. Glycerol, the main source of metabolized carbon in the medium, has a general role and contributes to all parts of the molecule. In addition, it has a specific role in supplying an intact three-carbon fragment which enters into the molecule of chloramphenicol as a unit. PMID:13949488

Optimized Unlike-Pair Interactions for Water-Carbon Dioxide Mixtures described by the SPC/E and EPM2 Models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vlcek, Lukas; Chialvo, Ariel A; Cole, David

The unlike- pair interaction parameters for the SPC/E- EPM2 models have been optimized to reproduce the mutual solubility of water and carbon dioxide at the conditions of liquid- supercritical fluid phase equilibria. An efficient global optimization of the parameters is achieved through an implementation of the coupling parameter approach, adapted to phase equilibria calculations in the Gibbs ensemble, that explicitly corrects for the over- polarization of the SPC/E water molecule in the non- polar CO2 environments. The resulting H2O- CO2 force field reproduces accurately the available experimental solubilities at the two fluid phases in equilibria as well as the correspondingmore » species tracer diffusion coefficients.« less

A Continuous Flow System for the Measurement of Ambient Nitrogen Oxides [NO + NO2] Using Rhodamine B Hydrazide as a Chemosensor.

PubMed

Malingappa, Pandurangappa; Yarradoddappa, Venkataramanappa

2014-01-01

A new chemosensor has been used to monitor atmospheric nitrogen oxides [NO + NO2] at parts per billion (ppb) level. It is based on the catalytic reaction of nitrogen oxides with rhodamine B hydrazide (RBH) to produce a colored compound through the hydrolysis of the amide bond of the molecule. A simple colorimeter has been used to monitor atmospheric nitrogen dioxide at ppb level. The air samples were purged through a sampling cuvette containing RBH solution using peristaltic pump. The proposed method has been successfully applied to monitor the ambient nitrogen dioxide levels at traffic junction points within the city limits and the results obtained are compared with the standard Griess-Ilosvay method.

Astronomical masers and lasers

NASA Astrophysics Data System (ADS)

Townes, C. H.

1997-12-01

A brief account is given of the discovery of the astronomical maser and laser effects in OH radicals and in molecules of water (H2O), carbon monoxide and dioxide (CO and CO2), ammonia (NH3), methyl alcohol (CH3OH), formaldehyde (CH2O), and silicon oxide (SiO). A detailed table is given of all the currently known molecular stimulated-emission lines.

Optimization of amino group density on surfaces of titanium dioxide nanoparticles covalently bonded to a silicone substrate for antibacterial and cell adhesion activities.

PubMed

Okada, Masahiro; Yasuda, Shoji; Kimura, Tsuyoshi; Iwasaki, Mitsunobu; Ito, Seishiro; Kishida, Akio; Furuzono, Tsutomu

2006-01-01

A composite consisting of titanium dioxide (TiO2) particle, the surface of which was modified with amino groups, and a silicone substrate through covalent bonding at their interface was developed, and antibacterial and cell adhesion activities of the composite were evaluated. The density of the amino groups on the TiO2 particle surface was controlled by the reaction time of the modification reaction. The degradation rate of CH3CHO in the presence of the TiO2 particles under UV irradiation decreased with an increase in the amino group density on the TiO2 surface. On the other hand, the number of L929 cells adhering on the TiO2/silicone composite increased with an increase in the amino group density. From the above two results, the optimum density of amino groups for both photoreactivity and cell adhesiveness was estimated to be 2.0-4.0 molecules/nm2. The optimum amino group-modified TiO2/silicone composite sheet (amino group density, 3.0 molecules/nm2) showed an effective antibacterial activity for Escherichia coli bacteria under UV irradiation. (c) 2005 Wiley Periodicals, Inc

High Resolution Spectroscopy to Support Atmospheric Measurements

NASA Technical Reports Server (NTRS)

Benner, D. Chris; Venkataraman, Malathy Devi

2000-01-01

The major research activities performed during the cooperative agreement enhanced our spectroscopic knowledge of molecules of atmospheric interest such as carbon dioxide, water vapor, ozone, methane, and carbon monoxide, to name a few. Measurements were made using the NASA Langley Tunable Diode Laser Spectrometer System (TDL) and several Fourier Transform Spectrometer Systems (FTS) around the globe. The results from these studies made remarkable improvements in the line positions and intensities for several molecules, particularly ozone and carbon dioxide in the 2 to 17-micrometer spectral region. Measurements of pressure broadening and pressure induced line shift coefficients and the temperature dependence of pressure broadening and pressure induced line shift coefficients for infrared transitions of ozone, methane, and water vapor were also performed. Results from these studies have been used for retrievals of stratospheric gas concentration profiles from data collected by several Upper Atmospheric Research satellite (UARS) infrared instruments as well as in the analysis of high resolution atmospheric spectra such as those acquired by space-based, ground-based, and various balloon- and aircraft-borne experiments. Our results made significant contributions in several updates of the HITRAN (HIgh resolution TRANsmission) spectral line parameters database. This database enjoys worldwide recognition in research involving diversified scientific fields.

High Resolution Spectroscopy to Support Atmospheric Measurements

NASA Technical Reports Server (NTRS)

Benner, D. Chris; Venkataraman, Malathy Devi

2000-01-01

The major research activities performed during the cooperative agreement enhanced our spectroscopic knowledge of molecules of atmospheric interest such as carbon dioxide, water vapor, ozone, methane, and carbon monoxide, to name a few. Measurements were made using the NASA Langley Tunable Diode Laser Spectrometer System (TDL) and several Fourier Transform Spectrometer Systems (FTS) around the globe. The results from these studies made remarkable improvements in the line positions and intensities for several molecules, particularly ozone and carbon dioxide in the 2 to 17-micrometer spectral region. Measurements of pressure broadening and pressure induced line shift coefficients and the temperature dependence of pressure broadening and pressure induced line shift coefficients for infrared transitions of ozone, methane, and water vapor were also performed. Results from these studies have been used for retrievals of stratospheric gas concentration profiles from data collected by several Upper Atmospheric Research satellite (UARS) infrared instruments as well as in the analysis of high resolution atmospheric spectra such as those acquired by space-based, ground-based, and various balloon-and aircraft-borne experiments. Our results made significant contributions in several updates of the HITRAN (HIgh resolution TRANsmission) spectral line parameters database. This database enjoys worldwide recognition in research involving diversified scientific fields.

Manipulating the Surface Chemistry of Quantum Dots for Sensitive Ratiometric Fluorescence Detection of Sulfur Dioxide.

PubMed

Li, Huihui; Zhu, Houjuan; Sun, Mingtai; Yan, Yehan; Zhang, Kui; Huang, Dejian; Wang, Suhua

2015-08-11

Herein, we report a novel approach to the rapid visual detection of gaseous sulfur dioxide (SO2) by manipulating the surface chemistry of 3-aminopropyltriethoxysilane (APTS)-modified quantum dots (QDs) using fluorescent coumarin-3-carboxylic acid (CCA) for specific reaction with SO2. The CCA molecules are attached to the surface amino groups of the QDs through electrostatic attraction, thus the fluorescence of CCA is greatly suppressed because of the formation of an ion-pair complex between the ATPS-modified QDs and CCA. Such an interaction is vulnerable to SO2 because SO2 can readily react with surface amino groups to form strong charge-transfer complexes and subsequently release the strongly fluorescent CCA molecules. The mechanism has been carefully verified through a series of control experiments. Upon exposure to different amounts of SO2, the fluorescent color of the nanoparticle-based sensor displays continuously changes from red to blue. Most importantly, the approach owns high selectivity for SO2 and a tolerance of interference, which enables the sensor to detect SO2 in a practical application. Using this fluorescence-based sensing method, we have achieved a visual detection limit of 6 ppb for gaseous SO2.

The upgrading of glass microballoons. [targets for laser fusion

NASA Technical Reports Server (NTRS)

Dunn, S. A.; Gunter, S.

1979-01-01

The processes and mechanisms involved in producing glass microballoons of acceptable quality for laser fusion by gas jet levitation and manipulation were studied. Glass microballoons (GMBs) levitated at temperatures below, as well as above the liquidus, appear to diffuse sulfur dioxide, a polar molecule with a moderately large diameter, and hydrogen, a much smaller molecule at comparable rates. Rates on the order of tens of atmospheres per hour (constant volume) per atmosphere of partial pressure differential have been observed at temperatures around the liquidus. Relatively rapid and convenient filling of molten GMBs by levitation in deuterium and tritium appears to be a possibility.

Polymer system for gettering hydrogen

DOEpatents

Shepodd, Timothy Jon; Whinnery, LeRoy L.

2000-01-01

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, Timothy Jon; Whinnery, LeRoy L.

1998-11-17

A novel composition comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen.

Nanofabrication technique based on localized photocatalytic reactions using a TiO2-coated atomic force microscopy probe

NASA Astrophysics Data System (ADS)

Shibata, Takayuki; Iio, Naohiro; Furukawa, Hiromi; Nagai, Moeto

2017-02-01

We performed a fundamental study on the photocatalytic degradation of fluorescently labeled DNA molecules immobilized on titanium dioxide (TiO2) thin films under ultraviolet irradiation. The films were prepared by the electrochemical anodization of Ti thin films sputtered on silicon substrates. We also confirmed that the photocurrent arising from the photocatalytic oxidation of DNA molecules can be detected during this process. We then demonstrated an atomic force microscopy (AFM)-based nanofabrication technique by employing TiO2-coated AFM probes to penetrate living cell membranes under near-physiological conditions for minimally invasive intracellular delivery.

A computational study of the TiO2 molecule

NASA Technical Reports Server (NTRS)

Ramana, M. V.; Phillips, D. H.

1988-01-01

A computational investigation of the ground 1A1 and lowest energy B2 states of the titanium dioxide molecule has been carried out. The treatment utilized SCF calculations in an extended basis followed by a CI treatment for each geometry. The ground state geometry agrees well with experiment, while the agreement between the computed vibrational frequency nu1 and the experimental value for a matrix isolated TiO2 is less satisfactory. Population analysis for the ground state indicates less than one excess electron on each oxygen atom. The first excited state has a linear geometry and the singlet and triplet are essentially degenerate.

Mechanistic aspects of ingested chlorine dioxide on thyroid function: impact of oxidants on iodide metabolism.

PubMed Central

Bercz, J P; Jones, L L; Harrington, R M; Bawa, R; Condie, L

1986-01-01

Toxicological studies dealing with recent findings of health effects of drinking water disinfectants are reviewed. Experiments with monkeys and rodents indicate that the biological activity of ingested disinfectants is expressed via their chemical interaction with the mucosal epithelia, secretory products, and nutritional contents of the alimentary tract. Evidence exists that a principal partner of this redox interaction is the iodide of nutritional origin that is ubiquitous in the gastrointestinal tract. Thus the observation that subchronic exposure to chlorine dioxide (ClO2) in drinking water decreases serum thyroxine levels in mammalian species can be best explained with changes produced in the chemical form of the bioavailable iodide. Ongoing and previously reported mechanistic studies indicate that oxidizing agents such as chlorine-based disinfectants oxidize the basal iodide content of the gastrointestinal tract. The resulting reactive iodine species readily attaches to organic matter by covalent bonding. Evidence suggests that the extent to which such iodinated organics are formed is proportional to the magnitude of the electromotive force and stoichiometry of the redox couple between iodide and the disinfectant. Because the extent of thyroid uptake of the bioavailable iodide does not decrease during ClO2 ingestion, it seems that ClO2 does not cause iodide deficiency of sufficient magnitude to account for the decrease in hormonogenesis. Absorption of one or more of iodinated molecules, e.g., nutrients, hormones, or cellular constituents of the alimentary tract having thyromimetic or thyroid inhibitory properties, is a better hypothesis for the effects seen. Images FIGURE 1. a FIGURE 1. b FIGURE 1. c PMID:3816729

Coiled tubing drilling with supercritical carbon dioxide

DOEpatents

Kolle , Jack J.

2002-01-01

A method for increasing the efficiency of drilling operations by using a drilling fluid material that exists as supercritical fluid or a dense gas at temperature and pressure conditions existing at a drill site. The material can be used to reduce mechanical drilling forces, to remove cuttings, or to jet erode a substrate. In one embodiment, carbon dioxide (CO.sub.2) is used as the material for drilling within wells in the earth, where the normal temperature and pressure conditions cause CO.sub.2 to exist as a supercritical fluid. Supercritical carbon dioxide (SC--CO.sub.2) is preferably used with coiled tube (CT) drilling equipment. The very low viscosity SC--CO.sub.2 provides efficient cooling of the drill head, and efficient cuttings removal. Further, the diffusivity of SC--CO.sub.2 within the pores of petroleum formations is significantly higher than that of water, making jet erosion using SC--CO.sub.2 much more effective than water jet erosion. SC--CO.sub.2 jets can be used to assist mechanical drilling, for erosion drilling, or for scale removal. A choke manifold at the well head or mud cap drilling equipment can be used to control the pressure within the borehole, to ensure that the temperature and pressure conditions necessary for CO.sub.2 to exist as either a supercritical fluid or a dense gas occur at the drill site. Spent CO.sub.2 can be vented to the atmosphere, collected for reuse, or directed into the formation to aid in the recovery of petroleum.

Comparison of Satellite Observations of Nitrogen Dioxide to Surface Monitor Nitrogen Dioxide Concentration

NASA Technical Reports Server (NTRS)

Kleb, Mary M.; Pippin, Margaret R.; Pierce, R. Bradley; Neil, Doreen O.; Lingenfelser, Gretchen; Szykman, James J.

2006-01-01

Nitrogen dioxide is one of the U. S. EPA s criteria pollutants, and one of the main ingredients needed for the production of ground-level ozone. Both ozone and nitrogen dioxide cause severe public health problems. Existing satellites have begun to produce observational data sets for nitrogen dioxide. Under NASAs Earth Science Applications Program, we examined the relationship between satellite observations and surface monitor observations of this air pollutant to examine if the satellite data can be used to facilitate a more capable and integrated observing network. This report provides a comparison of satellite tropospheric column nitrogen dioxide to surface monitor nitrogen dioxide concentration for the period from September 1996 through August 1997 at more than 300 individual locations in the continental US. We found that the spatial resolution and observation time of the satellite did not capture the variability of this pollutant as measured at ground level. The tools and processes developed to conduct this study will be applied to the analysis of advanced satellite observations. One advanced instrument has significantly better spatial resolution than the measurements studied here and operates with an afternoon overpass time, providing a more representative distribution for once-per-day sampling of this photochemically active atmospheric constituent.

I. Cognitive and instructional factors relating to students' development of personal models of chemical systems in the general chemistry laboratory II. Solvation in supercritical carbon dioxide/ethanol mixtures studied by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Anthony, Seth

Part I. Students' participation in inquiry-based chemistry laboratory curricula, and, in particular, engagement with key thinking processes in conjunction with these experiences, is linked with success at the difficult task of "transfer"---applying their knowledge in new contexts to solve unfamiliar types of problems. We investigate factors related to classroom experiences, student metacognition, and instructor feedback that may affect students' engagement in key aspects of the Model-Observe-Reflect-Explain (MORE) laboratory curriculum - production of written molecular-level models of chemical systems, describing changes to those models, and supporting those changes with reference to experimental evidence---and related behaviors. Participation in introductory activities that emphasize reviewing and critiquing of sample models and peers' models are associated with improvement in several of these key aspects. When students' self-assessments of the quality of aspects of their models are solicited, students are generally overconfident in the quality of their models, but these self-ratings are also sensitive to the strictness of grades assigned by their instructor. Furthermore, students who produce higher-quality models are also more accurate in their self-assessments, suggesting the importance of self-evaluation as part of the model-writing process. While the written feedback delivered by instructors did not have significant impacts on student model quality or self-assessments, students' resubmissions of models were significantly improved when students received "reflective" feedback prompting them to self-evaluate the quality of their models. Analysis of several case studies indicates that the content and extent of molecular-level ideas expressed in students' models are linked with the depth of discussion and content of discussion that occurred during the laboratory period, with ideas developed or personally committed to by students during the laboratory period being likely to appear in students' post-laboratory refined models. These discussions during the laboratory period are primarily prompted by factors external to the students or their laboratory groups such as questions posed by the instructor or laboratory materials. Part II. Solvation of polar molecules within non-polar supercritical carbon dioxide is often facilitated by the introduction of polar cosolvents as entrainers, which are believed to preferentially surround solute molecules. Molecular dynamics simulations of supercritical carbon dioxide/ethanol mixtures reveal that ethanol molecules form hydrogen-bonded aggregates of varying sizes and structures, with cyclic tetramers and pentamers being unusually prevalent. The dynamics of ethanol molecules within these mixtures at a range of thermodynamic conditions can largely be explained by differences in size and structure in these aggregates. Simulations that include solute molecules reveal enhancement of the polar cosolvent around hydrogen-bonding sites on the solute molecules, corroborating and helping to explain previously reported experimental trends in solute mobility.

DFT study on the interaction of TiO2 (001) surface with HCHO molecules

NASA Astrophysics Data System (ADS)

Wu, Guofei; Zhao, Cuihua; Guo, Changqing; Chen, Jianhua; Zhang, Yibing; Li, Yuqiong

2018-01-01

The interactions of formaldehyde (HCHO) molecule with TiO2 (001) surface were studied using density functional theory calculations. HCHO molecules are dissociated by the cleavage of Csbnd H bonds after adsorption on TiO2 surface. The strong interactions between HCHO melecules and TiO2 surface are largely attributed to the bonding of hydrogen of HCHO and oxygen of TiO2 surface, which is mainly from the hybridization of the H 1s, O 2p and O 2s. The newly formed Hsbnd O bonds cause the structure changes of TiO2 surface, and lead to the cleavage of Osbnd Ti bond of TiO2 surface. The Csbnd O bond that the dissociated remains of HCHO and newly formed Hsbnd O bond can be oxidized to form carbon dioxide and water in subsequent action by oxygen from the atomosphere. The charges transfer from HCHO to TiO2 surface, and the sum amount of the charges transferred from four HCHO molecules to TiO2 surface is bigger than that from one HCHO molecule to TiO2 surface due to the combined interaction of four HCHO molecules with TiO2 surface.

Elasticity and Stability of Clathrate Hydrate: Role of Guest Molecule Motions.

PubMed

Jia, Jihui; Liang, Yunfeng; Tsuji, Takeshi; Murata, Sumihiko; Matsuoka, Toshifumi

2017-05-02

Molecular dynamic simulations were performed to determine the elastic constants of carbon dioxide (CO 2 ) and methane (CH 4 ) hydrates at one hundred pressure-temperature data points, respectively. The conditions represent marine sediments and permafrost zones where gas hydrates occur. The shear modulus and Young's modulus of the CO 2 hydrate increase anomalously with increasing temperature, whereas those of the CH 4 hydrate decrease regularly with increase in temperature. We ascribe this anomaly to the kinetic behavior of the linear CO 2 molecule, especially those in the small cages. The cavity space of the cage limits free rotational motion of the CO 2 molecule at low temperature. With increase in temperature, the CO 2 molecule can rotate easily, and enhance the stability and rigidity of the CO 2 hydrate. Our work provides a key database for the elastic properties of gas hydrates, and molecular insights into stability changes of CO 2 hydrate from high temperature of ~5 °C to low decomposition temperature of ~-150 °C.

Geologic framework for the national assessment of carbon dioxide storage resources─South Florida Basin: Chapter L in Geologic framework for the national assessment of carbon dioxide storage resources

USGS Publications Warehouse

Roberts-Ashby, Tina L.; Brennan, Sean T.; Merrill, Matthew D.; Blondes, Madalyn S.; Freeman, P.A.; Cahan, Steven M.; DeVera, Christina A.; Lohr, Celeste D.; Warwick, Peter D.; Corum, Margo D.

2015-08-26

This report presents five storage assessment units (SAUs) that have been identified as potentially suitable for geologic carbon dioxide sequestration within a 35,075-square-mile area that includes the entire onshore and State-water portions of the South Florida Basin. Platform-wide, thick successions of laterally extensive carbonates and evaporites deposited in highly cyclic depositional environments in the South Florida Basin provide several massive, porous carbonate reservoirs that are separated by evaporite seals. For each storage assessment unit identified within the basin, the areal distribution of the reservoir-seal couplet identified as suitable for geologic Carbon dioxide sequestration is presented, along with a description of the geologic characteristics that influence the potential carbon dioxide storage volume and reservoir performance. On a case-by-case basis, strategies for estimating the pore volume existing within structurally and (or) stratigraphically closed traps are also discussed. Geologic information presented in this report has been employed to calculate potential storage capacities for carbon dioxide sequestration in the storage assessment units assessed herein, although complete assessment results are not contained in this report.

Domestic nitrogen oxide exposure, urinary nitrate, and asthma prevalence in preschool children.

PubMed

Ciuk, J; Volkmer, R E; Edwards, J W

2001-01-01

A South Australian preschool study carried out in 1993 showed that the prevalence of respiratory symptoms was significantly associated with use of unflued gas appliances for cooking and heating. The authors sought to determine an association between domestic exposure to nitrogen dioxide and the excretion of total urinary nitrate and nitrite, and their association with asthma prevalence. The results indicated that the geometric mean concentrations of nitrogen dioxide were much higher in homes that had natural gas appliance(s) and other types of appliances (i.e., electric and solid fuel). Higher levels of nitrogen dioxide were found in homes of suburban areas with higher prevalence of asthma and respiratory symptoms. Nitrogen dioxide levels were lower in the summer, and there was a higher level in kitchens than in bedrooms. Urinary nitrate excretion was evaluated in 1,335 preschool children from the same sampling areas. No association existed between nitrogen dioxide levels and urinary nitrates, nor was there a relationship between urinary nitrates and asthma prevalence. These findings confirm that there is a positive association between nitrogen dioxide exposure from gas appliances and the prevalence of respiratory symptoms, but urinary nitrate is not a useful biomarker of exposure at these levels.

Recycling of high purity selenium from CIGS solar cell waste materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gustafsson, Anna M.K., E-mail: anna.gustafsson@chalmers.se; Foreman, Mark R.StJ.; Ekberg, Christian

Highlights: • A new method for recycling of selenium from CIGS solar cell materials is presented. • Separation of selenium as selenium dioxide after heating in oxygen atmosphere. • Complete selenium separation after oxidation of <63 μm particles at 800 °C for 1 h. • After reduction of selenium dioxide the selenium purity was higher than 99.999 wt%. - Abstract: Copper indium gallium diselenide (CIGS) is a promising material in thin film solar cell production. To make CIGS solar cells more competitive, both economically and environmentally, in comparison to other energy sources, methods for recycling are needed. In addition tomore » the generally high price of the material, significant amounts of the metals are lost in the manufacturing process. The feasibility of recycling selenium from CIGS through oxidation at elevated temperatures was therefore examined. During oxidation gaseous selenium dioxide was formed and could be separated from the other elements, which remained in solid state. Upon cooling, the selenium dioxide sublimes and can be collected as crystals. After oxidation for 1 h at 800 °C all of the selenium was separated from the CIGS material. Two different reduction methods for reduction of the selenium dioxide to selenium were tested. In the first reduction method an organic molecule was used as the reducing agent in a Riley reaction. In the second reduction method sulphur dioxide gas was used. Both methods resulted in high purity selenium. This proves that the studied selenium separation method could be the first step in a recycling process aimed at the complete separation and recovery of high purity elements from CIGS.« less

Spectroscopic and Thermal Behavior of Chromium Soaps

NASA Astrophysics Data System (ADS)

Mehrotra, K. N.; Jain, Mamta

1996-02-01

The physicochemical characteristics of chromium soaps (myristate and stearate) were investigated in the solid state (thermal, X-ray, and IR measurements) and in solutions (spectrophotometric measurements). The thermal measurements showed that the decomposition of chromium soaps is a two-step process. The soap decomposed into chromium oxycarboxylate, ketone, and carbon dioxide in the first step and the intermediate oxycarboxylate underwent further decomposition to chromium trioxide in the second step. The results showed that the second step is kinetically of zero order and the values of energy of activation for the first and second steps lie in the ranges 6-7 and 17-18 kcal mol-1, respectively. The X-ray diffraction results showed that these soaps possess double-layer structure with molecular axes slightly inclined to the basal plane. The infrared results revealed that the fatty acids exist with dimeric structure through hydrogen bonding between two molecules of fatty acids whereas the metal-to-oxygen bonds in chromium soaps are not purely ionic but possess considerable covalent character. The results of spectrophotometric measurements also confirmed the somewhat covalent nature of chromium soaps in solutions in dichloromethane.

Fabrication of Integral Solar Cell Covers by the Plasma Activated Source.

DTIC Science & Technology

1981-01-01

1 Average Intrinsic Deposition Stress of Pyrolitic Silicon Oxynitride Films vs. Composition ................................... 7 2 Coefficient of...source for activated oxygen molecules which were reacted with, for example, silane at a solar cell surface to deposit amorphous silicon dioxide on the... Silicon Solar Cells ........ 51 44.6 SiO 2 Coatings in GaAs Solar Cells ........... 58 5.0 CONCLUSIONS..................................... 61 5.1

Photocatalytic oxidation of organic compounds on Mars

NASA Technical Reports Server (NTRS)

Chun, S. F. S.; Pang, K. D.; Cutts, J. A.; Ajello, J. M.

1978-01-01

Ultraviolet-stimulated catalytic oxidation is proposed as a mechanism for the destruction of organic compounds on Mars. The process involves the presence of gaseous oxygen, UV radiation, and a catalyst (titanium dioxide), and all three of these have been found to be present in the Martian environment. Therefore it seems plausible that UV-stimulated oxidation of organics is responsible for degrading organic molecules into inorganic end products.

Sol-gel method for encapsulating molecules

DOEpatents

Brinker, C. Jeffrey; Ashley, Carol S.; Bhatia, Rimple; Singh, Anup K.

2002-01-01

A method for encapsulating organic molecules, and in particular, biomolecules using sol-gel chemistry. A silica sol is prepared from an aqueous alkali metal silicate solution, such as a mixture of silicon dioxide and sodium or potassium oxide in water. The pH is adjusted to a suitably low value to stabilize the sol by minimizing the rate of siloxane condensation, thereby allowing storage stability of the sol prior to gelation. The organic molecules, generally in solution, is then added with the organic molecules being encapsulated in the sol matrix. After aging, either a thin film can be prepared or a gel can be formed with the encapsulated molecules. Depending upon the acid used, pH, and other processing conditions, the gelation time can be from one minute up to several days. In the method of the present invention, no alcohols are generated as by-products during the sol-gel and encapsulation steps. The organic molecules can be added at any desired pH value, where the pH value is generally chosen to achieve the desired reactivity of the organic molecules. The method of the present invention thereby presents a sufficiently mild encapsulation method to retain a significant portion of the activity of the biomolecules, compared with the activity of the biomolecules in free solution.

Quantum Chemical Study of Supercritical Carbon Dioxide Effects on Combustion Kinetics.

PubMed

Masunov, Artëm E; Wait, Elizabeth E; Atlanov, Arseniy A; Vasu, Subith S

2017-05-18

In oxy-fuel combustion, the pure oxygen (O 2 ), diluted with CO 2 is used as oxidant instead air. Hence, the combustion products (CO 2 and H 2 O) are free from pollution by nitrogen oxides. Moreover, high pressures result in the near-liquid density of CO 2 at supercritical state (sCO 2 ). Unfortunately, the effects of sCO 2 on the combustion kinetics are far from being understood. To assist in this understanding, in this work we are using quantum chemistry methods. Here we investigate potential energy surfaces of important combustion reactions in the presence of the carbon dioxide molecule. All transition states and reactant and product complexes are reported for three reactions: H 2 CO + HO 2 → HCO + H 2 O 2 (R1), 2HO 2 → H 2 O 2 + O 2 (R2), and CO + OH → CO 2 + H (R3). In reaction R3, covalent binding of CO 2 to the OH radical and then the CO molecule opens a new pathway, including hydrogen transfer from oxygen to carbon atoms followed by CH bond dissociation. Compared to the bimolecular OH + CO mechanism, this pathway reduces the activation barrier by 5 kcal/mol and is expected to accelerate the reaction. In the case of hydroperoxyl self-reaction 2HO 2 → H 2 O 2 + O 2 the intermediates, containing covalent bonds to CO 2 are found not to be competitive. However, the spectator CO 2 molecule can stabilize the cyclic transition state and lower the barrier by 3 kcal/mol. Formation of covalent intermediates is also discovered in the H 2 CO + HO 2 → HCO + H 2 O 2 reaction, but these species lead to substantially higher activation barriers, which makes them unlikely to play a role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide also stabilizes the transition state and reduces the reaction barrier. These results indicate that the CO 2 environment is likely to have a catalytic effect on combustion reactions, which needs to be included in kinetic combustion mechanisms in supercritical CO 2 .

An Optimal Centralized Carbon Dioxide Repository for Florida, USA

PubMed Central

Poiencot, Brandon; Brown, Christopher

2011-01-01

For over a decade, the United States Department of Energy, and engineers, geologists, and scientists from all over the world have investigated the potential for reducing atmospheric carbon emissions through carbon sequestration. Numerous reports exist analyzing the potential for sequestering carbon dioxide at various sites around the globe, but none have identified the potential for a statewide system in Florida, USA. In 2005, 83% of Florida’s electrical energy was produced by natural gas, coal, or oil (e.g., fossil fuels), from power plants spread across the state. In addition, only limited research has been completed on evaluating optimal pipeline transportation networks to centralized carbon dioxide repositories. This paper describes the feasibility and preliminary locations for an optimal centralized Florida-wide carbon sequestration repository. Linear programming optimization modeling is used to plan and route an idealized pipeline network to existing Florida power plants. Further analysis of the subsurface geology in these general locations will provide insight into the suitability of the subsurface conditions and the available capacity for carbon sequestration at selected possible repository sites. The identification of the most favorable site(s) is also presented. PMID:21695024

An optimal centralized carbon dioxide repository for Florida, USA.

PubMed

Poiencot, Brandon; Brown, Christopher

2011-04-01

For over a decade, the United States Department of Energy, and engineers, geologists, and scientists from all over the world have investigated the potential for reducing atmospheric carbon emissions through carbon sequestration. Numerous reports exist analyzing the potential for sequestering carbon dioxide at various sites around the globe, but none have identified the potential for a statewide system in Florida, USA. In 2005, 83% of Florida's electrical energy was produced by natural gas, coal, or oil (e.g., fossil fuels), from power plants spread across the state. In addition, only limited research has been completed on evaluating optimal pipeline transportation networks to centralized carbon dioxide repositories. This paper describes the feasibility and preliminary locations for an optimal centralized Florida-wide carbon sequestration repository. Linear programming optimization modeling is used to plan and route an idealized pipeline network to existing Florida power plants. Further analysis of the subsurface geology in these general locations will provide insight into the suitability of the subsurface conditions and the available capacity for carbon sequestration at selected possible repository sites. The identification of the most favorable site(s) is also presented.

Characterization of amine-functionalized electrode for aqueous carbon dioxide (CO2) direct detection

NASA Astrophysics Data System (ADS)

Sato, Hiroshi

2017-03-01

In this study, fabrication of amino groups and ferrocenes co-modified sensor electrode and electrochemical detection of carbon dioxide (CO2) in the saline solution is reported. Electrochemical detection of CO2 was carried out using cyclic voltammetry in saline solution containing sodium bicarbonate as CO2 source. Oxidation and reduction peak current intensities computed from cyclic voltammograms varied as a function of concentration of CO2 molecules. The calibration curve was obtained by plotting oxidation peak current intensities as a function of CO2 concentration. The sensor electrode prepared in this study can estimate the differences between concentrations of CO2 in normal seawater up to 10 times higher. Furthermore, the surface analysis was performed to clarify the CO2 detection mechanism.

A Continuous Flow System for the Measurement of Ambient Nitrogen Oxides [NO + NO2] Using Rhodamine B Hydrazide as a Chemosensor

PubMed Central

Malingappa, Pandurangappa; Yarradoddappa, Venkataramanappa

2014-01-01

A new chemosensor has been used to monitor atmospheric nitrogen oxides [NO + NO2] at parts per billion (ppb) level. It is based on the catalytic reaction of nitrogen oxides with rhodamine B hydrazide (RBH) to produce a colored compound through the hydrolysis of the amide bond of the molecule. A simple colorimeter has been used to monitor atmospheric nitrogen dioxide at ppb level. The air samples were purged through a sampling cuvette containing RBH solution using peristaltic pump. The proposed method has been successfully applied to monitor the ambient nitrogen dioxide levels at traffic junction points within the city limits and the results obtained are compared with the standard Griess-Ilosvay method. PMID:25210422

Formation of Gas-Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions.

PubMed

Jiang, Li-Xue; Zhao, Chongyang; Li, Xiao-Na; Chen, Hui; He, Sheng-Gui

2017-04-03

The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO 2 and formation of a C-H bond. Herein, we report that HCO 2 - and CO can be formed in the thermal reaction of CO 2 with a diatomic metal hydride species, FeH - . The FeH - anions were produced by laser ablation, and the reaction with CO 2 was analyzed by mass spectrometry and quantum-chemical calculations. Gas-phase HCO 2 - was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO 2 hydrogenation in this gas-phase study parallels similar behavior of a condensed-phase iron catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

N-Heterocyclic Olefins as Robust Organocatalyst for the Chemical Conversion of Carbon Dioxide to Value-Added Chemicals.

PubMed

Saptal, Vitthal B; Bhanage, Bhalchandra M

2016-08-09

In this report, the activity of N-heterocyclic olefins (NHOs) as a newly emerging class of organocatalyst is investigated for the chemical fixation of carbon dioxide through reactions with aziridines to form oxazolidinones and the N-formylation of amines with polymethylhydrosiloxane (PMHS) or 9-borabicyclo[3.3.1]nonane (9-BBN) as the reducing agent under mild conditions. The exocyclic carbon atoms of NHOs are highly nucleophilic owing to the electron-donating ability of the two nitrogen atoms. This high nucleophilicity of the NHOs activates CO2 molecules to form zwitterionic NHO-carboxylate (NHO-CO2 ) adducts, which are active in formylation reactions as well as the carboxylation of aziridines to oxazolidinones. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pulsed-discharge carbon dioxide lasers

NASA Technical Reports Server (NTRS)

Willetts, David V.

1990-01-01

The purpose is to attempt a general introduction to pulsed carbon dioxide lasers of the kind used or proposed for laser radar applications. Laser physics is an excellent example of a cross-disciplinary topic, and the molecular spectroscopy, energy transfer, and plasma kinetics of the devices are explored. The concept of stimulated emission and population inversions is introduced, leading on to the molecular spectroscopy of the CO2 molecule. This is followed by a consideration of electron-impact pumping, and the pertinent energy transfer and relaxation processes which go on. Since the devices are plasma pumped, it is necessary to introduce a complex subject, but this is restricted to appropriate physics of glow discharges. Examples of representative devices are shown. The implications of the foregoing to plasma chemistry and gas life are discussed.

Synthesis, characterization and thermodynamic study of carbon dioxide adsorption on akaganéite

DOE PAGES

Roque-Malherbe, R.; Lugo, F.; Rivera-Maldonado, C.; ...

2015-04-01

A mixture of akaganeite nanoparticles and sodium salts was synthesized and modi fied, first by washing, and then by Li exchange. The structural characterization of the produced materials was performed with: powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, thermogravimetric analysis, diffuse reflectance infrared Fourier transform spectrometry, Mossbauer spectros- € copy and magnetization measurements. Additionally low pressure nitrogen and high pressure carbon dioxide adsorption experiments were performed. The sum of the characterization information made possible to conclude that the produced akaganeite phases crystallized in a structure exhibiting the symmetry of the I2/m space group, where the measured equivalentmore » spherical diameter of the akaganeite crystallites yielded 9 nm, as well, the tested phases exhibited a standard behaviour under heating and displayed a superparamagnetic behaviour. Finally the high pressure carbon dioxide adsorption experiments demonstrated a pressure-responsive framework opening event due to a structural transformation of the adsorbent framework induced by the guest molecules. This fact opens new applications for akaganeite as a high pressure adsorbent.« less

High performing and stable supported nano-alloys for the catalytic hydrogenation of levulinic acid to γ-valerolactone

PubMed Central

Luo, Wenhao; Sankar, Meenakshisundaram; Beale, Andrew M.; He, Qian; Kiely, Christopher J.; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

2015-01-01

The catalytic hydrogenation of levulinic acid, a key platform molecule in many biorefinery schemes, into γ-valerolactone is considered as one of the pivotal reactions to convert lignocellulose-based biomass into renewable fuels and chemicals. Here we report on the development of highly active, selective and stable supported metal catalysts for this reaction and on the beneficial effects of metal nano-alloying. Bimetallic random alloys of gold-palladium and ruthenium-palladium supported on titanium dioxide are prepared with a modified metal impregnation method. Gold-palladium/titanium dioxide shows a marked,~27-fold increase in activity (that is, turnover frequency of 0.1 s−1) compared with its monometallic counterparts. Although ruthenium-palladium/titanium dioxide is not only exceptionally active (that is, turnover frequency of 0.6 s−1), it shows excellent, sustained selectivity to γ-valerolactone (99%). The dilution and isolation of ruthenium by palladium is thought to be responsible for this superior catalytic performance. Alloying, furthermore, greatly improves the stability of both supported nano-alloy catalysts. PMID:25779385

Mixing of sulfur between pyritic and organic phases during coal conversion processes: Annual final report, March 1, 1986-February 28, 1987

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunkerton, L.V.; Nigam, A.; Mitra, S.

1987-05-01

In preparation for using /sup 33/S NMR for characterization of organic sulfur types in coal, previously prepared substituted dibenzothiophene model compounds were converted to their corresponding sulfones and their sulfur-33 nmr recorded. The sulfur-33 NMR spectra of dibenzothiophene-5,5-dioxide (2), 2-(p-methylphenylsulfonyl) dibenzothiophene-5,5-dioxide (4), and 2-(methylsulfonyl) dibenzothiophene-5,5-dioxide (6) are reported. The chemical shifts were in the +2 to -21 ppM range. The line widths ranged 70 to 200 Hz. The changes in /sup 13/C chemical shift experienced by aromatic carbons upon oxidizing the sulfide to its sulfone were also studied and the data used to identify which sulfone was formed in multiplemore » thioether-containing aromatics after partial oxidation. Continuing results on the use of the substituted dibenzothiophenes to monitor mixing of sulfur between pyritic and organic phases are also reported. Non-isothermal hydrodesulfurization of model organic sulfur compounds was carried out in a cola-like environment. The model sulfur compounds represented different types of carbon-sulfur bonds commonly encountered in coal. Similar experiments were carried out in the presence of troilite (iron sulfide) to investigate the possibility of sulfur migration from the organic compound to the iron sulfide. Next, iron pyrite was hydrodesulfurized in the presence of some organic molecules to see if sulfur could be incorporated into the organic molecules during the process. Results show that sulfur from organic compounds can be absorbed by troilite, and, similarly, sulfur from pyrite can form new carbon-sulfur bonds during hydrodesulfurization. Based on these observations, it is suggested that during coal conversion reactions it is possible to have intermigration of sulfur between the organic and the inorganic phases.« less

Engineers Clean Mirror with Carbon Dioxide Snow

NASA Image and Video Library

2015-05-07

Just like drivers sometimes use snow to clean their car mirrors in winter, two Exelis Inc. engineers are practicing "snow cleaning'" on a test telescope mirror for the James Webb Space Telescope at NASA's Goddard Space Flight Center in Greenbelt, Maryland. By shooting carbon dioxide snow at the surface, engineers are able to clean large telescope mirrors without scratching them. "The snow-like crystals (carbon dioxide snow) knock contaminate particulates and molecules off the mirror," said Lee Feinberg, NASA optical telescope element manager. This technique will only be used if the James Webb Space Telescope's mirror is contaminated during integration and testing. The Webb telescope is the scientific successor to NASA's Hubble Space Telescope. It will be the most powerful space telescope ever built. With a mirror seven times as large as Hubble's and infrared capability, Webb will be capturing light from 13.5 billion light years away. To do this, its mirror must be kept super clean. "Small dust particles or molecules can impact the science that can be done with the Webb," said Feinberg. "So cleanliness especially on the mirrors is critical." Webb is an international project led by NASA with its partners, the European Space Agency and the Canadian Space Agency. Image credit: NASA/Goddard/Chris Gunn Text credit: Laura Betz, NASA's Goddard Space Flight Center, Greenbelt, Maryland NASA image use policy. NASA Goddard Space Flight Center enables NASA’s mission through four scientific endeavors: Earth Science, Heliophysics, Solar System Exploration, and Astrophysics. Goddard plays a leading role in NASA’s accomplishments by contributing compelling scientific knowledge to advance the Agency’s mission. Follow us on Twitter Like us on Facebook Find us on Instagram

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, T.J.; Whinnery, L.L.

1998-11-17

A novel composition is described comprising organic polymer molecules having carbon-carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces. Organic polymers molecules containing carbon-carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble catalyst composition, comprising a hydrogenation catalyst and a catalyst support, preferably Pd supported on carbon, provide a hydrogen getter composition useful for removing hydrogen from enclosed spaces even in the presence of contaminants such as common atmospheric gases, water vapor, carbon dioxide, ammonia, oil mists, and water. The hydrogen getter composition disclosed herein is particularly useful for removing hydrogen from enclosed spaces containing potentially explosive mixtures of hydrogen and oxygen. 1 fig.

Measurements of Polyatomic Molecule Formation on an Icy Grain Analog Using Fast Atoms

NASA Technical Reports Server (NTRS)

Chutjian, A.; Madsunkov, S.; Shortt, B. J.; MacAskill, J. A.; Darrach, M. R.

2006-01-01

Carbon dioxide has been produced from the impact of a monoenergetic O(P-3) beam upon a surface cooled to 4.8 K and covered with a CO ice. Using temperature-programmed desorption and mass spectrometer detection, we have detected increasing amounts of CO2 formation with O(P-3) energies of 2, 5, 10, and 14 eV. This is the first measurement of polyatomic molecule formation on a surface with superthermal atoms. The goal of this work is to detect other polyatomic species, such as CH3OH, which can be formed under conditions that simulate the grain temperature, surface coverage, and superthermal atoms present in shock-heated circumstellar and interstellar regions.

Overexpression of the truncated version of ILV2 enhances glycerol production in Saccharomyces cerevisiae.

PubMed

Murashchenko, Lidiia; Abbas, Charles; Dmytruk, Kostyantyn; Sibirny, Andriy

2016-08-01

Acetolactate synthase is a mitochondrial enzyme that catalyses the conversion of two pyruvate molecules to an acetolactate molecule with release of carbon dioxide. The overexpression of the truncated version of the corresponding gene, ILV2, that codes for presumably cytosolic acetolactate synthase in the yeast Saccharomyces cerevisiae, led to a decrease in intracellular pyruvate concentration. This recombinant strain was also characterized by a four-fold increase in glycerol production, with a concomitant 1.8-fold reduction in ethanol production, when compared to that of the wild-type strain under anaerobic conditions in a glucose alcoholic fermentation. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Electron impact dissociation of amorphous cis-methyl acetate ice analogs

NASA Astrophysics Data System (ADS)

Sivaraman, B.; Mukherjee, R.; Subramanian, K. P.; Banerjee, S. B.

2014-08-01

We have carried out, for the first time, electron irradiation on methyl acetate (CH3COOCH3) ices grown, under astrochemical condition, at 85 K and the chemical changes were probed by FTIR spectroscopy in the mid-IR region (4000-500 cm-1). Carbon dioxide (CO2), carbon monoxide (CO) molecules were found to be the major products indicating a competing dissociation pathway along with the by-products ethane (C2H6) and dimethyl ether (CH3OCH3), respectively. CH3OH (methyl alcohol) formation showed the possibility of acetate to alcohol conversion by keV electron irradiation. In addition irradiation induced aggregation of CH3COOCH3 molecules is also proposed.

The influence of biomass energy consumption on CO2 emissions: a wavelet coherence approach.

PubMed

Bilgili, Faik; Öztürk, İlhan; Koçak, Emrah; Bulut, Ümit; Pamuk, Yalçın; Muğaloğlu, Erhan; Bağlıtaş, Hayriye H

2016-10-01

In terms of today, one may argue, throughout observations from energy literature papers, that (i) one of the main contributors of the global warming is carbon dioxide emissions, (ii) the fossil fuel energy usage greatly contributes to the carbon dioxide emissions, and (iii) the simulations from energy models attract the attention of policy makers to renewable energy as alternative energy source to mitigate the carbon dioxide emissions. Although there appears to be intensive renewable energy works in the related literature regarding renewables' efficiency/impact on environmental quality, a researcher might still need to follow further studies to review the significance of renewables in the environment since (i) the existing seminal papers employ time series models and/or panel data models or some other statistical observation to detect the role of renewables in the environment and (ii) existing papers consider mostly aggregated renewable energy source rather than examining the major component(s) of aggregated renewables. This paper attempted to examine clearly the impact of biomass on carbon dioxide emissions in detail through time series and frequency analyses. Hence, the paper follows wavelet coherence analyses. The data covers the US monthly observations ranging from 1984:1 to 2015 for the variables of total energy carbon dioxide emissions, biomass energy consumption, coal consumption, petroleum consumption, and natural gas consumption. The paper thus, throughout wavelet coherence and wavelet partial coherence analyses, observes frequency properties as well as time series properties of relevant variables to reveal the possible significant influence of biomass usage on the emissions in the USA in both the short-term and the long-term cycles. The paper also reveals, finally, that the biomass consumption mitigates CO2 emissions in the long run cycles after the year 2005 in the USA.

Air quality aerometric data for the city of Cleveland from 1967 to 1970 for sulphur dioxide, suspended particulates, and nitrogen dioxide

NASA Technical Reports Server (NTRS)

Neustadter, H. E.; King, R. B.; Fordyce, J. S.; Burr, J. C., Jr.

1972-01-01

The NASA Lewis Research Center is assisting the City of Cleveland, Ohio, in its effort to monitor its air pollution. This report describes the Cleveland program of the past 4 years and the supportive Lewis program currently being developed. The data accumulated by Cleveland over the past 4 years are presented together with some preliminary statistical analyses indicating in a semiquantitive manner the degree of air pollution existing within the boundaries of Cleveland.

A Bee Guide to Complying with the Safe Drinking Water Act

DTIC Science & Technology

1991-08-01

disinfectants commonly used in water treatment. These disinfectants include chlorine, chloramine , chlorine dioxide, and ozone. Existing toxicological...to water systems that add a disinfectant (oxidant, such as chlorine, chlorine dioxide, chloramines or ozone) to any part of the treatment process. 6...AL-TR-1 991-0075 AD-A242 509 ^tLECTE II AR M A BEE GUIDE TO COMPLYING WITH THE S SAFE DRINKING WATER ACT T R Q John G. Garland III, Major, USAF, BSCN

Pollution Detection Devices

NASA Technical Reports Server (NTRS)

1980-01-01

Barringer Research, Inc.'s COSPEC IVB (correlation spectrometer) can sense from a considerable distance emissions from a volcanic eruption. Remote sensor is capable of measuring sulfur dioxide and nitrogen dioxide in the atmosphere. An associated product, GASPEC, a compression of Non-dispersive Gas Filter Spectrometer, is an infrared/ultraviolet gas analyzer which can be used as either a ground based detector or in aircraft/spacecraft applications. Extremely sensitive, it is useful in air pollution investigations for detecting a variety of trace elements, vapors, which exist in the atmosphere in small amounts.

Enantioseparation of novel chiral sulfoxides on chlorinated polysaccharide stationary phases in supercritical fluid chromatography.

PubMed

West, Caroline; Konjaria, Mari-Luiza; Shashviashvili, Natia; Lemasson, Elise; Bonnet, Pascal; Kakava, Rusudan; Volonterio, Alessandro; Chankvetadze, Bezhan

2017-05-26

Asymmetric sulfoxides is a particular case of chirality that may be found in natural as well as synthetic products. Twenty-four original molecules containing a sulfur atom as a centre of chirality were analyzed in supercritical fluid chromatography on seven polysaccharide-based chiral stationary phases (CSP) with carbon dioxide - methanol mobile phases. While all the tested CSP provided enantioseparation for a large part of the racemates, chlorinated cellulosic phases proved to be both highly retentive and highly enantioselective towards these species. Favourable structural features were determined by careful comparison of the enantioseparation of the probe molecules. Molecular modelling studies indicate that U-shaped (folded) conformations were most favorable to achieve high enantioresolution on these CSP, while linear (extended) conformations were not so clearly discriminated. For a subset of these species adopting different conformations, a broad range of mobile phase compositions, ranging from 20 to 100% methanol in carbon dioxide, were investigated. While retention decreased continuously in this range, enantioseparation varied in a non-monotonous fashion. Abrupt changes in the tendency curves of retention and selectivity were observed when methanol proportion reaches about 60%, suggesting that a change in the conformation of the analytes and/or chiral selector is occurring at this point. Copyright © 2017 Elsevier B.V. All rights reserved.

QSAR models for removal rates of organic pollutants adsorbed by in situ formed manganese dioxide under acid condition.

PubMed

Su, Pingru; Zhu, Huicen; Shen, Zhemin

2016-02-01

Manganese dioxide formed in oxidation process by potassium permanganate exhibits promising adsorptive capacity which can be utilized to remove organic pollutants in wastewater. However, the structure variances of organic molecules lead to wide difference of adsorption efficiency. Therefore, it is of great significance to find a general relationship between removal rate of organic compounds and their quantum parameters. This study focused on building up quantitative structure activity relationship (QSAR) models based on experimental removal rate (r(exp)) of 25 organic compounds and 17 quantum parameters of each organic compounds computed by Gaussian 09 and Material Studio 6.1. The recommended model is rpre = -0.502-7.742 f(+)x + 0.107 E HOMO + 0.959 q(H(+)) + 1.388 BOx. Both internal and external validations of the recommended model are satisfied, suggesting optimum stability and predictive ability. The definition of applicability domain and the Y-randomization test indicate all the prediction is reliable and no possibility of chance correlation. The recommended model contains four variables, which are closely related to adsorption mechanism. f(+)x reveals the degree of affinity for nucleophilic attack. E HOMO represents the difficulty of electron loss. q(H(+)) reflect the distribution of partial charge between carbon and hydrogen atom. BO x shows the stability of a molecule.

Sulfur dioxide alleviates programmed cell death in barley aleurone by acting as an antioxidant

PubMed Central

Yang, Feng; Huang, Zhong-Qin; Tang, Jun; Hu, Kang-Di

2017-01-01

Sulfur dioxide (SO2), a gaseous signaling molecule in animal cells, has recently been found to play a physiological role in plants. Here we studied the role of SO2 in gibberellic acid (GA3)-induced programmed cell death (PCD) in barley (Hordeum vulgare L.) aleurone layers. The application of the SO2 donor (NaHSO3/Na2SO3, 1:3 M/M) effectively alleviated PCD in barley aleurone layers in a dose-dependent manner with an optimal concentration of 50 μM. Further investigations showed that SO2 reduced the accumulation of hydrogen peroxide (H2O2), superoxide anion (⋅O2−) and malondialdehyde (MDA) in aleurone layers. Moreover, the activities of antioxidant enzymes such as superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APX), glutathione reductase (GR) and guaiacol peroxidase (POD) were enhanced by SO2 donor treatment. Meanwhile, lipoxygenase (LOX) activity was attenuated by SO2 donor treatment. Furthermore, an induction of endogenous H2S and NO were also observed in SO2-treated aleurone layers, suggesting interactions of SO2 with other well-known signaling molecules. Taken together, we show that SO2 negatively regulated PCD by acting as an antioxidant to scavenge excessive reactive oxygen species (ROS) generated during PCD. PMID:29155872

Carbonic acid as a reserve of carbon dioxide on icy moons: The formation of carbon dioxide (CO{sub 2}) in a polar environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, Brant M.; Kaiser, Ralf I.; Strazzulla, Giovanni, E-mail: brantmj@hawaii.edu

Carbon dioxide (CO{sub 2}) has been detected on the surface of several icy moons of Jupiter and Saturn via observation of the ν{sub 3} band with the Near-Infrared Mapping Spectrometer on board the Galileo spacecraft and the Visible-Infrared Mapping Spectrometer on board the Cassini spacecraft. Interestingly, the CO{sub 2} band for several of these moons exhibits a blueshift along with a broader profile than that seen in laboratory studies and other astrophysical environments. As such, numerous attempts have been made in order to clarify this abnormal behavior; however, it currently lacks an acceptable physical or chemical explanation. We present amore » rather surprising result pertaining to the synthesis of carbon dioxide in a polar environment. Here, carbonic acid was synthesized in a water (H{sub 2}O)-carbon dioxide (CO{sub 2}) (1:5) ice mixture exposed to ionizing radiation in the form of 5 keV electrons. The irradiated ice mixture was then annealed, producing pure carbonic acid which was then subsequently irradiated, recycling water and carbon dioxide. However, the observed carbon dioxide ν{sub 3} band matches almost exactly with that observed on Callisto; subsequent temperature program desorption studies reveal that carbon dioxide synthesized under these conditions remains in solid form until 160 K, i.e., the sublimation temperature of water. Consequently, our results suggest that carbon dioxide on Callisto as well as other icy moons is indeed complexed with water rationalizing the shift in peak frequency, broad profile, and the solid state existence on these relatively warm moons.« less

Investigation of acetone, butanol and carbon dioxide as new breath biomarkers for convenient and noninvasive diagnosis of obstructive sleep apnea syndrome.

PubMed

Bayrakli, Ismail; Öztürk, Önder; Akman, Hatice

2016-12-01

The objective of the present study was to investigate whether analysis of carbon dioxide, acetone and/or butanol present in human breath can be used as a simple and noninvasive diagnosis method for obstructive sleep apnea syndrome (OSAS). For this purpose, overnight changes in the concentrations of these breath molecules were measured before and after sleep in 10 patients who underwent polysomnography and were diagnosed with OSAS, and were compared with the levels of these biomarkers determined after sleep in 10 healthy subjects. The concentrations of exhaled carbon dioxide were measured using external cavity laser-based off-axis cavity enhanced absorption spectroscopy, whereas the levels of exhaled acetone and butanol were determined using thermal desorption gas chromatography mass spectrometry. We observed no significant changes in the levels of exhaled acetone and carbon dioxide in OSAS patients after sleep compared with pre-sleep values and compared with those in healthy control subjects. However, for the first time, to our knowledge, analyses of expired air showed an increased concentration of butanol after sleep compared with that before sleep and compared with that in healthy subjects. These results suggest that butanol can be established as a potential biomarker to enable the convenient and noninvasive diagnosis of OSAS in the future. Copyright © 2016 John Wiley & Sons, Ltd.

Dynamics and Fragmentation of Hydrogen Bonded and van der Waal Clusters upon 26.5 eV Soft X-ray Laser Ionization

NASA Astrophysics Data System (ADS)

Dong, Feng; Heinbuch, Scott; Bernstein, Elliot; Rocca, Jorge

2006-05-01

A desk-top soft x-ray laser is applied to the study of water, methanol, ammonia, sulfur dioxide, carbon dioxide, mixed sulfur dioxide-water, and mixed carbon dioxide-water clusters through single photon ionization time of flight mass spectroscopy. Almost all of the energy above the vertical ionization energy is removed by the ejected electron. Protonated water, methanol, and ammonia clusters dominate the mass spectra for the first three systems. The temperatures of the neutral water and methanol clusters can be estimated. In the case of pure SO2 and CO2, the mass spectra are dominated by (SO2)n^+ and (CO2)n^+ cluster series. When a high or low concentration of SO2/CO2 is mixed with water, we observe (SO2/CO2)nH2O^+ or SO2/CO2(H2O)nH^+ in the mass spectra, respectively. The unimolecular dissociation rate constants for reactions involving loss of one neutral molecule are calculated for the protonated water, methanol, and ammonia clusters as well as for SO2 and CO2 clusters. We find that the 26.5 eV soft x-ray laser is a nearly ideal tool for the study of hydrogen bonded and van der Waals cluster systems and we are currently exploring its usefulness for other more strongly bound systems.

40 CFR 63.702 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... tape manufacturing are: y-oxide, doped iron oxides, chromium dioxide, barium ferrite, and metallic... uncombined water, that exists as liquid or solid particles such as dust, smoke, mist, or fumes at standard...

40 CFR 63.702 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... tape manufacturing are: y-oxide, doped iron oxides, chromium dioxide, barium ferrite, and metallic... uncombined water, that exists as liquid or solid particles such as dust, smoke, mist, or fumes at standard...

Is the wall of a cellulose fiber saturated with liquid whether or not permeable with CO2 dissolved molecules? Application to bubble nucleation in champagne wines.

PubMed

Liger-Belair, Gérard; Topgaard, Daniel; Voisin, Cédric; Jeandet, Philippe

2004-05-11

In this paper, the transversal diffusion coefficient D perpendicular of CO2 dissolved molecules through the wall of a hydrated cellulose fiber was approached, from the liquid bulk diffusion coefficient of CO2 dissolved molecules modified by an obstruction factor. The porous network between the cellulose microfibrils of the fiber wall was assumed being saturated with liquid. We retrieved information from previous NMR experiments on the self-diffusion of water in cellulose fibers to reach an order of magnitude for the transversal diffusion coefficient of CO2 molecules through the fiber wall. A value of about D perpendicular approximately 0.2D0 was proposed, D0 being the diffusion coefficient of CO2 molecules in the liquid bulk. Because most of bubble nucleation sites in a glass poured with carbonated beverage are cellulose fibers cast off from paper or cloth which floated from the surrounding air, or remaining from the wiping process, this result directly applies to the kinetics of carbon dioxide bubble formation from champagne and sparkling wines. If the cellulose fiber wall was impermeable with regard to CO2 dissolved molecules, it was suggested that the kinetics of bubbling would be about three times less than it is.

Biological conversion of carbon dioxide and hydrogen into liquid fuels and industrial chemicals.

PubMed

Hawkins, Aaron S; McTernan, Patrick M; Lian, Hong; Kelly, Robert M; Adams, Michael W W

2013-06-01

Non-photosynthetic routes for biological fixation of carbon dioxide into valuable industrial chemical precursors and fuels are moving from concept to reality. The development of 'electrofuel'-producing microorganisms leverages techniques in synthetic biology, genetic and metabolic engineering, as well as systems-level multi-omic analysis, directed evolution, and in silico modeling. Electrofuel processes are being developed for a range of microorganisms and energy sources (e.g. hydrogen, formate, electricity) to produce a variety of target molecules (e.g. alcohols, terpenes, alkenes). This review examines the current landscape of electrofuel projects with a focus on hydrogen-utilizing organisms covering the biochemistry of hydrogenases and carbonic anhydrases, kinetic and energetic analyses of the known carbon fixation pathways, and the state of genetic systems for current and prospective electrofuel-producing microorganisms. Copyright © 2013 Elsevier Ltd. All rights reserved.

Plasma Cleaning

NASA Technical Reports Server (NTRS)

Hintze, Paul E.

2016-01-01

NASA's Kennedy Space Center has developed two solvent-free precision cleaning techniques: plasma cleaning and supercritical carbon dioxide (SCCO2), that has equal performance, cost parity, and no environmental liability, as compared to existing solvent cleaning methods.

Investigation of drift gas selectivity in high resolution ion mobility spectrometry with mass spectrometry detection.

PubMed

Matz, Laura M; Hill, Herbert H; Beegle, Luther W; Kanik, Isik

2002-04-01

Recent studies in electrospray ionization (ESI)/ion mobility spectrometry (IMS) have focussed on employing different drift gases to alter separation efficiency for some molecules. This study investigates four structurally similar classes of molecules (cocaine and metabolites, amphetamines, benzodiazepines, and small peptides) to determine the effect of structure on relative mobility changes in four drift gases (helium, nitrogen, argon, carbon dioxide). Collision cross sections were plotted against drift gas polarizability and a linear relationship was found for the nineteen compounds evaluated in the study. Based on the reduced mobility database, all nineteen compounds could be separated in one of the four drift gases, however, the drift gas that provided optimal separation was specific for the two compounds.

Sensing, physiological effects and molecular response to elevated CO2 levels in eukaryotes

PubMed Central

Sharabi, Kfir; Lecuona, Emilia; Helenius, Iiro Taneli; Beitel, Greg J; Sznajder, Jacob Iasha; Gruenbaum, Yosef

2009-01-01

Carbon dioxide (CO2) is an important gaseous molecule that maintains biosphere homeostasis and is an important cellular signalling molecule in all organisms. The transport of CO2 through membranes has fundamental roles in most basic aspects of life in both plants and animals. There is a growing interest in understanding how CO2 is transported into cells, how it is sensed by neurons and other cell types and in understanding the physiological and molecular consequences of elevated CO2 levels (hypercapnia) at the cell and organism levels. Human pulmonary diseases and model organisms such as fungi, C. elegans, Drosophila and mice have been proven to be important in understanding of the mechanisms of CO2 sensing and response. PMID:19863692

Burning trees and bridges

NASA Technical Reports Server (NTRS)

Levine, Joel S.

1990-01-01

Most burning of biomass is the result of human activity, and on a global scale it is increasing. Tropospheric concentrations of CO2, CO, CH4, non-methane hydrocarbons, and ozone are all increasing with time; global biomass burning may make an important contribution to this increase and thus to potential global climate change. The nitrogen cycle also can have important climatic effects. Nitrous oxide put into the atmosphere by biomass burning is a greenhouse gas 250 times more powerful (molecule for molecule) than carbon dioxide. Nitric oxide, as well as being a photochemical precursor of ozone, a major pollutant in the troposphere, produces nitric acid, the fastest-growing component of acid rain. Hence, the new bridge in the nitrogen cycle is of more than mere technical interest.

Hyperthermal Carbon Dioxide Interactions with Self-Assembled Monolayer Surfaces

DTIC Science & Technology

2013-09-08

comparison of the scattering behavior from the liquid and semi-solid surfaces to allow new insight into the pivotal initial step in gas -surface reaction...scattering dynamics of atoms and molecules on liquid and SAM surfaces, in order to deepen the understanding of gas -surface interactions at liquid and... gas - liquid and gas -SAM interface have developed a basic picture of the gas -surface collision dynamics. The previous experiments showed a bimodal

Using Vibrations to Probe and Control Photoisomerization in Liquids

DTIC Science & Technology

2014-08-07

Aniline in Supercritical CO2 The influence that different solvent environments have on the reaction dynamics of molecules in solution is a long...vibrationally excited stilbene, of a biomimetic switch, an N- alkylated indanylidene pyrroline Schiff base (NAIP), and of a model com- pound for excited...supercritical carbon dioxide, scCO2. Monitor- ing the excited-state isomerization of salicylidene aniline has shown the role of viscosity on the course of

Real-Time Prediction of Tropical Cyclone Intensity Using COAMPS-TC

DTIC Science & Technology

2012-01-01

tropospheric (UT) cloud fields (i.e., cirrus clouds) long after the initial eruption cycle from gradual particle settling and re-entrainment back into the... troposphere . Volcanic sul- fur dioxide and hydrogen sulfide vapor molecules are photo-oxidized in the LS, forming gaseous sulphuric acid, which in...concentration over the eastern United States at 1815 UTC on the 17th shown in Fig. 5(a), derived from NASA Ozone Monitoring Instrument (OMI) measurements

Probability model for atmospheric sulfur dioxide concentrations in the area of Venice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buttazzoni, C.; Lavagnini, I.; Marani, A.

1986-09-01

This paper deals with a comparative screening of existing air quality models based on their ability to simulate the distribution of sulfur dioxide data in the Venetian area. Investigations have been carried out on sulfur dioxide dispersion in the atmosphere of the Venetian area. The studies have been mainly focused on transport models (Gaussian, plume and K-models) aiming at meaningful correlations of sources and receptors. Among the results, a noteworthy disagreement of simulated and experimental data, due to the lack of thorough knowledge of source field conditions and of local meteorology of the sea-land transition area, has been shown. Investigationsmore » with receptor oriented models (based, e.g., on time series analysis, Fourier analysis, or statistical distributions) have also been performed.« less

Analysis of plume emissions after papovavirus irradiation with the carbon dioxide laser

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bellina, J.H.; Stjernholm, R.L.; Kurpel, J.E.

1982-05-01

This study was undertaken to evaluate potential inhalation hazards to operating room personnel after irradiation of tumors with the carbon dioxide laser. Cellular debris was analyzed for viability using labeled nucleotides and labeled glucose. In this way the plume was investigated for the presence of material with oncogenic potential. Most surgeons who have ablated venereal warts or certain tumors with the carbon dioxide laser have worried about possible hazards of inhaling the vapor that is produced as a result of their work. We utilized three methods to determine whether viable particles exist in the laser plume. Fortunately, it is mostmore » comforting that the metabolic studies, DNA and RNA studies and cytologic studies seem to indicate that the plume is biologically inactive.« less

46 CFR 108.444 - Lockout valves.

Code of Federal Regulations, 2013 CFR

2013-10-01

... dioxide to discharge in the event of equipment failure during maintenance. (c) The lockout valve design or... extinguishing system, when the valve must be locked in the closed position. (f) Lockout valves added to existing...

Influence of vibrational relaxation on perturbations in a shock layer on a plate

NASA Astrophysics Data System (ADS)

Kirilovskiy, S. V.; Maslov, A. A.; Poplavskaya, T. V.; Tsyryul'nikov, I. S.

2015-05-01

The influence of excitation of molecular vibrational degrees of freedom on the mean flow and perturbation development in a hypersonic (M = 6-14) viscous shock layer is studied. The layer originates on a plate placed in a flow of air, carbon dioxide, or their mixture at high stagnation temperatures (2000-3000 K). The mean flow and pressure pulsation on the surface of the plate are measured in an IT-302M pulsed wind tunnel (Khristianovich Institute of Theoretical and Applied Mechanics, Siberian Branch, Russian Academy of Sciences). Numerical simulation is carried out in terms of a model of a thermally perfect gas using the ANSYS Fluent program package based on solving nonstationary two-dimensional Navier-Stokes equations. External flow perturbations are introduced into the computational domain in the form of plane monochromatic acoustic waves using UDF modules built in the computational code. It is shown that the excitation of vibrational degrees of freedom in carbon dioxide molecules considerably influences the position of the head wave and intensifies perturbations in contrast to air in which the fraction of vibrationally excited molecules is low at the same parameters of the oncoming low. The influence of the excitation of vibrational degrees of freedom is studied both for equilibrium gas and for a vibrationally nonequilibrium gas. Nonequilibrium vibrational degrees of freedom are simulated using a two-temperature model of relaxation flows in which the time variation of the vibrational energy is described by the Landau-Teller equation with regard to a finite time of energy exchange between vibrational and translational-rotational degrees of freedom of molecules. It is found that the vibrational nonequilibrium has a damping effect on perturbations.

Molecular properties of metal difluorides and their interactions with CO2 and H2O molecules: a DFT investigation.

PubMed

Arokiyanathan, Agnes Lincy; Lakshmipathi, Senthilkumar

2017-11-18

A computational study of metal difluorides (MF 2 ; M = Ca to Zn) and their interactions with carbon dioxide and water molecules was performed. The structural parameter values obtained and the results of AIM analysis and energy decomposition analysis indicated that the Ca-F bond is weaker and less ionic than the bonds in the transition metal difluorides. A deformation density plot revealed the stablizing influence of the Jahn-Teller effect in nonlinear MF 2 molecules (e.g., where M= Sc, Ti, Cr). An anaysis of the metal K-edge peaks of the difluorides showed that shifts in the edge energy were due to the combined effects of the ionicity, effective nuclear charge, and the spin state of the metal. The interactions of CO 2 with ScF 2 (Scc3 geometry) and TiF 2 (Tic2 geometry) caused CO 2 to shift from its usual linear geometry to a bent geometry (η 2 (C=O) binding mode), while it retained its linear geometry (η 1 (O) binding mode) when it interacted with the other metal difluorides. Energy decomposition analysis showed that, among the various geometries considered, the Scc3 and Tic2 geometries possessed the highest interaction energies and orbital interaction energies. Heavier transition metal difluorides showed stronger affinities for H 2 O, whereas the lighter transition metal (Sc and Ti) difluorides preferred CO 2 . Overall, the results of this study suggest that fluorides of lighter transition metals with partially filled d orbitals (e.g., Sc and Ti) could be used for CO 2 capture under moist conditions. Graphical abstract Interaction of metal difluorides with carbon dioxide and water.

A study of alternative methods for reclaiming oxygen from carbon dioxide and water by a solid-electrolyte process for spacecraft applications

NASA Technical Reports Server (NTRS)

1971-01-01

Two alternative technical approaches were studied for application of an electrochemical process using a solid oxide electrolyte (zirconia stabilized by yttria or scandia) to oxygen reclamation from carbon dioxide and water, for spacecraft life support systems. Among the topics considered are the advisability of proceeding to engineering prototype development and fabrication of a full scale model for the system concept, the optimum choice of method or approach to be carried into prototype development, and the technical problem areas which exist.

Environmental impacts of the satellite power system (SPS) on the middle atmosphere

NASA Technical Reports Server (NTRS)

1980-01-01

The heavy lift launch vehicles (HLLV) proposed for use in constructing satellite power systems (SPS) would deposit various contaminants in the middle atmosphere, contaminants that would conceivable have adverse effects on climate and upper air structure. These contaminants consist of the major constitutents of water vapor, hydrogen, carbon dioxide, and carbon monoxide, and the minor constituents of sulfur dioxide and nitric oxide in the rocket effluent, as well as nitric oxide formed during reentry. To assess the magnitudes of the effects, new models or modified existing models were constructed.

Thermo Scientific Sulfur Dioxide Analyzer Instrument Handbook

DOE Office of Scientific and Technical Information (OSTI.GOV)

Springston, S. R.

The Sulfur Dioxide Analyzer measures sulfur dioxide based on absorbance of UV light at one wavelength by SO2 molecules which then decay to a lower energy state by emitting UV light at a longer wavelength. Specifically, SO2 + hυ1 →SO2 *→SO2 + hυ2 The emitted light is proportional to the concentration of SO2 in the optical cell. External communication with the analyzer is available through an Ethernet port configured through the instrument network of the AOS systems. The Model 43i-TLE is part of the i-series of Thermo Scientific instruments. The i-series instruments are designed to interface with external computers throughmore » the proprietary Thermo Scientific iPort Software. However, this software is somewhat cumbersome and inflexible. BNL has written an interface program in National Instruments LabView that both controls the Model 43i-TLE Analyzer AND queries the unit for all measurement and housekeeping data. The LabView vi (the software program written by BNL) ingests all raw data from the instrument and outputs raw data files in a uniform data format similar to other instruments in the AOS and described more fully in Section 6.0 below.« less

On the solvation of hydronium by carbon dioxide: Structural and infrared spectroscopic study of (H3O+)(CO2)n

NASA Astrophysics Data System (ADS)

Yang, Jianpeng; Kong, Xiangtao; Jiang, Ling

2018-02-01

Hydronium (H3O+) is the smallest member of protonated water. In this work, we use quantum chemical calculations to explore the solvation of H3O+ by adding one CO2 molecule at a time. The effect of stepwise solvation on infrared spectroscopy, structure, and energetics has been systematically studied. It has been found that the first solvation shell of H3O+ is completed at n = 6. Besides the hydrogen-bond interaction, the CCO2-OCO2 intermolecular interaction is also responsible for the stabilization of the larger clusters. The transfer of the proton from H3O+ onto CO2 with the formation of the OCOH+ moiety is not observed in the early stage of solvation process. Calculated IR spectra suggest that vibrational frequencies of H-bonded Osbnd H stretching would afford a sensitive probe for exploring the early stage solvation of hydronium by carbon dioxide. IR spectra for the (H3O+)(CO2)n (n = 1-7) clusters could be measured by the infrared photodissociation spectroscopic technique and thus provide a vivid physical picture about how carbon dioxide solvates the hydronium.

Biogas reforming over multi walled carbon nanotubes with Co-Mo/MgO nanoparticles

NASA Astrophysics Data System (ADS)

Khavarian, Mehrnoush; Mohamed, Abdul Rahman

2017-12-01

The utilization of biogas for the production of valuable chemicals is among the very important processes in the energy research field. The most suitable process for biogas reforming is dry reforming of methane. An obvious drawback is the variable composition of biogas rather than the stoichiometrically equimolar quantities of methane and carbon dioxide. Moreover, activating the methane and carbon dioxide molecules in the reforming reaction provides many challenges in exploring new concepts and opportunities for development of unique catalysts. In the present work, the catalytic activity behavior of Co-Mo-MgO/multi-walled carbon nanotubes (MWCNTs) nanocomposite in dry reforming was investigated with different CO2/CH4 feed ratio to evaluate the performance of this catalyst for biogas reforming reaction. It was found that conversions of methane and carbon dioxide were greatly influenced by the feed gas ratio. The CH4 and CO2 conversions are 83 % and 87 % at the reaction temperature of 825 °C, GHSV of 175 L/h.gcat and CO2/CH4 feed ratio of unity. The minimum carbon deposition rate is observed at the CO2/CH4 feed ratio of 0.6 which is 0.080 gc/gcat-h.

Novel scheme to compute chemical potentials of chain molecules on a lattice

NASA Astrophysics Data System (ADS)

Mooij, G. C. A. M.; Frenkel, D.

We present a novel method that allows efficient computation of the total number of allowed conformations of a chain molecule in a dense phase. Using this method, it is possible to estimate the chemical potential of such a chain molecule. We have tested the present method in simulations of a two-dimensional monolayer of chain molecules on a lattice (Whittington-Chapman model) and compared it with existing schemes to compute the chemical potential. We find that the present approach is two to three orders of magnitude faster than the most efficient of the existing methods.

Enhancing CO2 electrolysis through synergistic control of non-stoichiometry and doping to tune cathode surface structures

PubMed Central

Ye, Lingting; Zhang, Minyi; Huang, Ping; Guo, Guocong; Hong, Maochun; Li, Chunsen; Irvine, John T. S.; Xie, Kui

2017-01-01

Sustainable future energy scenarios require significant efficiency improvements in both electricity generation and storage. High-temperature solid oxide cells, and in particular carbon dioxide electrolysers, afford chemical storage of available electricity that can both stabilize and extend the utilization of renewables. Here we present a double doping strategy to facilitate CO2 reduction at perovskite titanate cathode surfaces, promoting adsorption/activation by making use of redox active dopants such as Mn linked to oxygen vacancies and dopants such as Ni that afford metal nanoparticle exsolution. Combined experimental characterization and first-principle calculations reveal that the adsorbed and activated CO2 adopts an intermediate chemical state between a carbon dioxide molecule and a carbonate ion. The dual doping strategy provides optimal performance with no degradation being observed after 100 h of high-temperature operation and 10 redox cycles, suggesting a reliable cathode material for CO2 electrolysis. PMID:28300066

A synthetic pathway for the fixation of carbon dioxide in vitro.

PubMed

Schwander, Thomas; Schada von Borzyskowski, Lennart; Burgener, Simon; Cortina, Niña Socorro; Erb, Tobias J

2016-11-18

Carbon dioxide (CO 2 ) is an important carbon feedstock for a future green economy. This requires the development of efficient strategies for its conversion into multicarbon compounds. We describe a synthetic cycle for the continuous fixation of CO 2 in vitro. The crotonyl-coenzyme A (CoA)/ethylmalonyl-CoA/hydroxybutyryl-CoA (CETCH) cycle is a reaction network of 17 enzymes that converts CO 2 into organic molecules at a rate of 5 nanomoles of CO 2 per minute per milligram of protein. The CETCH cycle was drafted by metabolic retrosynthesis, established with enzymes originating from nine different organisms of all three domains of life, and optimized in several rounds by enzyme engineering and metabolic proofreading. The CETCH cycle adds a seventh, synthetic alternative to the six naturally evolved CO 2 fixation pathways, thereby opening the way for in vitro and in vivo applications. Copyright © 2016, American Association for the Advancement of Science.

Science and Technology Review May 2004

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henson, V E

2004-04-02

This month's issue has the following articles: (1) ''A Multidisciplinary Attack on Bioterrorism''--Commentary by Tomas Diaz de la Rubia. (2) ''Life at the Nanoscale''--Livermore researchers are exploring the molecules of life at the nanoscale to fight bioterrorism, improve human health, and understand how proteins function. (3) ''Screening Cargo Containers to Remove a Terrorist Threat''--A detection system for cargo containers will search for hidden nuclear materials that terrorists might try to ship to U.S. seaports. (4) ''Improved Algorithms Speed It Up for Codes''--Recent changes to the algorithms used in Monte Carlo calculations are reducing the time needed to run the high-fidelitymore » simulations being developed for the nation's supercomputers. (5) ''The Siren Call of the Seas: Sequestering Carbon Dioxide''--Scientists at Livermore evaluate possible methods for removing carbon dioxide from Earth's atmosphere and storing it in the planet's waters.« less

Self-repairable polyurethane networks by atmospheric carbon dioxide and water.

PubMed

Yang, Ying; Urban, Marek W

2014-11-03

Sugar moieties were incorporated into cross-linked polyurethane (PUR) networks in an effort to achieve self-repairing in the presence of atmospheric carbon dioxide (CO2) and water (H2O). When methyl-α-D-glucopyranoside (MGP) molecules are reacted with hexamethylene diisocyanate trimer (HDI) and polyethylene glycol (PEG) to form cross-linked MGP-polyurethane (PUR) networks, these materials are capable of self-repairing in air. This process requires atmospheric amounts of CO2 and H2O, thus resembling plant behavior of carbon fixation during the photosynthesis cycle. Molecular processes responsible for this unique self-repair process involve physical diffusion of cleaved network segments as well as the formation of carbonate and urethane linkages. Unlike plants, MGP-PUR networks require no photo-initiated reactions, and they are thus capable of repair in darkness under atmospheric conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a New X-Ray Polarization Detection Device

NASA Astrophysics Data System (ADS)

Thompson, Jahreem R.; Hill, Joanne E.; Jahoda, Keith; Black, Kevin; Querrard, Rodney

2018-01-01

The aim of this research is to confirm the functionality of a Gas Electron Multiplier made of stainless steel in a detection medium of carbon dioxide and nitromethane through a series of X-ray tests in a vacuum chamber. Utilizing the photoelectric effect with carbon dioxide and nitromethane, we can confirm polarization of X-rays emitted from the most extreme astronomical conditions. We chose to use CO2 because we can confirm that it works well with the stainless-steel detector based on previous tests and nitromethane because we suspect that the ionization electrons created by the photoelectron during the photoelectric effect will experience less diffusion if they are bonded to a large molecule such as nitromethane as they diffuse towards the drift plate. The development of these new X-ray polarimeters will help to further the study of gravitational fields near black holes, their effects on matter they encounter, and the magnetic fields of neutron stars.

Driving Forces Controlling Host-Guest Recognition in Supercritical Carbon Dioxide Solvent.

PubMed

Ingrosso, Francesca; Altarsha, Muhannad; Dumarçay, Florence; Kevern, Gwendal; Barth, Danielle; Marsura, Alain; Ruiz-López, Manuel F

2016-02-24

The formation of supramolecular host-guest complexes is a very useful and widely employed tool in chemistry. However, supramolecular chemistry in non-conventional solvents such as supercritical carbon dioxide (scCO2 ), one of the most promising sustainable solvents, is still in its infancy. In this work, we explored a successful route to the development of green processes in supercritical CO2 by combining a theoretical approach with experiments. We were able to synthesize and characterize an inclusion complex between a polar aromatic molecule (benzoic acid) and peracetylated-β-cyclodextrin, which is soluble in the supercritical medium. This finding opens the way to wide, environmental friendly, applications of scCO2 in many areas of chemistry, including supramolecular synthesis, reactivity and catalysis, micro and nano-particle formation, molecular recognition, as well as enhanced extraction processes with increased selectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoluminescence from Amino-Containing Polymer in the Presence of CO2: Carbamato Anion Formed as a Fluorophore

PubMed Central

Pan, Xiaoyong; Wang, Guan; Lay, Chee Leng; Tan, Beng Hong; He, Chaobin; Liu, Ye

2013-01-01

Organic photoluminescent materials are important to many applications especially for diagnosis and detection, and most of organic photoluminescent materials contain fluorophores with extended conjugated structures. Recently some of amino-containing polymers without fluorophores with extended conjugated structure are observed to be photoluminescent, and one possible cause of the photoluminescence is oxidation of the amines. Here we show that photoluminescence can be produced by exposing a typical amino-containing polymer, polyethylenimine, to carbon dioxide. We demonstrate that carbamato anion formed via the reaction between the amine and carbon dioxide is a fluorophore; and the loosely-bound protonated water molecule can increase UV absorption but reduce the photoluminescence emission. Also carbamato anion shows solvent- and excitation wavelength-dependent emission of photoluminescence. The photoluminescence profile of carbamoto anion was discussed. These results will facilitate the understanding of photoluminescence observed from amino-containing materials and the design of new fluorophores. PMID:24067377

Molecular Simulations of Carbon Dioxide and Water: Cation Solvation and Wettability

NASA Astrophysics Data System (ADS)

Criscenti, L. J.; Bracco, J.; Cygan, R. T.

2010-12-01

Proposed carbon dioxide sequestration scenarios in sedimentary basins require investigation into the interaction between supercritical carbon dioxide, brines, and the mineral phases found in the basin and overlying caprock. Classical molecular dynamics (MD) simulations can be used to investigate some of these interactions such as the partitioning of metal cations between aqueous solutions and supercritical carbon dioxide, and the relative wettability of basin and caprock minerals with different fluid phases including water, carbon dioxide, and oil. Initial research has lead to the development of a new flexible carbon dioxide force field that successfully reproduces the vibrational properties of carbon dioxide, and a methodology for extracting contact angle information from large-scale MD simulations. Molecular simulations were performed to compare the solvation of alkali and alkaline metal cations in water and liquid carbon dioxide at 300K, using a flexible simple point charge (SPC) model for water and the new carbon dioxide force field. Solvation energies for Na+, Cs+, Mg2+, and Ba2+ are larger in water than in carbon dioxide, suggesting that these cations will partition preferentially into water. In both solutions, the solvation energy for the cations decreases with ion size and increases with ion charge. However, changes in solvation energy with increasing ionic radii are smaller in carbon dioxide than in water. Therefore, the overall partitioning of cations into carbon dioxide is predicted to increase with ion size. Molecular dynamics simulations are also useful to examine the relative wettability of minerals with different fluid phases. Large-scale MD simulations involving between 100,000 and 200,000 atoms have been conducted to establish a dynamic equilibrium between a drop of liquid water, water vapor, and kaolinite surfaces. The water drops consisted of at least 1700 molecules. Simulations were performed for five nanoseconds. The contact angle calculated for the siloxane surface of kaolinite is approximately 110°, and compares well with calculated contact angles for silica reported in the literature. The contact angle determined for the gibbsite surface of kaolinite is approximately 13° and compares favorably to reported experimental results. As expected, the siloxane surface is calculated to be hydrophobic and the gibbsite surface hydrophilic. This technique should prove useful to investigate the relative wettability of different minerals with subsurface fluids including supercritical CO2. This material is based upon work partially supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

Embedding of polyaniline molecules on adhesive tape using successive ionic layer adsorption and reaction (SILAR) technique

NASA Astrophysics Data System (ADS)

Pamatmat, J. K.; Gillado, A. V.; Herrera, M. U.

2017-05-01

Polyaniline molecules are embedded on adhesive tape using successive ionic layer adsorption and reaction (SILAR) technique. The infrared spectrum shows the existence of molecular vibrational modes associated with the presence of polyaniline molecules on the sample. With the addition of polyaniline molecules, the conductivity of adhesive tape increases. Surface conductivity increases with number of dipping cycle until it reaches a certain value. Beyond this value, surface conductivity begins to decrease. The surface conductivity of the sample is associated with the connectivity of the embedded polyaniline molecules. The connectivity increases as the number of dipping cycle progresses. Meanwhile, the decrease in surface conductivity is attributed to the eroding of existing embedded structure at higher number of dipping cycle.

Flow Field Mapping of Carbon Dioxide Nozzle Expansion into Vacuum

DTIC Science & Technology

1985-07-01

probe bow shock are adequately defined by the Rankine-Hugoniot relations. For flows that meet these requirements, the pitot probe is a simple and...nozzle lip [i.e. radial location 2.0 in. (5 cm)] could be attributable to the interaction of the probe bow shock with the nozzle lip. The similarity in...microbalance, free-molecule heat-transfer probe , free- m !olecule pressure probe , and a rotary pitot probe were used in this evaluation. (Cant)

Purification, crystallization and preliminary X-ray diffraction studies on goat (Capra hircus) hemoglobin - a low oxygen affinity species.

PubMed

Moorthy, Ponnuraj Sathya; Neelagandan, Kamariah; Balasubramanian, Moovarkumudalvan; Ponnuswamy, Mondikalipudur Nanjappa Gounder

2009-01-01

Hemoglobin is a vital protein present in almost all higher species. It is a transport protein involved in carrying oxygen from lungs to tissues and carbon dioxide back to lungs by an intrinsically coordinated manner. Even though a good amount of work has been carried out in this direction there exists scarcity of structural insight on low oxygen affinity species. Attempts are being made to unravel the structural insight of this low oxygen affinity species. Goat blood plasma was collected, treated with EDTA to avoid blood clotting and purification was accomplished using DEAE-anion chromatographic column. The goat hemoglobin was crystallized using 50mM of phosphate buffer at pH 6.7 with 1M NaCl and PEG 3350 as precipitant by hanging drop vapor diffusion method. Crystals obtained are screened and suitable crystals are taken for data collection using mar345dtb as image plate detector system. Goat hemoglobin crystal diffracted up to 2.61 A resolution. Goat hemoglobin crystallizes in orthorhombic space group P212(1)2(1) as a whole biological molecule in the asymmetric unit with cell dimensions a=53.568A, b=67.365A, c=154.183A.

Prebiotic Synthesis of Methionine and Other Sulfur-Containing Organic Compounds on the Primitive Earth: A Contemporary Reassessment Based on an Unpublished 1958 Stanley Miller Experiment

NASA Technical Reports Server (NTRS)

Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, Jason P.; Glavin, Daniel P.; Lazcano, Antonio

2010-01-01

Original extracts from an unpublished 1958 experiment conducted by the late Stanley L. Miller were recently found and analyzed using modern state-of-the-art analytical methods. The extracts were produced by the action of an electric discharge on a mixture of methane (CH4), hydrogen sulfide (H2S), ammonia (NH3), and carbon dioxide (CO2). Racemic methionine was farmed in significant yields, together with other sulfur-bearing organic compounds. The formation of methionine and other compounds from a model prebiotic atmosphere that contained H2S suggests that this type of synthesis is robust under reducing conditions, which may have existed either in the global primitive atmosphere or in localized volcanic environments on the early Earth. The presence of a wide array of sulfur-containing organic compounds produced by the decomposition of methionine and cysteine indicates that in addition to abiotic synthetic processes, degradation of organic compounds on the primordial Earth could have been important in diversifying the inventory of molecules of biochemical significance not readily formed from other abiotic reactions, or derived from extraterrestrial delivery.

Surface modification of TiO{sub 2} nanoparticles with carotenoids. EPR study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konovalova, T.A.; Kispert, L.D.; Konovalov, V.V.

1999-06-03

Among the semiconductors, titanium dioxide is the most suitable for many environmental applications. EPR measurements demonstrate efficient charge separation on carotenoid-modified titanium dioxide nanoparticles (7 nm). Strong complexation of carotenoids containing terminal carboxy groups ({minus}CO{sub 2}H) with the TiO{sub 2} surface leads to electron transfer from the adsorbed carotenoid molecule to the surface trapping site. For these systems, EPR signals of the carotenoid radical cations Car{sup {sm_bullet}+} and the electrons trapped on the TiO{sub 2} are observed before irradiation (77 K). Their UV-visible spectra show an absorption band with a maximum near 650 nm that is characteristic of the trappedmore » electrons. Surface modification of the TiO{sub 2} by other carotenoids results in the formation of a complex with an optical absorption band near 545 nm. These systems form charge-separated pairs [Car{sup {sm_bullet}+}{hor_ellipsis}TiO{sub 2}(e{sup {minus}}{sub tr}){sub surf}. TiO{sub 2}(e{sup {minus}}{sub tr}){sub latt}] only upon 365--600 nm illumination at 77 K. Complexation of the TiO{sub 2} colloids with carotenoids enhances spatial charge separation, shifts the absorption threshold into the visible region, and thus greatly improves the reducing ability of the semiconductor. Photoreduction of acceptor molecules such as 2,5-dichloro-1,4-benzoquinone, nitrobenzene, and oxygen is demonstrated.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherwitzl, Boris; Lassnig, Roman; Truger, Magdalena

The evaporation of quinacridone from a stainless steel Knudsen cell leads to the partial decomposition of this molecule in the cell, due to its comparably high sublimation temperature. At least one additional type of molecules, namely indigo, could be detected in the effusion flux. Thermal desorption spectroscopy and atomic force microscopy have been used to study the co-deposition of these molecules on sputter-cleaned and carbon-covered silicon dioxide surfaces. Desorption of indigo appears at temperatures of about 400 K, while quinacridone desorbs at around 510 K. For quinacridone, a desorption energy of 2.1 eV and a frequency factor for desorption ofmore » 1 × 10{sup 19} s{sup −1} were calculated, which in this magnitude is typical for large organic molecules. A fraction of the adsorbed quinacridone molecules (∼5%) decomposes during heating, nearly independent of the adsorbed amount, resulting in a surface composed of small carbon islands. The sticking coefficients of indigo and quinacridone were found to be close to unity on a carbon covered SiO{sub 2} surface but significantly smaller on a sputter-cleaned substrate. The reason for the latter can be attributed to insufficient energy dissipation for unfavorably oriented impinging molecules. However, due to adsorption via a hot-precursor state, the sticking probability is increased on the surface covered with carbon islands, which act as accommodation centers.« less

Solvent-driven reductive activation of carbon dioxide by gold anions.

PubMed

Knurr, Benjamin J; Weber, J Mathias

2012-11-14

Catalytic activation and electrochemical reduction of CO(2) for the formation of chemically usable feedstock and fuel are central goals for establishing a carbon neutral fuel cycle. The role of solvent molecules in catalytic processes is little understood, although solvent-solute interactions can strongly influence activated intermediate species. We use vibrational spectroscopy of mass-selected Au(CO(2))(n)(-) cluster ions to probe the solvation of AuCO(2)(-) as a model for a reactive intermediate in the reductive activation of a CO(2) ligand by a single-atom catalyst. For the first few solvent molecules, solvation of the complex preferentially occurs at the CO(2) moiety, enhancing reductive activation through polarization of the excess charge onto the partially reduced ligand. At higher levels of solvation, direct interaction of additional solvent molecules with the Au atom diminishes reduction. The results show how the solvation environment can enhance or diminish the effects of a catalyst, offering design criteria for single-atom catalyst engineering.

Use of bovine catalase and manganese dioxide for elimination of hydrogen peroxide from partly oxidized aqueous solutions of aromatic molecules - Unexpected complications

NASA Astrophysics Data System (ADS)

Kovács, Krisztina; Sági, Gyuri; Takács, Erzsébet; Wojnárovits, László

2017-10-01

Being a toxic substance, hydrogen peroxide (H2O2) formed during application of advanced oxidation processes disturbs the biological assessment of the treated solutions. Therefore, its removal is necessary when the concentration exceeds the critical level relevant to the biological tests. In this study, H2O2 removal was tested using catalase enzyme or MnO2 as catalysts and the concentration changes were measured by the Cu(II)/phenanthroline method. MnO2 and Cu(II) were found to react not only with H2O2 but also with the partly oxidized intermediates formed in the hydroxyl radical induced degradation of aromatic antibiotic and pesticide compounds. Catalase proved to be a milder oxidant, it did not show significant effects on the composition of organic molecules. The Cu(II)/phenanthroline method gives the correct H2O2 concentration only in the absence of easily oxidizable compounds, e.g. certain phenol type molecules.

Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Akshita; Tymi?ska, Nina; Zhu, Guanghui

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H 2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, bothmore » of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.« less

Influence of Hydrogen Sulfide Exposure on the Transport and Structural Properties of the Metal–Organic Framework ZIF-8

DOE PAGES

Dutta, Akshita; Tymi?ska, Nina; Zhu, Guanghui; ...

2018-03-09

In this paper, the interaction between hydrogen sulfide and ZIF-8 was studied via structural characterizations and guest molecule diffusion measurements. It was found that hydrogen sulfide reacts with the ZIF-8 external particle surface to form a surface barrier that excludes the uptake of larger molecules (ethanol) and slows down the uptake of smaller molecules (carbon dioxide). Nonetheless, bulk transport properties were unaltered, as supported by pulsed field gradient nuclear magnetic resonance studies. Dispersion-corrected density functional theory calculations revealed that H 2S is consumed by reactions occurring at the ZIF external surface. These reactions result in water and defect formation, bothmore » of which were found to be exothermic and independent of both crystallographic facets ({001} and {110}) and surface termination. Finally, we concluded that these surface reactions lead to structural and chemical changes to the ZIF-8 external surface that generate surface barriers to molecular transport.« less

Determination of Spectroscopic Properties of Atmospheric Molecules from High Resolution Vacuum Ultraviolet Cross Section and Wavelength Measurements

NASA Technical Reports Server (NTRS)

Parkinson, W. H.; Yoshino, K.

1999-01-01

We have studied the spectroscopy and the cross sections of the simple molecules of atmospheric interest such as oxygen, nitric oxide, carbon dioxide, and water. We have made cross section measurements on an absolute base without the effects from the limited instrumental resolution. We have used the following different instruments- the grating spectrometer (6.65-m at CfA, 3-m at Photon Factory), VUV Fourier transform spectrometer at Imperial College, and then moved the same one to the Photon Factory. Selection of the instruments depend on the appearance of molecular bands, and their wavelength region. For example, the cross section measurements of Doppler limited bands can been done with the Fourier transform spectrometer at the very high resolution (0.025/ cm resolution). All of these spectroscopic measurements are needed for accurate calculations of the production of atomic oxygen penetration of solar radiation into the Earth's atmosphere, and photochemistry of minor molecules.

Near-Infrared Band Strengths of Molecules Diluted in N2 and H2O Ice Mixtures Relevant to Interstellar and Planetary Ices

NASA Technical Reports Server (NTRS)

Richey, Christina Rae; Gerakines, P.A.

2012-01-01

The relative abundances of ices in astrophysical environments rely on accurate laboratory measurements of physical parameters, such as band strengths (or absorption intensities), determined for the molecules of interest in relevant mixtures. In an extension of our previous study on pure-ice samples, here we focus on the near-infrared absorption features of molecules in mixtures with the dominant components of interstellar and planetary ices, H2O and N2. We present experimentally measured near-infrared spectral information (peak positions, widths, and band strengths) for both H2O- and N2-dominated mixtures of CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), and NH3 (ammonia). Band strengths were determined during sample deposition by correlating the growth of near-infrared features (10,000-4000 per centimeter, 1-2.5 micrometers) with better-known mid-infrared features (4000-400 per centimeter, 2.5-25 micrometers) at longer wavelengths.

A flexible metal–organic framework: Guest molecules controlled dynamic gas adsorption

DOE PAGES

Mahurin, Shannon Mark; Li, Man -Rong; Wang, Hailong; ...

2015-04-13

A flexible metal–organic framework (MOF) of [Zn 3(btca) 2(OH) 2]·(guest) n (H 2btca = 1,2,3-benzotriazole-5-carboxylic acid) that exhibits guest molecule-controlled dynamic gas adsorption is reported in which carbon dioxide molecules rather than N 2, He, and Ar induce a structural transition with a corresponding appearance of additional steps in the isotherms. Physical insights into the dynamic adsorption behaviors of flexible compound 1 were detected by gas adsorption at different temperatures and different pressures and confirmed by Fourier transform infrared spectroscopy and molecular simulations. Interestingly, by taking advantage of the flexible nature inherent to the framework, this MOF material enables highlymore » selective adsorption of CO 2/N 2, CO 2/Ar, and CO 2/He of 36.3, 32.6, and 35.9, respectively, at 298 K. Furthermore, this class of flexible MOFs has potential applications for controlled release, molecular sensing, noble gas separation, smart membranes, and nanotechnological devices.« less

CO2 Compressor Requirements for Integration of Space Station Carbon Dioxide Removal and Carbon Dioxide Reduction Assemblies

NASA Technical Reports Server (NTRS)

Jeng, Frank F.; Lewis, John F.; Graf, John; LaFuse, Sharon; Nicholson, Leonard S. (Technical Monitor)

1999-01-01

This paper describes the analysis on integration requirements, CO2 compressor in particular, for integration of Carbon Dioxide Removal Assembly (CDRA) and CO2 Reduction Assembly (CRA) as a part of the Node 3 project previously conducted at JSC/NASA. A system analysis on the volume and operation pressure range of the CO2 accumulator was conducted. The hardware and operational configurations of the CO2 compressor were developed. The performance and interface requirements of the compressor were specified. An existing Four-Bed Molecular Sieve CO2 removal computer model was modified into a CDRA model and used in analyzing the requirements of the CDRA CO2 compressor. This CDRA model was also used in analyzing CDRA operation parameters that dictate CO2 pump sizing. Strategy for the pump activation was also analyzed.

Characterization of limonin glucoside metabolites from human prostate cell culture medium using high-performance liquid chromatography/electrospray ionization mass spectrometry and tandem mass spectrometry.

PubMed

Tian, Qingguo; Kent, Kyle D; Bomser, Joshua A; Schwartz, Steven J

2004-01-01

The metabolism of limonin 17-beta-D-glucopyranoside (LG) by non-cancerous (RWPE-1) and cancerous (PC-3) human prostate epithelial cells was investigated using high-performance liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) with in-source fragmentation and tandem mass spectrometry (MS/MS). During positive ion LC/ESI-MS, LG formed an abundant sodiated species ([M+Na]+) while the protonated molecule was barely observable. [M+Na]+ further fragmented into the less abundant [LARL+H]+ and a predominantly protonated aglycone molecule (limonin) due to in-source fragmentation. The major metabolite, limonin A-ring lactone (LARL), formed an abundant protonated molecule that was fragmented into a protonated molecule of limonin by loss of one molecule of water. In MS/MS by collisionally activated dissociation (CAD), LG produced the sodiated aglycone, [aglycone+Na]+, while LARL fragmented into [M+H]+ of limonin and fragment ions resulted by further loss of water, carbon monoxide and carbon dioxide, indicating the presence of oxygenated-ring structures. The limits of detection of LG were 0.4 and 20 fmol in selected-ion monitoring (SIM) and selected-reaction monitoring (SRM) detection, respectively. Copyright 2004 John Wiley & Sons, Ltd.

Electric Utility Generating Units: Repealing the Clean Power Plan

EPA Pesticide Factsheets

The Clean Power Plan established emission guidelines for states to follow in limiting carbon dioxide (CO2) emissions from existing power plants. EPA is proposing to repeal the CPP and rescind the accompanying legal memorandum.

Pollution's Price--The Cost in Human Health

ERIC Educational Resources Information Center

Newill, Vaun A.

1973-01-01

Discusses the detrimental effects of air pollution, and especially sulfur dioxide, on human health. Any relaxation of existing national air pollution standards because of the energy crisis could be costly in terms of the nation's health. (JR)

EVALUATION OF CARBON DIOXIDE CAPTURE FROM EXISTING COAL FIRED PLANTS BY HYBRID SORPTION USING SOLID SORBENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benson, Steven; Palo, Daniel; Srinivasachar, Srivats

2014-12-01

Under contract DE-FE0007603, the University of North Dakota conducted the project Evaluation of Carbon Dioxide Capture from Existing Coal Fired Plants by Hybrid Sorption Using Solid Sorbents. As an important element of this effort, an Environmental Health and Safety (EH&S) Assessment was conducted by Barr Engineering Co. (Barr) in association with the University of North Dakota. The assessment addressed air and particulate emissions as well as solid and liquid waste streams. The magnitude of the emissions and waste streams was estimated for evaluation purposes. EH&S characteristics of materials used in the system are also described. This document contains data basedmore » on the mass balances from both the 40 kJ/mol CO2 and 80 kJ/mol CO2 desorption energy cases evaluated in the Final Technical and Economic Feasibility study also conducted by Barr Engineering.« less

Nuclear Energy and Synthetic Liquid Transportation Fuels

NASA Astrophysics Data System (ADS)

McDonald, Richard

2012-10-01

This talk will propose a plan to combine nuclear reactors with the Fischer-Tropsch (F-T) process to produce synthetic carbon-neutral liquid transportation fuels from sea water. These fuels can be formed from the hydrogen and carbon dioxide in sea water and will burn to water and carbon dioxide in a cycle powered by nuclear reactors. The F-T process was developed nearly 100 years ago as a method of synthesizing liquid fuels from coal. This process presently provides commercial liquid fuels in South Africa, Malaysia, and Qatar, mainly using natural gas as a feedstock. Nuclear energy can be used to separate water into hydrogen and oxygen as well as to extract carbon dioxide from sea water using ion exchange technology. The carbon dioxide and hydrogen react to form synthesis gas, the mixture needed at the beginning of the F-T process. Following further refining, the products, typically diesel and Jet-A, can use existing infrastructure and can power conventional engines with little or no modification. We can then use these carbon-neutral liquid fuels conveniently long into the future with few adverse environmental impacts.

Amine-pillared Nanosheet Adsorbents for CO2 Capture Applications

NASA Astrophysics Data System (ADS)

Jiang, Hui

Amine-functionalized solid adsorbents have gained attention within the last decade for their application in carbon dioxide capture, due to their many advantages such as low energy cost for regeneration, tunable structure, elimination of corrosion problems, and additional advantages. However, one of the challenges facing this technology is to accomplish both high CO 2 capture capacity along with high CO2 diffusion rates concurrently. Current amine-based solid sorbents such as porous materials similar to SBA-15 have large pores diffusion entering molecules; however, the pores become clogged upon amine inclusion. To meet this challenge, our group's solution involves the creation of a new type of material which we are calling-amino-pillared nanosheet (APN) adsorbents which are generated from layered nanosheet precursors. These materials are being proposed because of their unique lamellar structure which exhibits ability to be modified by organic or inorganic pillars through consecutive swelling and pillaring steps to form large mesoporous interlayer spaces. After the expansion of the layer space through swelling and pillaring, the large pore space can be functionalized with amine groups. This selective functionalization is possible by the choice of amine group introduced. Our choice, large amine molecules, do not access the micropore within each layer; however, either physically or chemically immobilized onto the surface of the mesoporous interlayer space between each layer. The final goal of the research is to investigate the ability to prepare APN adsorbents from a model nanoporous layered materials including nanosheets precursor material MCM-22(P) and nanoporous layered silicate material AMH-3. MCM-22(P) contains 2-dimensional porous channels, 6 membered rings (MB) openings perpendicular to the layers and 10 MB channels in the plane of the layers. However, the transport limiting openings (6 MB) to the layers is smaller than CO2 gas molecules. In contrast, AMH-3 has 3D microporous layers with 8 MB openings in the plane of the layers, as well as perpendicular to the layers, which are larger than CO2 molecules. Based on the structure differences between nanosheets precursor material MCM-22(P) and nanoporous layered silicate material AMH-3, the latter might be more suitable for CO 2 capturer application as an APN candidate material. However, none of the assumptions above have been approved experimentally. In this study, the influence of the amine loading on adsorption capacity and kinetics of adsorption for the mixed porosity material pillared MCM-22 (P) (also called MCM-36) is studied systematically, in order to determine a potential route to achieve a final material with both high amine loading and high adsorption capacity. We first synthesized MCM-22(P), followed by swelling and pillaring to create MCM-36. Polymeric amines such as polyethylenimine (PEI) are used as an organic component of the supported amine adsorbents, with varying polymer loadings within the adsorbents used. The kinetics and diffusion properties of carbon dioxide capture on a MCM-36 pillared material impregnated with amine containing Polyethylenimine polymers has been investigated. It was determined that the introduction of amine polymer cannot be used to improve the capture capacity of the support over that of the bare material, due to the fact that with the addition of a high loading of amine polymer the large pore diffusion channels become impossible for carbon dioxide molecules to diffuse through. This sets an upper limit to the capture capacity of polymer impregnated MCM-36 for carbon dioxide which does not surpass that for the initial bare material, and greatly reduces the utility of using this sort of amine-solid adsorbent for carbon capture plans in the future.

Degradation of lindane and hexachlorobenzene in supercritical carbon dioxide using palladium nanoparticles stabilized in microcellular high-density polyethylene.

PubMed

Wu, Bei-Zen; Chen, GuanYu; Yak, HwaKwang; Liao, Weisheng; Chiu, KongHwa; Peng, Shie-Ming

2016-06-01

Palladium nanoparticles stabilized in microcellular high-density polyethylene prepared through supercritical foaming, supercritical impregnation, and H2 reduction are used for the hydrodechlorination of lindane and hexachlorobenzene in supercritical carbon dioxide below 100 °C. Both lindane and hexachlorobenzene can be almost 100% transformed to cyclohexane in 1 h. Reaction intermediates, such as lower chlorinated products or benzene, are not observed or exist in trace amount indicating that most of them may undergo reactions without leaving the metal surface. Copyright © 2016 Elsevier Ltd. All rights reserved.

MULTIPOLLUTANT EMISSION CONTROL TECHNOLOGY OPTIONS FOR COAL-FIRED POWER PLANTS

EPA Science Inventory

The report presents and analyzes various existing and novel control technologies designed to achieve multipollutant [sulfur dioxide (SO2), nitrogen oxide (NOX), and mercury (Hg)] emission reductions. Summary descriptions are included of 23 multipollutant control technologies that...

Prediction technologies for assessment of climate change impacts

USDA-ARS?s Scientific Manuscript database

Temperatures, precipitation, and weather patterns are changing, in response to increasing carbon dioxide in the atmosphere. With these relatively rapid changes, existing soil erosion prediction technologies that rely upon climate stationarity are potentially becoming less reliable. This is especiall...

Solvation of Esters and Ketones in Supercritical CO2.

PubMed

Kajiya, Daisuke; Imanishi, Masayoshi; Saitow, Ken-ichi

2016-02-04

Vibrational Raman spectra for the C═O stretching modes of three esters with different functional groups (methyl, a single phenyl, and two phenyl groups) were measured in supercritical carbon dioxide (scCO2). The results were compared with Raman spectra for three ketones involving the same functional groups, measured at the same thermodynamic states in scCO2. The peak frequencies of the Raman spectra of these six solute molecules were analyzed by decomposition into the attractive and repulsive energy components, based on the perturbed hard-sphere theory. For all solute molecules, the attractive energy is greater than the repulsive energy. In particular, a significant difference in the attractive energies of the ester-CO2 and ketone-CO2 systems was observed when the methyl group is attached to the ester or ketone. This difference was significantly reduced in the solute systems with a single phenyl group and was completely absent in those with two phenyl groups. The optimized structures among the solutes and CO2 molecules based on quantum chemical calculations indicate that greater attractive energy is obtained for a system where the oxygen atom of the ester is solvated by CO2 molecules.

Reactive Shear Layer Mixing and Growth Rate Effects on Afterburning Properties for Axisymetric Rocket Engine Plumes

DTIC Science & Technology

2006-09-01

water, carbon monoxide and carbon dioxide . The ratio of specific heats is reduced as the number of atoms in the molecule increases and as the...The flow of the jet is faster than the surrounding air, and since gas turbine engines run fuel lean, the exhaust products have generally fully reacted...previous types by several characteristics. The core of the rocket exhaust flowfield is fuel rich, and unlike gas turbine engines, which burn fuel

Carbon Dioxide Management on the International Space Station

NASA Technical Reports Server (NTRS)

Burlingame, Katie

2016-01-01

The International Space Station (ISS) is a manned laboratory operating in orbit around the Earth that was built and is currently operated by several countries across the world. The ISS is a platform for novel scientific research as well as a testbed for technologies that will be required for the next step in space exploration. In order for astronauts to live on ISS for an extended period of time, it is vital that on board systems consistently provide a clean atmosphere. One contaminant that must be removed from the atmosphere is carbon dioxide (CO2). CO2 levels on ISS are higher than those on Earth and can cause crew members to experience symptoms such as headaches, lethargy and mental slowness. A variety of systems exist on ISS to remove carbon dioxide, including adsorbent technologies which can be reused and testbed technologies for future space vehicles.

Carbon Dioxide Observational Platform System (CO-OPS), feasibility study

NASA Technical Reports Server (NTRS)

Bouquet, D. L.; Hall, D. W.; Mcelveen, R. P.

1987-01-01

The Carbon Dioxide Observational Platform System (CO-OPS) is a near-space, geostationary, multi-user, unmanned microwave powered monitoring platform system. This systems engineering feasibility study addressed identified existing requirements such as: carbon dioxide observational data requirements, communications requirements, and eye-in-the-sky requirements of other groups like the Defense Department, the Forestry Service, and the Coast Guard. In addition, potential applications in: earth system science, space system sciences, and test and verification (satellite sensors and data management techniques) were considered. The eleven month effort is summarized. Past work and methods of gathering the required observational data were assessed and rough-order-of magnitude cost estimates have shown the CO-OPS system to be most cost effective (less than $30 million within a 10 year lifetime). It was also concluded that there are no technical, schedule, or obstacles that would prevent achieving the objectives of the total 5-year CO-OPS program.

Reducing the Carbon Footprint of Commercial Refrigeration Systems Using Life Cycle Climate Performance Analysis: From System Design to Refrigerant Options

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fricke, Brian A; Abdelaziz, Omar; Vineyard, Edward Allan

In this paper, Life Cycle Climate Performance (LCCP) analysis is used to estimate lifetime direct and indirect carbon dioxide equivalent gas emissions of various refrigerant options and commercial refrigeration system designs, including the multiplex DX system with various hydrofluorocarbon (HFC) refrigerants, the HFC/R744 cascade system incorporating a medium-temperature R744 secondary loop, and the transcritical R744 booster system. The results of the LCCP analysis are presented, including the direct and indirect carbon dioxide equivalent emissions for each refrigeration system and refrigerant option. Based on the results of the LCCP analysis, recommendations are given for the selection of low GWP replacement refrigerantsmore » for use in existing commercial refrigeration systems, as well as for the selection of commercial refrigeration system designs with low carbon dioxide equivalent emissions, suitable for new installations.« less

Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media

PubMed Central

Moret, Séverine; Dyson, Paul J.; Laurenczy, Gábor

2014-01-01

The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic acid using a homogeneous ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO), without any additives. In water, at 40 °C, 0.2 M formic acid can be obtained under 200 bar, however, in DMSO the same catalyst affords 1.9 M formic acid. In both solvents the catalysts can be reused multiple times without a decrease in activity. Worldwide demand for formic acid continues to grow, especially in the context of a renewable energy hydrogen carrier, and its production from CO2 without base, via the direct catalytic carbon dioxide hydrogenation, is considerably more sustainable than the existing routes. PMID:24886955

Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media.

PubMed

Moret, Séverine; Dyson, Paul J; Laurenczy, Gábor

2014-06-02

The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic acid using a homogeneous ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO), without any additives. In water, at 40 °C, 0.2 M formic acid can be obtained under 200 bar, however, in DMSO the same catalyst affords 1.9 M formic acid. In both solvents the catalysts can be reused multiple times without a decrease in activity. Worldwide demand for formic acid continues to grow, especially in the context of a renewable energy hydrogen carrier, and its production from CO2 without base, via the direct catalytic carbon dioxide hydrogenation, is considerably more sustainable than the existing routes.

Theoretical analysis of uranium-doped thorium dioxide: Introduction of a thoria force field with explicit polarization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shields, A. E.; Ruiz Hernandez, S. E.; Leeuw, N. H. de, E-mail: DeLeeuwN@Cardiff.ac.uk

2015-08-15

Thorium dioxide is used industrially in high temperature applications, but more insight is needed into the behavior of the material as part of a mixed-oxide (MOX) nuclear fuel, incorporating uranium. We have developed a new interatomic potential model including polarizability via a shell model, and commensurate with a prominent existing UO{sub 2} potential, to conduct configurational analyses and to investigate the thermophysical properties of uranium-doped ThO{sub 2}. Using the GULP and Site Occupancy Disorder (SOD) computational codes, we have analyzed the distribution of low concentrations of uranium in the bulk material, where we have not observed the formation of uraniummore » clusters or the dominance of a single preferred configuration. We have calculated thermophysical properties of pure thorium dioxide and Th{sub (1−x)}U{sub x}O{sub 2} which generated values in very good agreement with experimental data.« less

TiO2, SiO2 and ZrO2 Nanoparticles Synergistically Provoke Cellular Oxidative Damage in Freshwater Microalgae

PubMed Central

Liu, Yinghan; Ye, Nan; Fang, Hao; Wang, Degao

2018-01-01

Metal-based nanoparticles (NPs) are the most widely used engineered nanomaterials. The individual toxicities of metal-based NPs have been plentifully studied. However, the mixture toxicity of multiple NP systems (n ≥ 3) remains much less understood. Herein, the toxicity of titanium dioxide (TiO2) nanoparticles (NPs), silicon dioxide (SiO2) NPs and zirconium dioxide (ZrO2) NPs to unicellular freshwater algae Scenedesmus obliquus was investigated individually and in binary and ternary combination. Results show that the ternary combination systems of TiO2, SiO2 and ZrO2 NPs at a mixture concentration of 1 mg/L significantly enhanced mitochondrial membrane potential and intracellular reactive oxygen species level in the algae. Moreover, the ternary NP systems remarkably increased the activity of the antioxidant defense enzymes superoxide dismutase and catalase, together with an increase in lipid peroxidation products and small molecule metabolites. Furthermore, the observation of superficial structures of S. obliquus revealed obvious oxidative damage induced by the ternary mixtures. Taken together, the ternary NP systems exerted more severe oxidative stress in the algae than the individual and the binary NP systems. Thus, our findings highlight the importance of the assessment of the synergistic toxicity of multi-nanomaterial systems. PMID:29419775

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wackett, LP

The current biofuels landscape is chaotic. It is controlled by the rules imposed by economic forces and driven by the necessity of finding new sources of energy, particularly motor fuels. The need is bringing forth great creativity in uncovering new candidate fuel molecules that can be made via metabolic engineering. These next generation fuels include long-chain alcohols, terpenoid hydrocarbons, and diesel-length alkanes. Renewable fuels contain carbon derived from carbon dioxide. The carbon dioxide is derived directly by a photosynthetic fuel-producing organism(s) or via intermediary biomass polymers that were previously derived from carbon dioxide. To use the latter economically, biomass depolymerizationmore » processes must improve and this is a very active area of research. There are competitive approaches with some groups using enzyme based methods and others using chemical catalysts. With the former, feedstock and end-product toxicity loom as major problems. Advances chiefly rest on the ability to manipulate biological systems. Computational and modular construction approaches are key. For example, novel metabolic networks have been constructed to make long-chain alcohols and hydrocarbons that have superior fuel properties over ethanol. A particularly exciting approach is to implement a direct utilization of solar energy to make a usable fuel. A number of approaches use the components of current biological systems, but re-engineer them for more direct, efficient production of fuels.« less

UV-Vis, infrared, and mass spectroscopy of electron irradiated frozen oxygen and carbon dioxide mixtures with water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, Brant M.; Kaiser, Ralf I.; Strazzulla, Giovanni

2014-02-01

Ozone has been detected on the surface of Ganymede via observation of the Hartley band through the use of ultraviolet spectroscopy and is largely agreed upon to be formed by radiolytic processing via interaction of magnetospheric energetic ions and/or electrons with oxygen-bearing ices on Ganymede's surface. Interestingly, a clearly distinct band near 300 nm within the shoulder of the UV-Vis spectrum of Ganymede was also observed, but currently lacks an acceptable physical or chemical explanation. Consequently, the primary motivation behind this work was the collection of UV-Vis absorption spectroscopy of ozone formation by energetic electron bombardment of a variety ofmore » oxygen-bearing ices (oxygen, carbon dioxide, water) relevant to this moon as well as other solar system. Ozone was indeed synthesized in pure ices of molecular oxygen, carbon dioxide and a mixture of water and oxygen, in agreement with previous studies. The Hartley band of the ozone synthesized in these ice mixtures was observed in the UV-Vis spectra and compared with the spectrum of Ganymede. In addition, a solid state ozone absorption cross section of 6.0 ± 0.6 × 10{sup –17} cm{sup 2} molecule{sup –1} was obtained from the UV-Vis spectral data. Ozone was not produced in the irradiated carbon dioxide-water mixtures; however, a spectrally 'red' UV continuum is observed and appears to reproduce well what is observed in a large number of icy moons such as Europa.« less

Loosely-Bound Diatomic Molecules.

ERIC Educational Resources Information Center

Balfour, W. J.

1979-01-01

Discusses concept of covalent bonding as related to homonuclear diatomic molecules. Article draws attention to the existence of bound rare gas and alkaline earth diatomic molecules. Summarizes their molecular parameters and offers spectroscopic data. Strength and variation with distance of interatomic attractive forces is given. (Author/SA)

Influence of oxygen concentration on ethylene removal using dielectric barrier discharge

NASA Astrophysics Data System (ADS)

Takahashi, Katsuyuki; Motodate, Takuma; Takaki, Koichi; Koide, Shoji

2018-01-01

Ethylene gas is decomposed using a dielectric barrier discharge plasma reactor for long-period preservation of fruits and vegetables. The oxygen concentration in ambient gas is varied from 2 to 20% to simulate the fruit and vegetable transport container. The experimental results show that the efficiency of ethylene gas decomposition increases with decreasing oxygen concentration. The reactions of ethylene molecules with ozone are analyzed by Fourier transform infrared spectrometry. The analysis results show that the oxidization process by ozone is later than that by oxygen atoms. The amount of oxygen atoms that contribute to ethylene removal increases with decreasing oxygen concentration because the reaction between oxygen radicals and oxygen molecules is suppressed at low oxygen concentrations. Ozone is completely removed and the energy efficiency of C2H4 removal is increased using manganese dioxide as a catalyst.

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, Timothy J.; Even, Jr., William R.

2000-01-01

A novel method for preparing a hydrogenation composition comprising organic polymer molecules having carbon--carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces and particularly from atmospheres within enclosed spaces that contain air, water vapor, oxygen, carbon dioxide or ammonia. The organic polymers molecules containing carbon--carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble noble metal catalyst composition. High molecular weight polymers may be added to the organic polymer/catalyst mixture in order to improve their high temperature performance. The hydrogenation composition is prepared by dispersing the polymers in a suitable solvent, forming thereby a solution suspension, flash-freezing droplets of the solution in a liquid cryogen, freeze-drying the frozen droplets to remove frozen solvent incorporated in the droplets, and recovering the dried powder thus formed.

High Level ab initio Predictions of the Energetics of mCO2•(H2O)n (n = 1-3, m = 1-12) Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thanthiriwatte, Sahan; Duke, Jessica R.; Jackson, Virgil E.

Electronic structure calculations at the correlated molecular orbital theory and density functional theory levels have been used to generate a reliable set of clustering energies for up to three water molecules in carbon dioxide clusters up to n = 12. The structures and energetics are dominated by Lewis acid-base interactions with hydrogen bonding interactions playing a lesser energetic role. The actual binding energies are somewhat larger than might be expected. The correlated molecular orbital MP2 method and density functional theory with the ωB97X exchange-correlation functional provide good results for the energetics of the clusters but the B3LYP and ωB97X-D functionalsmore » do not. Seven CO2 molecules form the first solvent shell about a single H2O with four CO2 molecules interacting with the H2O via Lewis acid-base interactions, two CO2 interacting with the H2O by hydrogen bonds, and the seventh CO2 completing the shell. The Lewis acid-base and weak hydrogen bond interactions between the water molecules and the CO2 molecules are strong enough to disrupt the trimer ring configuration for as few as seven CO2 molecules. Calculated 13C NMR chemical shifts for mCO2•(H2O)n show little change with respect to the number of H2O or CO2 molecules in the cluster. The O-H stretching frequencies do exhibit shifts that can provide information about the interactions between water and CO2 molecules.« less

Portable Unit for Metabolic Analysis

NASA Technical Reports Server (NTRS)

Dietrich, Daniel L.; Pitch, Nancy D.; Lewis, Mark E.; Juergens, Jeffrey R.; Lichter, Michael J.; Stuk, Peter M.; Diedrick, Dale M.; Valentine, Russell W.; Pettegrew, Richard D.

2007-01-01

The Portable Unit for Metabolic Analysis (PUMA) is an instrument that measures several quantities indicative of human metabolic function. Specifically, this instrument makes time-resolved measurements of temperature, pressure, flow, and the partial pressures of oxygen and carbon dioxide in breath during both inhalation and exhalation. Portable instruments for measuring these quantities have been commercially available, but the response times of those instruments are too long to enable temporal resolution of phenomena on the time scales of human respiration cycles. In contrast, the response time of the PUMA is significantly shorter than characteristic times of human respiration phenomena, making it possible to analyze varying metabolic parameters, not only on sequential breath cycles but also at successive phases of inhalation and exhalation within the same breath cycle. In operation, the PUMA is positioned to sample breath near the subject s mouth. Commercial off-the-shelf sensors are used for three of the measurements: a miniature pressure transducer for pressure, a thermistor for temperature, and an ultrasonic sensor for flow. Sensors developed at Glenn Research Center are used for measuring the partial pressures of oxygen and carbon dioxide: The carbon dioxide sensor exploits the relatively strong absorption of infrared light by carbon dioxide. Light from an infrared source passes through the stream of inhaled or exhaled gas and is focused on an infrared- sensitive photodetector. The oxygen sensor exploits the effect of oxygen in quenching the fluorescence of ruthenium-doped organic molecules in a dye on the tip of an optical fiber. A blue laser diode is used to excite the fluorescence, and the optical fiber carries the fluorescent light to a photodiode, the temporal variation of the output of which bears a known relationship with the rate of quenching of fluorescence and, hence, with the partial pressure of oxygen. The outputs of the sensors are digitized, preprocessed by a small onboard computer, and then sent wirelessly to a desktop computer, where the collected data are analyzed and displayed. In addition to the raw data on temperature, pressure, flow, and mole fractions of oxygen and carbon dioxide, the display can include volumetric oxygen consumption, volumetric carbon dioxide production, respiratory equivalent ratio, and volumetric flow rate of exhaled gas.

Intermittent Control Systems

ERIC Educational Resources Information Center

Montgomery, Thomas L.; And Others

1975-01-01

The technique of intermittent control systems for air quality control as developed and used by the Tennessee Valley Authority is investigated. Although controversial, all Tennessee Valley Authority sulfur dioxide elimination programs are scheduled to be operational this year. Existing or anticipated intermittent control systems are identified. (BT)

Reactions of Copper and Silver Cations with Carbon Dioxide: An Infrared Photodissociation Spectroscopic and Theoretical Study.

PubMed

Zhao, Zhi; Kong, Xiangtao; Yang, Dong; Yuan, Qinqin; Xie, Hua; Fan, Hongjun; Zhao, Jijun; Jiang, Ling

2017-05-04

The reaction of copper and silver cations with carbon dioxide was studied by mass-selected infrared photodissociation spectroscopy. Quantum chemical calculations were performed on these products, which aided the experimental assignments of the infrared spectra and helped to elucidate the geometrical and electronic structures. The Cu + and Ag + cations bind to an oxygen atom of CO 2 in an end-on configuration via a charge-quadrupole electrostatic interaction in the [M(CO 2 ) n ] + complexes. The formation of oxide-carbonyl and carbonyl-carbonate structures is not favored for the interaction of CO 2 with Cu + and Ag + . For n = 3 and 4, the n + 0 structure is preferred. [Note on the nomenclature: Using i + j, i denotes the number of CO 2 molecules in the first coordination shell, and j denotes the number of CO 2 molecules in the second coordination shell.] The two nearly energy-identical n + 0 and (n - 1) + 1 structures coexist in n = 5 and 6. While the six-coordinated structure is favored for [Cu(CO 2 ) n=7,8 ] + , the n + 0 configuration is dominated in [Ag(CO 2 ) n=7,8 ] + . The reaction of CO 2 with the cationic metal atoms has been compared to that with the neutral and anionic metal atoms, which would have important implications for understanding the interaction of CO 2 with reduction catalysts and rationally designing catalysts for CO 2 reduction based on cost-effective transition metals.

Endocannabinoid 2-arachidonoylglycerol protects inflammatory insults from sulfur dioxide inhalation via cannabinoid receptors in the brain.

PubMed

Li, Ben; Chen, Minjun; Guo, Lin; Yun, Yang; Li, Guangke; Sang, Nan

2017-01-01

Sulfur dioxide (SO 2 ) pollution in the atmospheric environment causes brain inflammatory insult and inflammatory-related microvasculature dysfunction. However, there are currently no effective medications targeting the harmful outcomes from chemical inhalation. Endocannabinoids (eCBs) are involved in neuronal protection against inflammation-induced neuronal injury. The 2-arachidonoylglycerol (2-AG), the most abundant eCBs and a full agonist for cannabinoid receptors (CB1 and CB2), is also capable of suppressing proinflammatory stimuli and improving microvasculature dysfunction. Here, we indicated that endogenous 2-AG protected against neuroinflammation in response to SO 2 inhalation by inhibiting the activation of microglia and astrocytes and attenuating the overexpression of inflammatory cytokines, including tumor necrosis factor alpha (TNF-a), interleukin (IL)-1β, and inducible nitric oxide synthase (iNOS). In addition, endogenous 2-AG prevented cerebral vasculature dysfunction following SO 2 inhalation by inhibiting endothelin 1 (ET-1), vascular cell adhesion molecule-1 (VCAM-1) and intercellular adhesion molecule 1 (ICAM-1) expression, elevating endothelial nitric oxide synthase (eNOS) level, and restoring the imbalance between thromboxane A2 (TXA2) and prostaglandin I2 (PGI2). In addition, the action of endogenous 2-AG on the suppression of inflammatory insult and inflammatory-related microvasculature dysfunction appeared to be mainly mediated by CB1 and CB2 receptors. Our results provided a mechanistic basis for the development of new therapeutic approaches for protecting brain injuries from SO 2 inhalation. Copyright © 2016. Published by Elsevier B.V.

Carbon Exchange and Loss Processes on Mars

NASA Image and Video Library

2015-11-24

This graphic depicts paths by which carbon has been exchanged between Martian interior, surface rocks, polar caps, waters and atmosphere, and also depicts a mechanism by which carbon is lost from the atmosphere with a strong effect on isotope ratio. Carbon dioxide (CO2) to generate the Martian atmosphere originated in the planet's mantle and has been released directly through volcanoes or trapped in rocks crystallized from magmas and released later. Once in the atmosphere, the CO2 can exchange with the polar caps, passing from gas to ice and back to gas again. The CO2 can also dissolve into waters, which can then precipitate out solid carbonates, either in lakes at the surface or in shallow aquifers. Carbon dioxide gas in the atmosphere is continually lost to space at a rate controlled in part by the sun's activity. One loss mechanism is called ultraviolet photodissociation. It occurs when ultraviolet radiation (indicated on the graphic as "hv") encounters a CO2 molecule, breaking the bonds to first form carbon monoxide (CO) molecules and then carbon (C) atoms. The ratio of carbon isotopes remaining in the atmosphere is affected as these carbon atoms are lost to space, because the lighter carbon-12 (12C) isotope is more easily removed than the heavier carbon-13 (13C) isotope. This fractionation, the preferential loss of carbon-12 to space, leaves a fingerprint: enrichment of the heavy carbon-13 isotope, measured in the atmosphere of Mars today. http://photojournal.jpl.nasa.gov/catalog/PIA20163

Extracellular hemoglobin: the case of a friend turned foe

PubMed Central

Quaye, Isaac K.

2015-01-01

Hemoglobin (Hb) is a highly conserved molecule present in all life forms and functionally tied to the complexity of aerobic organisms on earth in utilizing oxygen from the atmosphere and delivering to cells and tissues. This primary function sustains the energy requirements of cells and maintains cellular homeostasis. Decades of intensive research has presented a paradigm shift that shows how the molecule also functions to facilitate smooth oxygen delivery through the cardiovascular system for cellular bioenergetic homeostasis and signaling for cell function and defense. These roles are particularly highlighted in the binding of Hb to gaseous molecules carbon dioxide (CO2), nitric oxide (NO) and carbon monoxide (CO), while also serving indirectly or directly as sources of these signaling molecules. The functional activities impacted by Hb outside of bioenergetics homeostasis, include fertilization, signaling functions, modulation of inflammatory responses for defense and cell viability. These activities are efficiently executed while Hb is sequestered safely within the confines of the red blood cell (rbc). Outside of rbc confines, Hb disaggregates and becomes a danger molecule to cell survival. In these perpectives, Hb function is broadly dichotomous, either a friend in its natural environment providing and facilitating the means for cell function or foe when dislocated from its habitat under stress or pathological condition disrupting cell function. The review presents insights into how this dichotomy in function manifests. PMID:25941490

International Space Station Carbon Dioxide Removal Assembly (ISS CDRA) Concepts and Advancements

NASA Technical Reports Server (NTRS)

ElSherif, Dina; Knox, James C.

2005-01-01

An important aspect of air revitalization for life support in spacecraft is the removal of carbon dioxide from cabin air. Several types of carbon dioxide removal systems are in use in spacecraft life support. These systems rely on various removal techniques that employ different architectures and media for scrubbing CO2, such as permeable membranes, liquid amine, adsorbents, and absorbents. Sorbent systems have been used since the first manned missions. The current state of key technology is the existing International Space Station (ISS) Carbon Dioxide Removal Assembly (CDRA), a system that selectively removes carbon dioxide from the cabin atmosphere. The CDRA system was launched aboard UF-2 in February 2001 and resides in the U.S. Destiny Laboratory module. During the past four years, the CDRA system has operated with varying degrees of success. There have been several approaches to troubleshooting the CDRA system aimed at developing work-around solutions that would minimize the impact on astronaut time required to implement interim solutions. The paper discusses some of the short-term fixes applied to promote hardware life and restore functionality, as well as long-term plans and solutions for improving operability and reliability. The CDRA is a critical piece of life support equipment in the air revitalization system of the ISS, and is demonstrated technology that may ultimately prove well-suited for use in lunar or Mars base, and Mars transit life support applications.

CDRA-4EU Testing in Support of ISS

NASA Technical Reports Server (NTRS)

Peters, Warren; Stanley, Christine; Knox, Jim

2016-01-01

NASA's Marshall Space Flight Center (MSFC) recently conducted tests on two desiccant beds of the four-bed molecular sieve carbon dioxide removal assembly (CDRA) returned from the International Space Station (ISS). MSFC had previously characterized the relationship between CDRA-4EU inlet conditions and the dewpoint at the desiccant bed exit and between the compressor and accumulator that make up the Carbon Dioxide Management Assembly (CDMA). MSFC installed the flight desiccant beds into the existing Exploration Test Chamber (E-chamber) using a suite of instrumentation not available on orbit to investigate the orbital performance of the desiccant beds. Test objectives, facility design and test results are presented.

Multi-physics transient simulation of monolithic niobium dioxide-tantalum dioxide memristor-selector structures

NASA Astrophysics Data System (ADS)

Sevic, John F.; Kobayashi, Nobuhiko P.

2017-10-01

Self-assembled niobium dioxide (NbO2) thin-film selectors self-aligned to tantalum dioxide (TaO2) memristive memory cells are studied by a multi-physics transient solution of the heat equation coupled to the nonlinear current continuity equation. While a compact model can resolve the quasi-static bulk negative differential resistance (NDR), a self-consistent coupled transport formulation provides a non-equilibrium picture of NbO2-TaO2 selector-memristor operation ab initio. By employing the drift-diffusion transport approximation, a finite element method is used to study the dynamic electrothermal behavior of our experimentally obtained selector-memristor devices, showing that existing conditions are suitable for electroformation of NbO2 selector thin-films. Both transient and steady-state simulations support our theory, suggesting that the phase change due to insulator-metal transition is responsible for NbO2 selector NDR in our as-fabricated selector-memristor devices. Simulation results further suggest that TiN nano-via may play a central role in electroforming, as its dimensions and material properties establish the mutual electrothermal interaction between TiN nano-via and the selector-memristor.

First-principles investigation on defect-induced silicene nanoribbons - A superior media for sensing NH3, NO2 and NO gas molecules

NASA Astrophysics Data System (ADS)

Walia, Gurleen Kaur; Randhawa, Deep Kamal Kaur

2018-04-01

In this paper, the electronic and transport properties of armchair silicene nanoribbons (ASiNRs) are analyzed for their application as highly selective and sensitive gas molecule sensors. The study is focused on sensing three nitrogen based gases; ammonia (NH3), nitrogen dioxide (NO2) and nitric oxide (NO), which depending upon their adsorption energy and charge transfer, form bonds of varying strength with ASiNRs. The negligible band gap of ASiNRs is tuned by adding a defect in ASiNRs. Adsorption of NH3 leads to the opening of band gap whereas on adsorption of NO2 and NO, ASiNRs exhibit metallic nature. Distinctly divergent electronic and transport properties of ASiNRs are observed and on adsorption of NH3, NO2 and NO, renders them suitable for sensing them. All gas molecules show stronger adsorption on defective ASiNRs (D-ASiNRs) as compared to pristine ASiNRs (P-ASiNRs). The work reveals that introduction of defect can drastically improve the sensitivity of ASiNRs.

Asymmetric Top Rotors in Superfluid Para-Hydrogen Nano-Clusters

NASA Astrophysics Data System (ADS)

Zeng, Tao; Li, Hui; Roy, Pierre-Nicholas

2012-06-01

We present the first simulation study of bosonic clusters doped with an asymmetric top molecule. A variation of the path-integral Monte Carlo method is developed to study a para-water (pH_2O) impurity in para-hydrogen (pH_2) clusters. The growth pattern of the doped clusters is similar in nature to that of the pure clusters. The pH_2O molecule appears to rotate freely in the cluster due to its large rotational constants and the lack of adiabatic following. The presence of pH_2O substantially quenches the superfluid response of pH_2 with respect to the space fixed frame. We also study the behaviour of a sulphur dioxide (32S16O_2) dopant in the pH_2 clusters. For such a heavy rotor, the adiabatic following of the pH_2 molecules is established and the superfluid renormalization of the rotational constants is observed. The rotational structure of the SO_2-p(H_2)_N clusters' ro-vibrational spectra is predicted. The connection between the superfluid response respect to the external boundary rotation and the dopant rotation is discussed.

The origin of intermediary metabolism

NASA Technical Reports Server (NTRS)

Morowitz, H. J.; Kostelnik, J. D.; Yang, J.; Cody, G. D.

2000-01-01

The core of intermediary metabolism in autotrophs is the citric acid cycle. In a certain group of chemoautotrophs, the reductive citric acid cycle is an engine of synthesis, taking in CO(2) and synthesizing the molecules of the cycle. We have examined the chemistry of a model system of C, H, and O that starts with carbon dioxide and reductants and uses redox couples as the energy source. To inquire into the reaction networks that might emerge, we start with the largest available database of organic molecules, Beilstein on-line, and prune by a set of physical and chemical constraints applicable to the model system. From the 3.5 million entries in Beilstein we emerge with 153 molecules that contain all 11 members of the reductive citric acid cycle. A small number of selection rules generates a very constrained subset, suggesting that this is the type of reaction model that will prove useful in the study of biogenesis. The model indicates that the metabolism shown in the universal chart of pathways may be central to the origin of life, is emergent from organic chemistry, and may be unique.

Study of oxygen/tetraethoxysilane plasmas in a helicon reactor using optical emission spectroscopy and mass spectrometry

NASA Astrophysics Data System (ADS)

Aumaille, K.; Granier, A.; Schmidt, M.; Grolleau, B.; Vallée, C.; Turban, G.

2000-08-01

Oxygen/tetraethoxysilane (O2/TEOS) plasmas created in a low-pressure (2 mTorr) rf helicon reactor have been studied by optical emission spectroscopy and mass spectrometry as a function of the rf (13.56 MHz) power injected into the plasma, which is varied from 25 to 300 W. Complementary measurements for the interpretation of the mass spectrometric data have also been carried out using the threshold ionization mass spectrometry technique. It is shown that valuable information on the parent molecules is obtained by both optical emission spectroscopy and threshold ionization mass spectrometry techniques. At low rf power TEOS molecules and organic compounds like hydrocarbons (CH4, C2H2) and alcohols (CH3CH2OH) as well as H2, H2O, CO, O2, CO2 are observed. At high rf power TEOS and O2 molecules are totally or mostly depleted, the share of hydrocarbons decreases and carbon monoxide, carbon dioxide, water and hydrogen become the essential parts of the gas phase.

Structure of solvates of o-hydroxybenzoic acid in supercritical CO2-cosolvent media, according to molecular dynamics data

NASA Astrophysics Data System (ADS)

Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.

2015-03-01

Three-component supercritical carbon dioxide-cosolvent (methanol, ethanol, water)- o-hydroxybenzoic acid ( o-HBA) mixtures at a density of 0.7 g/cm3 and temperatures of 318 and 348 K are simulated by means of molecular dynamics. The solvate structures are investigated. It is shown that the solvation mechanism of o-HBA (particularly the o-HBA molecule forming a stable solvate complex with one molecule of a cosolvent via a hydrogen bond through the carboxyl group) does not depend on the temperature or the cosolvent. It is noted that the form of the cosolvent in a supercritical fluid varies: alcohols are distributed in the bulk in the form of monomers and hydrogen-bonded dimers, and water molecules tend to form microclusters along with chained and spatially branched structures by means of hydrogen bonds. It is established that the local molar fraction of cosolvent around the solvate complexes grows. It is concluded that the solvation of o-HBA is determined by the behavior of cosolvent in media of supercritical CO2.

Spectroscopic investigation of a dielectric barrier discharge in modified atmosphere packaging

NASA Astrophysics Data System (ADS)

Milosavljević, Vladimir; Cullen, Patrick J.

2017-11-01

Diagnostics of a dielectric barrier discharge (DBD), in a sealed package (with and without meat) filled with gas mixtures of oxygen and carbon-dioxide (O2-CO2), is reported. The generation and evaluation of the plasma chemistry induced within the confines of the sealed package is studied. The plasma discharges were analyzed by optical emission spectroscopy (OES) and optical absorption spectroscopy (OAS) over a range of plasma process parameters. The study includes a detailed experimental investigation of the spatial and temporal spectroscopic data and links them with plasma kinetics. The results from the spectral radiation from package provide information about the electron energy distribution function. The experimental data indicates that the humidity level in the package with and without meat is unchanged, and that the gas temperature was not significantly modified. Oxygen and nitrogen radicals (trapped gas atmosphere and modified atmosphere) are increased in the package containing meat; at the same time there is no evidence of the presence of carbon monoxide molecules. The role of the nitrogen molecule in the quenching of O2 and CO2 molecules is also evaluated.

Computational Recreation of Carbon Dioxide Hydrates at Habitable Planetary Conditions

NASA Astrophysics Data System (ADS)

Recio, J. M.; Izquierdo-Ruiz, F.; Prieto-Ballesteros, O.

2017-12-01

Gas clathrate hydrates are proposed as constituents of the icy moons of the giant planets in the Solar System [1]. Carbon dioxide has been detected on the surface of the moons of Jupiter, supposedly originated by internal degasification. In Ganymede, an aqueous ocean is proposed to exist under a thick ice crust in coexistence with several forms of ice, with pressure reaching up to 1.3 GPa [2]. Due to the limited available data on these systems under these conditions, we propose a combination of computational and experimental studies to describe microscopically and macroscopically the structural and chemical behavior of CO2@H2O polymorphs. This will allow us to understand how their presence affects the geophysical structure and activity and their impact on the habitability of the icy moon. A transition from the sI cubic structure to a high pressure phase at around 0.7 GPa has been found for CO2@H2O. In spite of different attempts to characterize the new structure, a definite answer has not been provided yet. A MH-III Filled Ice Structure type was proposed after neutron diffraction experiments in contrast with an alternative structure similar to the hexagonal C0 type for H2 hydrates [3]. It has an estimated hydration level ratio up to 2H2O:1CO2 and 6 water molecules per unit cell. In the figure below, our optimized unit cell based on this hexagonal C0 structure is displayed. Ab initio calculations using the XDM approximation to include van der Waals effects are performed in our search for the pressure evolution of the equilibrium geometries of the C0-CO2@H2O phase and those of a close related structure to this one called Ih-C0, with 8 water molecules per unit cell. We obtain occupation energies at different hydration ratios, densities, equations of state parameters, and stability energies with respect to decomposition. Raman and IR frequencies are also computed in the 0-2 GPa range. High pressure experiments are also being done in a newly designed chamber able to reach 1 GPa. It is equipped with a sapphire window to allow the measurements of Raman spectra. We believe that these results may throw light into gas hydrates of the habitable bodies of our Solar System. [1] Buffet B. A., Ann. Rev. Earth Plan. Sci. 28, 477, 2010. [2] Bland, M.T. et al. Icarus 200, 207, 2009. [3] Smirnov G. S. et al., J. Phys. Chem. Lett., 2013, 4, 3560

Exploration of sensing of nitrogen dioxide and ozone molecules using novel TiO2/Stanene heterostructures employing DFT calculations

NASA Astrophysics Data System (ADS)

Abbasi, Amirali; Sardroodi, Jaber Jahanbin

2018-06-01

Based on the density functional theory (DFT) calculations, we explored the sensing capabilities and electronic structures of TiO2/Stanene heterostructures as novel and highly efficient materials for detection of toxic NO2 and O3 molecules in the environment. Studied gas molecules were positioned at different sites and orientations towards the nanocomposite, and the adsorption process was examined based on the most stable structures. We found that both of these molecules are chemically adsorbed on the TiO2/Stanene heterostructures. The calculations of the adsorption energy indicate that the fivefold coordinated titanium sites of the TiO2/Stanene are the most stable sites for the adsorption of NO2 and O3 molecules. The side oxygen atoms of the gas molecules were found to be chemically bonded to these titanium atoms. The adsorption of gas molecules is an exothermic process, and the adsorption on the pristine nanocomposite is more favorable in energy than that on the nitrogen-doped nanocomposite. The effects of van der Waals interactions were taken into account, which indicate the adsorption energies were increased for the most sable configurations. The gas sensing response and charge transfers were analyzed in detail. The pristine nanocomposites have better sensing response than the doped ones. The spin density distribution plots indicate that the magnetization was mainly located over the adsorbed gas molecules. Mulliken charge analysis reveals that both NO2 and O3 molecules behave as charge acceptors, as evidenced by the accumulation of electronic charges on the adsorbed molecules predicted by charge density difference calculations. Our DFT results provide a theoretical basis for an innovative gas sensor system designed from a sensitive TiO2/Stanene heterostructures for efficient detection of harmful air pollutants such as NO2 and O3.

Sequestration and utilization of carbon dioxide by chemical and biological methods for biofuels and biomaterials by chemoautotrophs: Opportunities and challenges.

PubMed

Thakur, Indu Shekhar; Kumar, Manish; Varjani, Sunita J; Wu, Yonghong; Gnansounou, Edgard; Ravindran, Sindhu

2018-05-01

To meet the CO 2 emission reduction targets, carbon dioxide capture and utilization (CCU) comes as an evolve technology. CCU concept is turning into a feedstock and technologies have been developed for transformation of CO 2 into useful organic products. At industrial scale, utilization of CO 2 as raw material is not much significant as compare to its abundance. Mechanisms in nature have evolved for carbon concentration, fixation and utilization. Assimilation and subsequent conversion of CO 2 into complex molecules are performed by the photosynthetic and chemolithotrophic organisms. In the last three decades, substantial research is carry out to discover chemical and biological conversion of CO 2 in various synthetic and biological materials, such as carboxylic acids, esters, lactones, polymer biodiesel, bio-plastics, bio-alcohols, exopolysaccharides. This review presents an over view of catalytic transformation of CO 2 into biofuels and biomaterials by chemical and biological methods. Copyright © 2018 Elsevier Ltd. All rights reserved.

First analysis of the rotationally-resolved ν 2 and 2ν 2-ν 2 bands of sulfur dioxide, 33S 16O 2

DOE PAGES

Blake, T. A.; Flaud, J. -M.; Lafferty, W. J.

2017-01-03

A Fourier transform spectrum of sulfur dioxide 33S 16O 2 has been recorded in the 18.3 μm spectral region at a resolution of 0.002 cm $-$1 using a Bruker IFS 125HR spectrometer leading to the observation of the ν 2 and 2ν 2-ν 2 vibrational bands of the 33S 16O 2 molecule. The corresponding upper state ro-vibrational levels were fit using Watson-type Hamiltonians. In this way it was possible to reproduce the upper state ro-vibrational levels to within the experimental uncertainty; i.e., ~ 0.20 × 10 $-$3 cm $-$1. Finally, very accurate rotational and centrifugal distortion constants were derived frommore » the fit together with the following band centers: ν 0 (ν 2) = 515.659089(50) cm $-$1, ν 0 (2ν 2) = 1030.697723(20) cm $-$1.« less

Thinning and opening of carbon nanotubes by oxidation using carbon dioxide

NASA Astrophysics Data System (ADS)

Tsang, S. C.; Harris, P. J. F.; Green, M. L. H.

1993-04-01

THE discovery1 and bulk synthesis2 of carbon nanotubes has stimulated great interest. It has been suggested that these structures may have useful electronic3-5 and mechanical6 properties, and these might be modified by introducing foreign materials into the nanotubes. But the tubes are invariably capped at the ends. Ajayan and lijima7 have succeeded in drawing molten material (lead or one of its compounds) into the tubes by heating them in the presence of lead and oxygen; less than 1% of the tubes in the sample studied could be filled in this way. Here we report that heating in carbon dioxide gas can result in the partial or complete destruction of the tube caps and stripping of the outer layers to produce thinner tubes. In some cases, we have thinned the extremity of tubes to a single layer. The opened tubes can be regarded as nanoscale test-tubes for adsorption of other molecules, and this controlled method of thinning may allow studies of the properties of single tubes.

Carbon dioxide hydrogenation on Ni(110).

PubMed

Vesselli, Erik; De Rogatis, Loredana; Ding, Xunlei; Baraldi, Alessandro; Savio, Letizia; Vattuone, Luca; Rocca, Mario; Fornasiero, Paolo; Peressi, Maria; Baldereschi, Alfonso; Rosei, Renzo; Comelli, Giovanni

2008-08-27

We demonstrate that the key step for the reaction of CO 2 with hydrogen on Ni(110) is a change of the activated molecule coordination to the metal surface. At 90 K, CO 2 is negatively charged and chemically bonded via the carbon atom. When the temperature is increased and H approaches, the H-CO 2 complex flips and binds to the surface through the two oxygen atoms, while H binds to the carbon atom, thus yielding formate. We provide the atomic-level description of this process by means of conventional ultrahigh vacuum surface science techniques combined with density functional theory calculations and corroborated by high pressure reactivity tests. Knowledge about the details of the mechanisms involved in this reaction can yield a deeper comprehension of heterogeneous catalytic organic synthesis processes involving carbon dioxide as a reactant. We show why on Ni the CO 2 hydrogenation barrier is remarkably smaller than that on the common Cu metal-based catalyst. Our results provide a possible interpretation of the observed high catalytic activity of NiCu alloys.

CO2 sensing properties of electro-spun Ca-doped ZnO fibres.

PubMed

Pantò, Fabiola; Leonardi, Salvatore Gianluca; Fazio, Enza; Frontera, Patrizia; Bonavita, Anna; Neri, Giovanni; Antonucci, Pierluigi; Neri, Fortunato; Santangelo, Saveria

2018-07-27

The availability of low-cost, high-performing sensors for carbon dioxide detection in the environment may play a crucial role for reducing CO 2 emissions and limiting global warming. In this study, calcium-doped zinc oxide nanofibres with different Ca to Zn loading ratios (1:40 or 1:20) are synthesised via electro-spinning, thoroughly characterised and, for the first time, tested as an active material for the detection of carbon dioxide. The results of their characterisation show that the highly porous fibres consist of interconnected grains of oxide with the hexagonal wurtzite structure of zincite. Depending on the Ca:Zn loading ratio, calcium fully or partly segregates to form calcite on the fibre surface. The high response of the sensor based on the fibres with the highest Ca-doping level can be attributed to the synergy between the fibre morphology and the basicity of Ca-ion sites, which favour the diffusion of the gas molecules within the sensing layer and the CO 2 adsorption, respectively.

Investigation of atmospheric pressure capillary non-thermal plasmas and their applications to the degradation of volatile organic compounds

NASA Astrophysics Data System (ADS)

Yin, Shu-Min

Atmospheric pressure capillary non-thermal plasma (AP-CNTP) has been investigated as a potential technology far the removal of volatile organic compounds (VOCs) in Advanced Life Support Systems (ALS). AP-CNTP is a destructive technology far the removal of VOCs from air streams by active plasma species, such as electrons, ions, and excited molecules. Complete VOC destruction ideally results in the formation of water, carbon dioxide (CO2), and other by-product's may also form, including ozone (O3), nitrous oxide (N2O), nitrogen dioxide (NO2), and decomposed hydrocarbons. Several organic compounds, such as BTEX, ethylene, n-heptane, isooctane, methanol and NH3, were tested in an AP-CNTP system. Parametric experiments were carried out by varying plasma discharge power, flowrates, and initial concentrations. The degradation efficiency varied depending on the chemical nature of the compounds. A plasmochemical kinetic model was derived for toluene, ethylbenzene, and m-xylene and n-heptane.

Probing adsorption sites of carbon dioxide in metal organic framework of [Zn(bdc)(dpds)]n: A molecular simulation study

NASA Astrophysics Data System (ADS)

Lu, Shih-I.; Liao, Jian-Min; Huang, Xiao-Zhuang; Lin, Chia-Hsun; Ke, Szu-Yu; Wang, Chih-Chieh

2017-11-01

We used force-field based grand-canonical Monte Carlo simulation method and density functional theory to study adsorption characteristics of carbon dioxide (CO2) molecules in a metal-organic framework (MOF) compound, [Zn(bdc)(dpds)]n. The studied MOF include a metal ion (Zn(II)), an anion organic linker (dianion of benzene dicarboxylicacid, bdc2-) and a neutral organic linker (4,4‧-dipyridyldisulfide, dpds). Results from calculated adsorption isotherms and enthalpies of adsorption agree with the experimental data. The interactions between the adsorbed CO2 and the organic linkers were examined in simulations. Calculated results show available absorption sites are surrounded by two dpds ligands in which an S-S bond as an N-N‧ spacer connect two pyridines. In contrast, the bdc2- ligand does not give a significant contribution to the substantial adsorption amount even though it contains the carboxylate group that provides available bonding site to CO2.

Effects of supercritical carbon dioxide on immobile bound polymer chains on solid substrates

NASA Astrophysics Data System (ADS)

Sen, Mani; Asada, Mitsunori; Jiang, Naisheng; Endoh, Maya K.; Akgun, Bulent; Satija, Sushil; Koga, Tadanori

2013-03-01

Adsorbed polymer layers formed on flat solid substrates have recently been the subject of extensive studies because it is postulated to control the dynamics of technologically relevant polymer thin films, for example, in lithography. Such adsorbed layers have been reported to hinder the mobility of polymer chains in thin films even at a large length scale. Consequently, this bound layer remains immobile regardless of processing techniques (i.e. thermal annealing, solvent dissolution, etc). Here, we investigate the use of supercritical carbon dioxide (scCO2) as a novel plasticizer for bound polystyrene layers formed on silicon substrates. In-situ swelling and interdiffusion experiments using neutron reflectivity were performed. As a result, we found the anomalous plasticization effects of scCO2 on the bound polymer layers near the critical point where the anomalous adsorption of CO2 molecules in polymer thin films has been reported previously. Acknowledgement: We acknowledge the financial support from NSF Grant No. CMMI-084626.

Amino acid adsorption on anatase (101) surface at vacuum and aqueous solution: a density functional study.

PubMed

Liu, Liuxie; Li, Kai; Chen, Xiao; Liang, Xiaoqin; Zheng, Yan; Li, Laicai

2018-03-29

The adsorption of 20 amino acids (AAs) on the (101) surface of anatase titanium dioxide (TiO 2 ) has been investigated under the scheme of density functional theory. Through the analysis of adsorption geometries, amino group and side chains of AAs have been identified as the major side to adsorb on TiO 2 , while the carboxyl group prefers to stay outside to avoid the repulsion between negatively charged oxygen from TiO 2 and AAs. On the surface, two-coordinated oxygen is the major site to stabilize AAs through O-H interactions. The above conclusion does not change when it is in the aqueous solution based on the calculations with AAs surrounded by explicit water molecules. The above knowledge is helpful in predicting how AAs and even peptides adsorb on inorganic materials. Graphical abstract The adsorption of 20 amino acids (AAs) on the (101) surface of anatase titanium dioxide (TiO 2 ) has been investigated under the scheme of density functional theory.

Light-driven carbon dioxide reduction to methane by nitrogenase in a photosynthetic bacterium

PubMed Central

Fixen, Kathryn R.; Zheng, Yanning; Harris, Derek F.; Shaw, Sudipta; Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C.

2016-01-01

Nitrogenase is an ATP-requiring enzyme capable of carrying out multielectron reductions of inert molecules. A purified remodeled nitrogenase containing two amino acid substitutions near the site of its FeMo cofactor was recently described as having the capacity to reduce carbon dioxide (CO2) to methane (CH4). Here, we developed the anoxygenic phototroph, Rhodopseudomonas palustris, as a biocatalyst capable of light-driven CO2 reduction to CH4 in vivo using this remodeled nitrogenase. Conversion of CO2 to CH4 by R. palustris required constitutive expression of nitrogenase, which was achieved by using a variant of the transcription factor NifA that is able to activate expression of nitrogenase under all growth conditions. Also, light was required for generation of ATP by cyclic photophosphorylation. CH4 production by R. palustris could be controlled by manipulating the distribution of electrons and energy available to nitrogenase. This work shows the feasibility of using microbes to generate hydrocarbons from CO2 in one enzymatic step using light energy. PMID:27551090

Nitrogen Dioxide Exposure and Airway Responsiveness in Individuals with Asthma

EPA Science Inventory

Controlled human exposure studies evaluating the effect of inhaled NO2 on the inherent responsiveness of the airways to challenge by bronchoconstricting agents have had mixed results. In general, existing meta-analyses show statistically significant effects of NO2 on the airway r...

Climate Change, Carbon Dioxide, and Pest Biology: Monitor, Mitigate, Manage.

PubMed

Ziska, Lewis H; McConnell, Laura L

2016-01-13

Rising concentrations of atmospheric carbon dioxide ([CO2]) and subsequent changes in climate, including temperature and precipitation extremes, are very likely to alter pest pressures in both managed and unmanaged plant communities. Such changes in pest pressures can be positive (migration from a region) or negative (new introductions), but are likely to be accompanied by significant economic and environmental consequences. Recent studies indicate the range of invasive weeds such as kudzu and insects such as mountain pine beetle have already expanded to more northern regions as temperatures have risen. To reduce these consequences, a better understanding of the link between CO2/climate and pest biology is needed in the context of existing and new strategies for pest management. This paper provides an overview of the probable biological links and the vulnerabilities of existing pest management (especially chemical control) and provides a preliminary synthesis of research needs that could potentially improve the ability to monitor, mitigate, and manage pest impacts.

Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator

PubMed Central

Zhao, Yixin; Swierk, John R.; Megiatto, Jackson D.; Sherman, Benjamin; Youngblood, W. Justin; Qin, Dongdong; Lentz, Deanna M.; Moore, Ana L.; Moore, Thomas A.; Gust, Devens; Mallouk, Thomas E.

2012-01-01

Photoelectrochemical water splitting directly converts solar energy to chemical energy stored in hydrogen, a high energy density fuel. Although water splitting using semiconductor photoelectrodes has been studied for more than 40 years, it has only recently been demonstrated using dye-sensitized electrodes. The quantum yield for water splitting in these dye-based systems has, so far, been very low because the charge recombination reaction is faster than the catalytic four-electron oxidation of water to oxygen. We show here that the quantum yield is more than doubled by incorporating an electron transfer mediator that is mimetic of the tyrosine-histidine mediator in Photosystem II. The mediator molecule is covalently bound to the water oxidation catalyst, a colloidal iridium oxide particle, and is coadsorbed onto a porous titanium dioxide electrode with a Ruthenium polypyridyl sensitizer. As in the natural photosynthetic system, this molecule mediates electron transfer between a relatively slow metal oxide catalyst that oxidizes water on the millisecond timescale and a dye molecule that is oxidized in a fast light-induced electron transfer reaction. The presence of the mediator molecule in the system results in photoelectrochemical water splitting with an internal quantum efficiency of approximately 2.3% using blue light. PMID:22547794

TRP channels: sensors and transducers of gasotransmitter signals

PubMed Central

Takahashi, Nobuaki; Kozai, Daisuke; Mori, Yasuo

2012-01-01

The transient receptor potential (trp) gene superfamily encodes cation channels that act as multimodal sensors for a wide variety of stimuli from outside and inside the cell. Upon sensing, they transduce electrical and Ca2+ signals via their cation channel activities. These functional features of TRP channels allow the body to react and adapt to different forms of environmental changes. Indeed, members of one class of TRP channels have emerged as sensors of gaseous messenger molecules that control various cellular processes. Nitric oxide (NO), a vasoactive gaseous molecule, regulates TRP channels directly via cysteine (Cys) S-nitrosylation or indirectly via cyclic GMP (cGMP)/protein kinase G (PKG)-dependent phosphorylation. Recent studies have revealed that changes in the availability of molecular oxygen (O2) also control the activation of TRP channels. Anoxia induced by O2-glucose deprivation and severe hypoxia (1% O2) activates TRPM7 and TRPC6, respectively, whereas TRPA1 has recently been identified as a novel sensor of hyperoxia and mild hypoxia (15% O2) in vagal and sensory neurons. TRPA1 also detects other gaseous molecules such as hydrogen sulfide (H2S) and carbon dioxide (CO2). In this review, we focus on how signaling by gaseous molecules is sensed and integrated by TRP channels. PMID:22934072

Spectral-kinetic characteristics of luminescence of pentaerythritol tetranitrate with inclusions of iron nanoparticles upon explosion induced by laser pulses

NASA Astrophysics Data System (ADS)

Aduev, B. P.; Nurmukhametov, D. R.; Belokurov, G. M.; Nelyubina, N. V.; Gudilin, A. V.

2017-03-01

Spectral-kinetic characteristics of luminescence of tetranitropentaeritrite with inclusions of iron nanoparticles upon an explosion induced by laser pulses are measured with high temporal resolution. It is shown that the luminescence occurring during exposure to the laser pulse is a result of initiating a chemical reaction in tetranitropentaeritrite and is chemiluminescence. The glow is presumably associated with the excited nitrogen dioxide, NO2, which is formed by the rupture of O-NO2 bond in the tetranitropentaeritrite molecule.

Propiedades espectroscópicas de planetas extrasolares y de enanas marrones

NASA Astrophysics Data System (ADS)

Martínez, C. F.; Gómez, M.

In this contribution we present a comparison of the spectroscopic properties of three groups of objects: brown dwarfs, "Hot Jupiter" extrasolar planets and giant solar system planets, in particular Jupiter and Saturn. We col- lect all published spectra from the literature and compare their characteris- tics. Elements such as water vapor (H2 O) and methane (CH4 ) are present in practical all analyzed objects. On the contrary molecules such as carbon monoxide (CO) and carbon dioxide (CO2 ) are only detected in the spectra of planets. FULL TEXT IN SPANISH

Silica diatom shells tailored with Au nanoparticles enable sensitive analysis of molecules for biological, safety and environment applications.

PubMed

Onesto, V; Villani, M; Coluccio, M L; Majewska, R; Alabastri, A; Battista, E; Schirato, A; Calestani, D; Coppedé, N; Cesarelli, M; Amato, F; Di Fabrizio, E; Gentile, F

2018-04-10

Diatom shells are a natural, theoretically unlimited material composed of silicon dioxide, with regular patterns of pores penetrating through their surface. For their characteristics, diatom shells show promise to be used as low cost, highly efficient drug carriers, sensor devices or other micro-devices. Here, we demonstrate diatom shells functionalized with gold nanoparticles for the harvesting and detection of biological analytes (bovine serum albumin-BSA) and chemical pollutants (mineral oil) in low abundance ranges, for applications in bioengineering, medicine, safety, and pollution monitoring.

Insights into the mechanical properties of a silicone oil gel with a 'latent' gelator, 1-octadecylamine, and CO(2) as an 'activator'.

PubMed

Carretti, Emiliano; George, Mathew; Weiss, Richard G

2010-10-15

A detailed study of the rheological properties of silicone oil gels, made from a low-molecular-mass organic gelator, a combination of 1-octadecylamine (a latent gelator) and carbon dioxide (an 'activating' molecule), is reported. Information gleaned from the mechanical measurements is used to characterize the gel networks and how they respond to temperature and strain. It is shown, for example, that very precise measurements of the gel-to-sol transitions can be obtained from plots of viscosity versus temperature.

A mechanistic study and computational prediction of iron, cobalt and manganese cyclopentadienone complexes for hydrogenation of carbon dioxide.

PubMed

Ge, Hongyu; Chen, Xiangyang; Yang, Xinzheng

2016-10-13

A series of cobalt and manganese cyclopentadienone complexes are proposed and examined computationally as promising catalysts for hydrogenation of CO 2 to formic acid with total free energies as low as 20.0 kcal mol -1 in aqueous solution. Density functional theory study of the newly designed cobalt and manganese complexes and experimentally reported iron cyclopentadienone complexes reveals a stepwise hydride transfer mechanism with a water or a methanol molecule assisted proton transfer for the cleavage of H 2 as the rate-determining step.

Arcsecond Resolution Mapping of Sulfur Dioxide Emission in the Circumstellar Envelope of VY Canis Majoris

NASA Astrophysics Data System (ADS)

Fu, Roger R.; Moullet, Arielle; Patel, Nimesh A.; Biersteker, John; Derose, Kimberly L.; Young, Kenneth H.

2012-02-01

We report Submillimeter Array observations of SO2 emission in the circumstellar envelope (CSE) of the red supergiant VY Canis Majoris, with an angular resolution of ≈1''. SO2 emission appears in three distinct outflow regions surrounding the central continuum peak emission that is spatially unresolved. No bipolar structure is noted in the sources. A fourth source of SO2 is identified as a spherical wind centered at the systemic velocity. We estimate the SO2 column density and rotational temperature assuming local thermal equilibrium (LTE) as well as perform non-LTE radiative transfer analysis using RADEX. Column densities of SO2 are found to be ~1016 cm-2 in the outflows and in the spherical wind. Comparison with existing maps of the two parent species OH and SO shows the SO2 distribution to be consistent with that of OH. The abundance ratio f_{SO_{2}}/f_{SO} is greater than unity for all radii larger than 3 × 1016 cm. SO2 is distributed in fragmented clumps compared to SO, PN, and SiS molecules. These observations lend support to specific models of circumstellar chemistry that predict f_{SO_{2}}/f_{SO}>1 and may suggest the role of localized effects such as shocks in the production of SO2 in the CSE.

An Astrobiological View on Sustainable Life

NASA Astrophysics Data System (ADS)

Naganuma, Takeshi

2009-10-01

Life on a global biosphere basis is substantiated in the form of organics and organisms, and defined as the intermediate forms (briefly expressed as CH2O) hovering between the reduced (CH4, methane) and (CO2, carbon dioxide) ends, different from the classical definition of life as a complex organization maintaining ordered structure and information. Both definitions consider sustenance of life meant as protection of life against chaos through an input of external energy. The CH2O-life connection is maintained as long as the supply of H and O lasts, which is in turn are provided by the splitting of the water molecule H2O. Water is split by electricity, as well-known from school-level experiments, and by solar radiation and geothermal heat on a global scale. In other words, the Sun's radiation and the Earth's heat as well as radioactivity split water to supply H and O for continued existence of life on the Earth. These photochemical, radiochemical and geothermal processes have influences on the evolution and current composition of the Earth's atmosphere, compared with those of Venus and Mars, and influences on the planetary climatology. This view of life may be applicable to the "search-for-life in space" and to sustainability assessment of astrobiological habitats.

Carbon Dioxide Hydrogenation into Higher Hydrocarbons and Oxygenates: Thermodynamic and Kinetic Bounds and Progress with Heterogeneous and Homogeneous Catalysis.

PubMed

Prieto, Gonzalo

2017-03-22

Under specific scenarios, the catalytic hydrogenation of CO 2 with renewable hydrogen is considered a suitable route for the chemical recycling of this environmentally harmful and chemically refractory molecule into added-value energy carriers and chemicals. The hydrogenation of CO 2 into C 1 products, such as methane and methanol, can be achieved with high selectivities towards the corresponding hydrogenation product. More challenging, however, is the selective production of high (C 2+ ) hydrocarbons and oxygenates. These products are desired as energy vectors, owing to their higher volumetric energy density and compatibility with the current fuel infrastructure than C 1 compounds, and as entry platform chemicals for existing value chains. The major challenge is the optimal integration of catalytic functionalities for both reductive and chain-growth steps. This Minireview summarizes the progress achieved towards the hydrogenation of CO 2 to C 2+ hydrocarbons and oxygenates, covering both solid and molecular catalysts and processes in the gas and liquid phases. Mechanistic aspects are discussed with emphasis on intrinsic kinetic limitations, in some cases inevitably linked to thermodynamic bounds through the concomitant reverse water-gas-shift reaction, which should be considered in the development of advanced catalysts and processes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of a nanobubble and its effect on the structural ordering of water in a CH4-N2-CO2-H2O mixture.

PubMed

Kaur, Surinder Pal; Sujith, K S; Ramachandran, C N

2018-04-04

The replacement of methane (CH4) from its hydrate by a mixture of nitrogen (N2) and carbon dioxide (CO2) involves the dissociation of methane hydrate leading to the formation of a CH4-N2-CO2-H2O mixture that can significantly influence the subsequent steps of the replacement process. In the present work, we study the evolution of dissolved gas molecules in this mixture by applying classical molecular dynamics simulations. Our study shows that a higher CO2 : N2 ratio in the mixture enhances the formation of nanobubbles composed of N2, CH4 and CO2 molecules. To understand how the CO2 : N2 ratio affects nanobubble nucleation, the distribution of molecules in the bubble formed is examined. It is observed that unlike N2 and CH4, the density of CO2 in the bubble reaches a maximum at the surface of the bubble. The accumulation of CO2 molecules at the surface makes the bubble more stable by decreasing the excess pressure inside the bubble as well as surface tension at its interface with water. It is found that a frequent exchange of gas molecules takes place between the bubble and the surrounding liquid and an increase in concentration of CO2 in the mixture leads to a decrease in the number of such exchanges. The effect of nanobubbles on the structural ordering of water molecules is examined by determining the number of water rings formed per unit volume in the mixture. The role of nanobubbles in water structuring is correlated to the dynamic nature of the bubble arising from the exchange of gas molecules between the bubble and the liquid.

Ab initio studies of methane and carbon dioxide affinity to carbon compounds and minerals

NASA Astrophysics Data System (ADS)

Wlazlo, Mateusz; Siklitskaya, Alexandra; Majewski, Jacek

2017-04-01

Understanding of physico-chemistry of capture and storage of carbon dioxide and methane might be crucial for development of the novel technologies meant: (i) to deal with the global warming process through the reduction of the CO2 atmospheric concentration by sequestration, and (ii) to enhance oil recovery, on the other hand. The accurate description of CO2 and CH4 adsorption to minerals and carbonaceous systems (which constitute the main component of sedimentary rocks) is essential to reach this goal. We have employed the ab initio molecular dynamics AIMD) based on the density functional theory (DFT) to study the affinity of CO2 and CH4 from gaseous phase, also at elevated temperatures and hydrostatic pressure, to pristine and defected graphene, spiral carbon nanoparticles (spiroids), calcite rocks (represented by the most stable (10-14) surface of CaCoO3), CaO, MgO, illite, and kaolonite. In the case of kaolonite that exhibits layered crystallographic structure, we have also studied the intercalation of CO2. These studies provide valuable quantitative predictions and shed light on physical mechanisms governing the processes of chemisorption and physisorption of the CO2 and CH4 molecules, revealing also the essential role of Van der Waals interaction. In particular, we find out that CO2 molecules in supercritical gaseous phase (i.e. at temperature of order 60oC and moderate hydrostatic pressure of 20-30 MPa) change their shape from linear one to the water like bended V-shape with angle between C-O chemical bonds smaller than 180 degrees. This shape change of CO2 molecules facilitates the CO2 adsorption. Therefore, in the temperature-pressure conditions of shale deposits, the adsorption probability of CO2 can be enhanced in comparison to the ambient conditions. It turns out that the carbon atoms in the surrounding of characteristic Stone-Wales (or 5-7) defects in graphene are more reactive towards adsorption of CO2 and CH4 molecules. In the case of CO2 adsorption to the most stable (10-14) surface of CaCO3, the AIMD studies demonstrate that the carbon atom of CO2 is attracted to calcium atoms at the (10-14) calcite surface. The performed studies also show that CH4 molecule can be accumulated at the calcite surface in parallel to CO3 groups at low temperatures, and even it can induce reconfiguration of the surface by dehydrogenation process with the increase of temperature.

An Ultrahigh CO2-Loaded Silicalite-1 Zeolite: Structural Stability and Physical Properties at High Pressures and Temperatures.

PubMed

Marqueño, Tomas; Santamaria-Perez, David; Ruiz-Fuertes, Javier; Chuliá-Jordán, Raquel; Jordá, Jose L; Rey, Fernando; McGuire, Chris; Kavner, Abby; MacLeod, Simon; Daisenberger, Dominik; Popescu, Catalin; Rodriguez-Hernandez, Placida; Muñoz, Alfonso

2018-06-04

We report the formation of an ultrahigh CO 2 -loaded pure-SiO 2 silicalite-1 structure at high pressure (0.7 GPa) from the interaction of empty zeolite and fluid CO 2 medium. The CO 2 -filled structure was characterized in situ by means of synchrotron powder X-ray diffraction. Rietveld refinements and Fourier recycling allowed the location of 16 guest carbon dioxide molecules per unit cell within the straight and sinusoidal channels of the porous framework to be analyzed. The complete filling of pores by CO 2 molecules favors structural stability under compression, avoiding pressure-induced amorphization below 20 GPa, and significantly reduces the compressibility of the system compared to that of the parental empty one. The structure of CO 2 -loaded silicalite-1 was also monitored at high pressures and temperatures, and its thermal expansivity was estimated.

Crystallized and amorphous vortices in rotating atomic-molecular Bose-Einstein condensates

PubMed Central

Liu, Chao-Fei; Fan, Heng; Gou, Shih-Chuan; Liu, Wu-Ming

2014-01-01

Vortex is a topological defect with a quantized winding number of the phase in superfluids and superconductors. Here, we investigate the crystallized (triangular, square, honeycomb) and amorphous vortices in rotating atomic-molecular Bose-Einstein condensates (BECs) by using the damped projected Gross-Pitaevskii equation. The amorphous vortices are the result of the considerable deviation induced by the interaction of atomic-molecular vortices. By changing the atom-molecule interaction from attractive to repulsive, the configuration of vortices can change from an overlapped atomic-molecular vortices to carbon-dioxide-type ones, then to atomic vortices with interstitial molecular vortices, and finally into independent separated ones. The Raman detuning can tune the ratio of the atomic vortex to the molecular vortex. We provide a phase diagram of vortices in rotating atomic-molecular BECs as a function of Raman detuning and the strength of atom-molecule interaction. PMID:24573303

Initial stages of organic film growth characterized by thermal desorption spectroscopy

PubMed Central

Winkler, Adolf

2015-01-01

In the wake of the increasing importance of organic electronics, a more in-depth understanding of the early stages of organic film growth is indispensable. In this review a survey of several rod-like and plate-like organic molecules (p-quaterphenyl, p-sexiphenyl, hexaazatriphenylene-hexacarbonitrile (HATCN), rubicene, indigo) deposited on various application relevant substrates (gold, silver, mica, silicon dioxide) is given. The focus is particularly put on the application of thermal desorption spectroscopy to shed light on the kinetics and energetics of the molecule-substrate interaction. While each adsorption system reveals a manifold of features that are specific for the individual system, one can draw some general statements on the early stages of organic film formation from the available datasets. Among the important issues in this context is the formation of wetting layers and the dewetting as a function of the substrate surface conditions, organic film thickness and temperature. PMID:26778860

Organic Matter in the Outer Solar System

NASA Technical Reports Server (NTRS)

Cruiskshank, Dale P.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Many solid bodies in the outer Solar System are covered with ices of various compositions, including water, carbon dioxide, methane, nitrogen, and other molecules that are solid at the low temperatures that prevail there. These ices have all been detected by remote sensing observations made with telescopes on Earth, or more recently, spacecraft in orbit (notably Galileo at Jupiter). The data also reveal other solid materials that could be minerals or complex carbon-bearing organic molecules. A study in progress using large ground-based telescopes to acquire infrared spectroscopic data, and laboratory results on the optical properties of complex organic matter, seeks to identify the non-icy materials on several satellites of Saturn, Uranus, and Neptune. The work on the satellites of Saturn is in part preparatory to the Cassini spacecraft investigation of the Saturn system, which will begin in 2004 and extend for four years.

Unveiling the Interplay Between Diffusing CO2 and Ethanol Molecules in Champagne Wines by Classical Molecular Dynamics and (13)C NMR Spectroscopy.

PubMed

Bonhommeau, David A; Perret, Alexandre; Nuzillard, Jean-Marc; Cilindre, Clara; Cours, Thibaud; Alijah, Alexander; Liger-Belair, Gérard

2014-12-18

The diffusion coefficients of carbon dioxide (CO2) and ethanol (EtOH) in carbonated hydroalcoholic solutions and Champagne wines are evaluated as a function of temperature by classical molecular dynamics (MD) simulations and (13)C NMR spectroscopy measurements. The excellent agreement between theoretical and experimental diffusion coefficients suggest that ethanol is the main molecule, apart from water, responsible for the value of the CO2 diffusion coefficients in typical Champagne wines, a result that could likely be extended to most sparkling wines with alike ethanol concentrations. CO2 and EtOH hydrodynamical radii deduced from viscometry measurements by applying the Stokes-Einstein relationship are found to be mostly constant and in close agreement with MD predictions. The reliability of our approach should be of interest to physical chemists aiming to model transport phenomena in supersaturated aqueous solutions or water/alcohol mixtures.

Raman Spectra of Nitrogen, Carbon Dioxide, and Hydrogen in a Methane Environment

NASA Astrophysics Data System (ADS)

Petrov, D. V.; Matrosov, I. I.; Sedinkin, D. O.; Zaripov, A. R.

2018-01-01

Changes in the Raman spectra of N2, H2, and CO2 are studied in the range of 200-3800 cm-1 depending on the concentration of surrounding CH4 molecules at a fixed medium pressure of 25 atm and temperature of 300 K. It has been found that changes in the spectral characteristics of purely rotational H2 lines in a CH4 medium are negligible, while the Q-branches of the v 1/2 v 2 Fermi dyad in CO2 become narrower and wavenumbers of its high-frequency component and v 1 band of N2 decrease. In addition, under these conditions, the ratio of intensities of the CO2 Fermi dyad Q-branch varies in proportion to the concentration of surrounding molecules of CH4. The obtained data will be used in diagnosing the composition of natural gas using Raman spectroscopy.

110 Years of the Meyer–Overton Rule: Predicting Membrane Permeability of Gases and Other Small Compounds

PubMed Central

Missner, Andreas; Pohl, Peter

2010-01-01

The transport of gaseous compounds across biological membranes is essential in all forms of life. Although it was generally accepted that gases freely penetrate the lipid matrix of biological membranes, a number of studies challenged this doctrine as they found biological membranes to have extremely low gas-permeability values. These observations led to the identification of several membrane-embedded “gas” channels, which facilitate the transport of biological active gases, such as carbon dioxide, nitric oxide, and ammonia. However, some of these findings are in contrast to the well-established solubility–diffusion model (also known as the Meyer–Overton rule), which predicts membrane permeabilities from the molecule's oil–water partition coefficient. Herein, we discuss recently reported violations of the Meyer–Overton rule for small molecules, including carboxylic acids and gases, and show that Meyer and Overton continue to rule. PMID:19514034

Metal Insulator transition in Vanadium Dioxide

NASA Astrophysics Data System (ADS)

Jovaini, Azita; Fujita, Shigeji; Suzuki, Akira; Godoy, Salvador

2012-02-01

MAR12-2011-000262 Abstract Submitted for the MAR12 Meeting of The American Physical Society Sorting Category: 03.9 (T) On the metal-insulator-transition in vanadium dioxide AZITA JOVAINI, SHIGEJI FUJITA, University at Buffalo, SALVADOR GODOY, UNAM, AKIRA SUZUKI, Tokyo University of Science --- Vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340 K with the structural change from tetragonal to monoclinic crystal. The conductivity _/ drops at MIT by four orders of magnitude. The low temperature monoclinic phase is known to have a lower ground-state energy. The existence of the k-vector k is prerequisite for the conduction since the k appears in the semiclassical equation of motion for the conduction electron (wave packet). The tetragonal (VO2)3 unit is periodic along the crystal's x-, y-, and z-axes, and hence there is a three-dimensional k-vector. There is a one-dimensional k for a monoclinic crystal. We believe this difference in the dimensionality of the k-vector is the cause of the conductivity drop. Prefer Oral Session X Prefer .

Pulsed TEA CO2 Laser Irradiation of Titanium in Nitrogen and Carbon Dioxide Gases

NASA Astrophysics Data System (ADS)

Ciganovic, J.; Matavulj, P.; Trtica, M.; Stasic, J.; Savovic, J.; Zivkovic, S.; Momcilovic, M.

2017-12-01

Surface changes created by interaction of transversely excited atmospheric carbon dioxide (TEA CO2) laser with titanium target/implant in nitrogen and carbon dioxide gas were studied. TEA CO2 laser operated at 10.6 μm, pulse length of 100 ns and fluence of ˜17 J/cm2 which was sufficient for inducing surface modifications. Induced changes depend on the gas used. In both gases the grain structure was produced (central irradiated zone) but its forms were diverse, (N2: irregular shape; CO2: hill-like forms). Hydrodynamic features at peripheral zone, like resolidified droplets, were recorded only in CO2 gas. Elemental analysis of the titanium target surface indicated that under a nitrogen atmosphere surface nitridation occurred. In addition, irradiation in both gases was followed by appearance of plasma in front of the target. The existence of plasma indicates relatively high temperatures created above the target surface offering a sterilizing effect.

Three approaches for estimating recovery factors in carbon dioxide enhanced oil recovery

USGS Publications Warehouse

Verma, Mahendra K.

2017-07-17

PrefaceThe Energy Independence and Security Act of 2007 authorized the U.S. Geological Survey (USGS) to conduct a national assessment of geologic storage resources for carbon dioxide (CO2) and requested the USGS to estimate the “potential volumes of oil and gas recoverable by injection and sequestration of industrial carbon dioxide in potential sequestration formations” (42 U.S.C. 17271(b)(4)). Geologic CO2 sequestration associated with enhanced oil recovery (EOR) using CO2 in existing hydrocarbon reservoirs has the potential to increase the U.S. hydrocarbon recoverable resource. The objective of this report is to provide detailed information on three approaches that can be used to calculate the incremental recovery factors for CO2-EOR. Therefore, the contents of this report could form an integral part of an assessment methodology that can be used to assess the sedimentary basins of the United States for the hydrocarbon recovery potential using CO2-EOR methods in conventional oil reservoirs.

Monitoring gaseous exchange: implications for nursing care.

PubMed

Martin, Susan; Wilson, Michael

2002-02-01

The purpose of this study is to examine whether a relationship exists between arterial and end-tidal carbon dioxide tension (PaCO2 and PETCO2 respectively) in patients admitted to intensive care units (ICUs), and what the implications it has for nursing care. PaCO2 and PETCO2 are indicators of ventilatory adequacy which is an important aspect of respiratory function. These measures of carbon dioxide tension are obtained via invasive and non-invasive monitoring tools. Measurement of PETCO2 has only recently been introduced into ICUs and its usefulness in these environments is open to debate. A population of 30 intubated patients had 214 simultaneous measurements of PaCO2 and PETCO2 taken over a period of 10 months. The findings indicate that, despite strong significant correlations, PETCO2 cannot be used safely as a substitute for PaCO2 as the arterial/end-tidal carbon dioxide gradient is not constant, nor does capnography provide a consistently reliable indicator of PaCO2.

Fabry-Perot Based Radiometers for Precise Measurement of Greenhouse Gases

NASA Technical Reports Server (NTRS)

Heaps, William S.; Wilson, Emily L.; Georgieva, Elena

2007-01-01

Differential radiometers based upon the Fabry-Perot interferometer have been developed and demonstrated that exhibit very great sensitivity to changes in the atmospheric column of carbon dioxide, oxygen, and water vapor. These instruments employ a solid Fabry-Perot etalon that is tuned to the proper wavelength by changing the temperature. By choosing the thickness of the etalon its multiple pass bands can be made to align with regularly space absorption features of the molecule under investigation. Use of multiple absorption features improves the optical throughput of the instrument and improves the stability of the instrument response with respect to environmental changes. Efforts are underway at Goddard to extend this technique to the carbon 13 isotope of carbon dioxide and to methane. These instruments are intrinsically rugged and can be made rather small and inexpensively. They therefore hold promise for widespread use in ground based networks for calibration of satellite instruments such as OCO and GOSAT. Results will be presented for ground based and airborne operations for these systems. The effects of atmospheric scattering, pointing errors, pressure broadening and temperature effects will be discussed with regard to achieving precision better than .5% required for validation of carbon dioxide column measured from space. Designs permitting the extension of the technique to an even larger number of atmospheric species will be discussed along with theoretical analysis of potential system performance.

Assessment of the UV camera sulfur dioxide retrieval for point source plumes

USGS Publications Warehouse

Dalton, M.P.; Watson, I.M.; Nadeau, P.A.; Werner, C.; Morrow, W.; Shannon, J.M.

2009-01-01

Digital cameras, sensitive to specific regions of the ultra-violet (UV) spectrum, have been employed for quantifying sulfur dioxide (SO2) emissions in recent years. The instruments make use of the selective absorption of UV light by SO2 molecules to determine pathlength concentration. Many monitoring advantages are gained by using this technique, but the accuracy and limitations have not been thoroughly investigated. The effect of some user-controlled parameters, including image exposure duration, the diameter of the lens aperture, the frequency of calibration cell imaging, and the use of the single or paired bandpass filters, have not yet been addressed. In order to clarify methodological consequences and quantify accuracy, laboratory and field experiments were conducted. Images were collected of calibration cells under varying observational conditions, and our conclusions provide guidance for enhanced image collection. Results indicate that the calibration cell response is reliably linear below 1500 ppm m, but that the response is significantly affected by changing light conditions. Exposure durations that produced maximum image digital numbers above 32 500 counts can reduce noise in plume images. Sulfur dioxide retrieval results from a coal-fired power plant plume were compared to direct sampling measurements and the results indicate that the accuracy of the UV camera retrieval method is within the range of current spectrometric methods. ?? 2009 Elsevier B.V.

Crystal structure of 5-{4'-[(2-{2-[2-(2-ammonio-eth-oxy)eth-oxy]eth-oxy}eth-yl)carbamo-yl]-4-meth-oxy-[1,1'-biphen-yl]-3-yl}-3-oxo-1,2,5-thia-diazo-lidin-2-ide 1,1-dioxide: a potential inhibitor of the enzyme protein tyrosine phosphatase 1B (PTP1B).

PubMed

Ruddraraju, Kasi Viswanatharaju; Hillebrand, Roman; Barnes, Charles L; Gates, Kent S

2015-04-01

The title compound, C24H32N4O8S, (I), crystallizes as a zwitterion. The terminal amine N atom of the [(2-{2-[2-(2-ammonio-eth-oxy)eth-oxy]eth-oxy}eth-yl)carbamo-yl] side chain is protonated, while the 1,2,5-thia-diazo-lidin-3-one 1,1-dioxide N atom is deprotonated. The side chain is turned over on itself with an intra-molecular N-H⋯O hydrogen bond. The 1,2,5-thia-diazo-lidin-3-one 1,1-dioxide ring has an envelope conformation with the aryl-substituted N atom as the flap. Its mean plane is inclined by 62.87 (8)° to the aryl ring to which it is attached, while the aryl rings of the biphenyl unit are inclined to one another by 20.81 (8)°. In the crystal, mol-ecules are linked by N-H⋯O and N-H⋯N hydrogen bonds, forming slabs lying parallel to (010). Within the slabs there are C-H⋯O and C-H⋯N hydrogen bonds and C-H⋯π inter-actions present.

Comparing the catalytic oxidation of ethanol at the solid-gas and solid-liquid interfaces over size-controlled Pt nanoparticles: striking differences in kinetics and mechanism.

PubMed

Sapi, Andras; Liu, Fudong; Cai, Xiaojun; Thompson, Christopher M; Wang, Hailiang; An, Kwangjin; Krier, James M; Somorjai, Gabor A

2014-11-12

Pt nanoparticles with controlled size (2, 4, and 6 nm) are synthesized and tested in ethanol oxidation by molecular oxygen at 60 °C to acetaldehyde and carbon dioxide both in the gas and liquid phases. The turnover frequency of the reaction is ∼80 times faster, and the activation energy is ∼5 times higher at the gas-solid interface compared to the liquid-solid interface. The catalytic activity is highly dependent on the size of the Pt nanoparticles; however, the selectivity is not size sensitive. Acetaldehyde is the main product in both media, while twice as much carbon dioxide was observed in the gas phase compared to the liquid phase. Added water boosts the reaction in the liquid phase; however, it acts as an inhibitor in the gas phase. The more water vapor was added, the more carbon dioxide was formed in the gas phase, while the selectivity was not affected by the concentration of the water in the liquid phase. The differences in the reaction kinetics of the solid-gas and solid-liquid interfaces can be attributed to the molecular orientation deviation of the ethanol molecules on the Pt surface in the gas and liquid phases as evidenced by sum frequency generation vibrational spectroscopy.

Isolation, Preliminary Characterization and Preliminary Assessment of Scale-Up Potential of Photosynthetic Microalgae for the Production of Both Biofuels and Bio-Active Molecules in the U.S. and Canada: Cooperative Research and Development Final Report, CRADA Number CRD-10-372

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pienkos, P.

2012-09-01

Combustion flue gases are a major contributor to carbon dioxide emissions into the Earth's atmosphere, a factor that has been linked to the possible global climate change. It is, therefore, critical to begin thinking seriously about ways to reduce this influx into the atmosphere. Using carbon dioxide from fossil fuel combustion as a feedstock for the growth, photosynthetic microorganisms can provide a large sink for carbon assimilation as well as a feedstock for the production of significant levels of biofuels. Combining microalgal farming with fossil fuel energy production has great potential to diminish carbon dioxide releases into the atmosphere, asmore » well as contribute to the production of biofuels (e.g., biodiesel, renewable diesel and gasoline and jet fuel) as well as valuable co-products such as animal feeds and green chemicals. CO2 capture may be a regulatory requirement in future new coal or natural gas power plants and will almost certainly become an opportunity for commerce, the results of such studies may provide industries in the US and Canada with both regulatory relief and business opportunities as well as the ability to meet environmental and regulatory requirements, and to produce large volumes of fuels and co-products.« less

Association between air pollution and acute childhood wheezy episodes: prospective observational study.

PubMed Central

Buchdahl, R.; Parker, A.; Stebbings, T.; Babiker, A.

1996-01-01

OBJECTIVE--To examine the association between the air pollutants ozone, sulphur dioxide, and nitrogen dioxide and the incidence of acute childhood wheezy episodes. DESIGN--Prospective observational study over one year. SETTING--District general hospital. SUBJECTS--1025 children attending the accident and emergency department with acute wheezy episodes; 4285 children with other conditions as the control group. MAIN OUTCOME MEASURES--Daily incidence of acute wheezy episodes. RESULTS--After seasonal adjustment, day to day variations in daily average concentrations of ozone and sulphur dioxide were found to have significant associations with the incidence of acute wheezy episodes. The strongest association was with ozone, for which a non-linear U shaped relation was seen. In terms of the incidence rate ratio (1 at a mean 24 hour ozone concentration of 40 microg/m3 (SD=19.1)), children were more likely to attend when the concentration was two standard deviations below the mean (incidence rate ratio=3.01; 95% confidence interval 2.17 to 4.18) or two standard deviations above the mean (1.34; 1.09 to 1.66). Sulphur dioxide had a weaker log-linear relation with incidence (1.12; 1.05 to 1.19 for each standard deviation (14.1) increase in sulphur dioxide concentration). Further adjustment for temperature and wind speed did not significantly alter these associations. CONCLUSIONS--Independent of season, temperature, and wind speed, fluctuations in concentrations of atmospheric ozone and sulphur dioxide are strongly associated with patterns of attendance at accident and emergency departments for acute childhood wheezy episodes. A critical ozone concentration seems to exist in the atmosphere above or below which children are more likely to develop symptoms. PMID:8597731

Recent advances in the study of the UO2-PuO2 phase diagram at high temperatures

NASA Astrophysics Data System (ADS)

Böhler, R.; Welland, M. J.; Prieur, D.; Cakir, P.; Vitova, T.; Pruessmann, T.; Pidchenko, I.; Hennig, C.; Guéneau, C.; Konings, R. J. M.; Manara, D.

2014-05-01

Recently, novel container-less laser heating experimental data have been published on the melting behaviour of pure PuO2 and PuO2-rich compositions in the uranium dioxide-plutonium dioxide system. Such data showed that previous data obtained by more traditional furnace heating techniques were affected by extensive interaction between the sample and its containment. It is therefore paramount to check whether data so far used by nuclear engineers for the uranium-rich side of the pseudo-binary dioxide system can be confirmed or not. In the present work, new data are presented both in the UO2-rich part of the phase diagram, most interesting for the uranium-plutonium dioxide based nuclear fuel safety, and in the PuO2 side. The new results confirm earlier furnace heating data in the uranium-dioxide rich part of the phase diagram, and more recent laser-heating data in the plutonium-dioxide side of the system. As a consequence, it is also confirmed that a minimum melting point must exist in the UO2-PuO2 system, at a composition between x(PuO2) = 0.4 and x(PuO2) = 0.7 and 2900 K ⩽ T ⩽ 3000 K. Taking into account that, especially at high temperature, oxygen chemistry has an effect on the reported phase boundary uncertainties, the current results should be projected in the ternary U-Pu-O system. This aspect has been extensively studied here by X-ray diffraction and X-ray absorption spectroscopy. The current results suggest that uncertainty bands related to oxygen behaviour in the equilibria between condensed phases and gas should not significantly affect the qualitative trend of the current solid-liquid phase boundaries.

Demonstrating Chirality: Using a Mirror with Physical Models To Show Non-superimposability of Chiral Molecules with Their Mirror Images.

ERIC Educational Resources Information Center

Collins, Michael J.

2001-01-01

Presents a remarkable demonstration on chiralty in molecules and the existence of enantiomers, also known as non-superimposable mirror images. Uses a mirror, a physical model of a molecule, and a bit of trickery involving the non-superimposable mirror image. (Author/NB)

Quantum Chemical Study of Supercritical Carbon Dioxide Effects on Combustion Kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masunov, Artëm E.; Wait, Elizabeth E.; Atlanov, Arseniy A.

In oxy-fuel combustion, the pure oxygen (O 2), diluted with CO 2 is used as oxidant instead air. Hence, the combustion products (CO 2 and H 2O) are free from pollution by nitrogen oxides. Moreover, high pressures results in the near-liquid density of CO 2 at supercritical state (sCO 2). Unfortunately, the effects of sCO 2 on the combustion kinetics are far from being understood. In order to assist in this understanding, in this work we are using quantum chemistry methods. Here we investigate potential energy surfaces of important combustion reactions in the presence of carbon dioxide melocule. All transitionmore » states, reactant and product complexes are reported for three reactions: H 2CO+HO 2→HCO+H 2O 2 (R1), 2HO 2→H 2O 2+O 2 (R2), and CO+OH→CO 2+H (R3). In the reaction R3, covalent binding of CO 2 to OH radical and then CO molecule opens a new pathway, including hydrogen transfer from oxygen to carbon atoms followed by CH bond dissociation. Compared to bimolecular OH+CO mechanism, this pathway reduces the activation barrier by 5 kcal/mol, and is expected to accelerate the reaction. This is the first report of autocatalytic effect in combustion. In case of hydroperoxyl self-reaction 2HO 2→H 2O 2+O 2 the intermediates, containing covalent bonds to CO 2 were found not to be competitive. However, the spectator CO 2 molecule is able to stabilize the cyclic transition state and lower the barrier by 3 kcal/mol. Formation of covalent intermediates was also discovered in H 2CO+HO 2→HCO+H 2O 2 reaction, but these specie lead to substantially higher activation barriers which makes them unlikely to play role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide also stabilized transition state and reduces reaction barrier. Lastly, these results indicate that CO 2 environment is likely to have catalytic effect on combustion reactions, which needs to be included in kinetic combustion mechanisms in supercritical CO 2.« less

Quantum Chemical Study of Supercritical Carbon Dioxide Effects on Combustion Kinetics

DOE PAGES

Masunov, Artëm E.; Wait, Elizabeth E.; Atlanov, Arseniy A.; ...

2017-05-03

In oxy-fuel combustion, the pure oxygen (O 2), diluted with CO 2 is used as oxidant instead air. Hence, the combustion products (CO 2 and H 2O) are free from pollution by nitrogen oxides. Moreover, high pressures results in the near-liquid density of CO 2 at supercritical state (sCO 2). Unfortunately, the effects of sCO 2 on the combustion kinetics are far from being understood. In order to assist in this understanding, in this work we are using quantum chemistry methods. Here we investigate potential energy surfaces of important combustion reactions in the presence of carbon dioxide melocule. All transitionmore » states, reactant and product complexes are reported for three reactions: H 2CO+HO 2→HCO+H 2O 2 (R1), 2HO 2→H 2O 2+O 2 (R2), and CO+OH→CO 2+H (R3). In the reaction R3, covalent binding of CO 2 to OH radical and then CO molecule opens a new pathway, including hydrogen transfer from oxygen to carbon atoms followed by CH bond dissociation. Compared to bimolecular OH+CO mechanism, this pathway reduces the activation barrier by 5 kcal/mol, and is expected to accelerate the reaction. This is the first report of autocatalytic effect in combustion. In case of hydroperoxyl self-reaction 2HO 2→H 2O 2+O 2 the intermediates, containing covalent bonds to CO 2 were found not to be competitive. However, the spectator CO 2 molecule is able to stabilize the cyclic transition state and lower the barrier by 3 kcal/mol. Formation of covalent intermediates was also discovered in H 2CO+HO 2→HCO+H 2O 2 reaction, but these specie lead to substantially higher activation barriers which makes them unlikely to play role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide also stabilized transition state and reduces reaction barrier. Lastly, these results indicate that CO 2 environment is likely to have catalytic effect on combustion reactions, which needs to be included in kinetic combustion mechanisms in supercritical CO 2.« less

Virtual Rewards for Driving Green

ERIC Educational Resources Information Center

Pritchard, Josh

2010-01-01

Carbon dioxide from automobiles is a major contributor to global climate change. In "Virtual Rewards for Driving Green," Josh Pritchard proposes a computer application that will enable fuel-efficient drivers to earn "green" dollars with which to buy digital merchandise on the Web. Can getting items that exist only in cyberspace actually change a…

76 FR 77225 - Agency Information Collection Activities OMB Responses

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-12

... Intake Structures; was approved on 11/04/2011; OMB Number 2040-0283; expires on 07/31/2013; Approved... Requirements under the Underground Injection Control (UIC) Program for Carbon Dioxide Geologic Sequestration... filed comment on 11/10/2011. EPA ICR Number 2060.05; Cooling Water Intake Structures Existing Facility...

The CO2 laser frequency stability measurements

NASA Technical Reports Server (NTRS)

Johnson, E. H., Jr.

1973-01-01

Carbon dioxide laser frequency stability data are considered for a receiver design that relates to maximum Doppler frequency and its rate of change. Results show that an adequate margin exists in terms of data acquisition, Doppler tracking, and bit error rate as they relate to laser stability and transmitter power.

The Improvement of the Resistance to Candida albicans and Trichophyton interdigitale of Some Woven Fabrics Based on Cotton.

PubMed

Surdu, Lilioara; Stelescu, Maria Daniela; Manaila, Elena; Nicula, Gheorghe; Iordache, Ovidiu; Dinca, Laurentiu Christian; Berechet, Mariana-Daniela; Vamesu, Mariana; Gurau, Dana

2014-01-01

This paper presents the improvement of the antimicrobial character of woven fabrics based on cotton. The woven fabrics were cleaned in oxygen plasma and treated by padding with silver chloride and titanium dioxide particles. The existence of silver and titanium on woven fabrics was evidenced by electronic microscope images (SEM, EDAX) and by flame atomic absorption spectrophotometry. The antimicrobial tests were performed with two fungi: Candida albicans and Trichophyton interdigitale. The obtained antimicrobial effect was considerably higher compared to the raw fabrics. Treatment of dyed fabrics with a colloidal solution based on silver chloride and titanium dioxide particles does not considerably influence colour resistance of dyes.

The Improvement of the Resistance to Candida albicans and Trichophyton interdigitale of Some Woven Fabrics Based on Cotton

PubMed Central

Stelescu, Maria Daniela; Manaila, Elena; Nicula, Gheorghe; Iordache, Ovidiu; Dinca, Laurentiu Christian; Berechet, Mariana-Daniela; Vamesu, Mariana; Gurau, Dana

2014-01-01

This paper presents the improvement of the antimicrobial character of woven fabrics based on cotton. The woven fabrics were cleaned in oxygen plasma and treated by padding with silver chloride and titanium dioxide particles. The existence of silver and titanium on woven fabrics was evidenced by electronic microscope images (SEM, EDAX) and by flame atomic absorption spectrophotometry. The antimicrobial tests were performed with two fungi: Candida albicans and Trichophyton interdigitale. The obtained antimicrobial effect was considerably higher compared to the raw fabrics. Treatment of dyed fabrics with a colloidal solution based on silver chloride and titanium dioxide particles does not considerably influence colour resistance of dyes. PMID:25276112

[Detection of occupational hazards in a large shipbuilding factory].

PubMed

Du, Weijia; Wang, Zhi; Zhang, Hai; Zhou, Liping; Huang, Minzhi; Liu, Yimin

2014-03-01

To provide evidence for the prevention and treatment of occupational diseases by the analysis of existing major occupational hazards and health conditions of workers in a large shipbuilding factory. Field investigation of occupational conditions was conducted to examine the existence of occupational hazards from 2009 to 2012 in a large shipbuilding factory, and then the results of physical examination among its workers were analyzed. Other than the metal dust (total dust), the levels of other dusts and manganese dioxide were beyond the national standard to various degrees, and through a sampling point detection, it was found that the levels of manganese dioxide exceeded the standard by 42.8%. The maximum time-weighted average concentration in individuals was 27.927 mg/m(3), much higher than the national standard limit. For harmful gas detection in individuals, xylene was 38.4%above the standard level (the highest concentration reached 1447.7 mg/m(3)); moreover, both toluene and ethylbenzene exceeded the national standard at different levels. Among the noise-exposed workers, 71%worked in the environment where the daily noise was above the limit of the national standard (85 dB). Physical examinations in 2010 and 2012 showed that the abnormal rate of audiometry in workers was higher than 15%. Dust (total dust), manganese dioxide, benzene, and noise are the main occupational hazards among the workers in the large shipbuilding factory, and strict protection and control for these hazards should be implemented for the workers in the factory.

A Wunda-full world? Carbon dioxide ice deposits on Umbriel and other Uranian moons

NASA Astrophysics Data System (ADS)

Sori, Michael M.; Bapst, Jonathan; Bramson, Ali M.; Byrne, Shane; Landis, Margaret E.

2017-07-01

Carbon dioxide has been detected on the trailing hemispheres of several Uranian satellites, but the exact nature and distribution of the molecules remain unknown. One such satellite, Umbriel, has a prominent high albedo annulus-shaped feature within the 131-km-diameter impact crater Wunda. We hypothesize that this feature is a solid deposit of CO2 ice. We combine thermal and ballistic transport modeling to study the evolution of CO2 molecules on the surface of Umbriel, a high-obliquity (∼98°) body. Considering processes such as sublimation and Jeans escape, we find that CO2 ice migrates to low latitudes on geologically short (100s-1000 s of years) timescales. Crater morphology and location create a local cold trap inside Wunda, and the slopes of crater walls and a central peak explain the deposit's annular shape. The high albedo and thermal inertia of CO2 ice relative to regolith allows deposits 15-m-thick or greater to be stable over the age of the solar system. We conclude that Wunda, located at low latitude (7.9° S) and near the center of the trailing hemisphere where CO2 detections are strongest, likely contains a solid CO2 ice deposit. We discuss prospects for similar CO2 ice deposits on crater floors on the other major Uranian moons, and predict that they are present on Ariel, Titania, and possibly Oberon (but not Miranda or smaller satellites). Such deposits have likely not been observed due to the limited nature of Voyager 2 image coverage.

Lanthanide Complexes with Multidentate Oxime Ligands as Single-Molecule Magnets and Atmospheric Carbon Dioxide Fixation Systems.

PubMed

Hołyńska, Małgorzata; Clérac, Rodolphe; Rouzières, Mathieu

2015-09-14

The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 (1: [La2 (pop)2 (acac)4 (CH3 OH)], 2: [Dy2 (pop)(acac)5 ]) are synthesized from the 2-hydroxyimino-N-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3, 4, and 5 (3: [Dy2 (naphthsaoH)2 (acac)4 H(OH)]⋅0.85 CH3 CN⋅1.58 H2 O; 4: [Tb2 (naphthsaoH)2 (acac)4 H(OH)]⋅0.52 CH3 CN⋅1.71 H2 O; 5: [La6 (CO3 )2 (naphthsao)5 (naphthsaoH)0.5 (acac)8 (CO3 )0.5 (CH3 OH)2.76 H5.5 (H2 O)1.24 ]⋅2.39 CH3 CN⋅0.12 H2 O) contain 1-(1-hydroxynaphthalen-2-yl)-ethanone oxime (naphthsaoH2 ). In 1-4, dinuclear [Ln2 ] complexes crystallize, whereas hexanuclear La(III) complex 5 is formed after fixation of atmospheric carbon dioxide. Dy(III) -based complexes 2 and 3 display single-molecule-magnet properties with energy barriers of 27 and 98 K, respectively. The presence of a broad and unsymmetrical relaxation mode observed in the ac susceptibility data for 3 suggest two different dynamics of the magnetization which might be a consequence of independent relaxation processes of the two different Dy(3+) ions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

PubMed Central

Reda, Torsten; Plugge, Caroline M.; Abram, Nerilie J.; Hirst, Judy

2008-01-01

Carbon dioxide (CO2) is a kinetically and thermodynamically stable molecule. It is easily formed by the oxidation of organic molecules, during combustion or respiration, but is difficult to reduce. The production of reduced carbon compounds from CO2 is an attractive proposition, because carbon-neutral energy sources could be used to generate fuel resources and sequester CO2 from the atmosphere. However, available methods for the electrochemical reduction of CO2 require excessive overpotentials (are energetically wasteful) and produce mixtures of products. Here, we show that a tungsten-containing formate dehydrogenase enzyme (FDH1) adsorbed to an electrode surface catalyzes the efficient electrochemical reduction of CO2 to formate. Electrocatalysis by FDH1 is thermodynamically reversible—only small overpotentials are required, and the point of zero net catalytic current defines the reduction potential. It occurs under thoroughly mild conditions, and formate is the only product. Both as a homogeneous catalyst and on the electrode, FDH1 catalyzes CO2 reduction with a rate more than two orders of magnitude faster than that of any known catalyst for the same reaction. Formate oxidation is more than five times faster than CO2 reduction. Thermodynamically, formate and hydrogen are oxidized at similar potentials, so formate is a viable energy source in its own right as well as an industrially important feedstock and a stable intermediate in the conversion of CO2 to methanol and methane. FDH1 demonstrates the feasibility of interconverting CO2 and formate electrochemically, and it is a template for the development of robust synthetic catalysts suitable for practical applications. PMID:18667702

Encapsulation of lutein in liposomes using supercritical carbon dioxide.

PubMed

Zhao, Lisha; Temelli, Feral; Curtis, Jonathan M; Chen, Lingyun

2017-10-01

Liposomes loaded with lutein were prepared utilizing supercritical carbon dioxide (SC-CO 2 ). The effects of pressure, depressurization rate, temperature and lutein-to-lipid ratio on particle size distribution, zeta potential, encapsulation efficiency (EE), bioactive loading, morphology, phase transition and crystallinity were investigated. Liposomes prepared by the SC-CO 2 method had a particle size of 147.6±1.9nm-195.4±2.3nm, an encapsulation efficiency of 56.7±0.7%-97.0±0.8% and a zeta potential of -54.5±1.2mV to -61.7±0.6mV. A higher pressure (200-300bar) and depressurization rate (90-200bar/min) promoted a higher encapsulation of lutein whereas the lutein-to-lipid ratio had the dominant effect on the morphology of vesicles along with size distribution and EE. X-ray diffraction data implied a substantial drop in the crystallinity of lutein upon its redistribution in the liposome membranes. Differential scanning calorimetry indicated a broadened phase transition upon the simultaneous rearrangement of lutein and phospholipid molecules into liposomal vesicles. The SC-CO 2 method resulted in particle characteristics highly associated with the ability of CO 2 to disperse phospholipids and lutein molecules. It offers a promising approach to use dense phase CO 2 to homogenize hydrophobic or amphiphilic aggregates suspended in an aqueous medium and regulate the vesicular characteristics via pressure and depressurization rate. The SC-CO 2 method has potential for scalable production of liposomal nanovesicles with desirable characteristics and free of organic solvents. Copyright © 2017 Elsevier Ltd. All rights reserved.

A new interstellar molecule - Tricarbon monoxide

NASA Technical Reports Server (NTRS)

Matthews, H. E.; Irvine, W. M.; Friberg, P.; Brown, R. D.; Godfrey, P. D.

1984-01-01

The C3O molecule, whose pure rotational spectrum has only recently been studied in the laboratory, has been detected in the cold, dark interstellar Taurus Molecular Cloud 1. Since C3O is the first interstelar carbon chain molecule to contain oxygen, its existence places an important new constraint on chemical schemes for cold interstellar clouds. The abundance of C3O can be understood in terms of purely gas-phase ion-molecule chemistry.

Young organic matter as a source of carbon dioxide outgassing from Amazonian rivers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayorga, E; Aufdenkampe, A K; Masiello, C A

2005-06-23

Rivers are generally supersaturated with respect to carbon dioxide, resulting in large gas evasion fluxes that can be a significant component of regional net carbon budgets. Amazonian rivers were recently shown to outgas more than ten times the amount of carbon exported to the ocean in the form of total organic carbon or dissolved inorganic carbon. High carbon dioxide concentrations in rivers originate largely from in situ respiration of organic carbon, but little agreement exists about the sources or turnover times of this carbon. Here we present results of an extensive survey of the carbon isotope composition ({sup 13}C andmore » {sup 14}C) of dissolved inorganic carbon and three size-fractions of organic carbon across the Amazonian river system. We find that respiration of contemporary organic matter (less than 5 years old) originating on land and near rivers is the dominant source of excess carbon dioxide that drives outgassing in mid-size to large rivers, although we find that bulk organic carbon fractions transported by these rivers range from tens to thousands of years in age. We therefore suggest that a small, rapidly cycling pool of organic carbon is responsible for the large carbon fluxes from land to water to atmosphere in the humid tropics.« less

Carbon Mineralization Using Phosphate and Silicate Ions

NASA Astrophysics Data System (ADS)

Gokturk, H.

2013-12-01

Carbon dioxide (CO2) reduction from combustion of fossil fuels has become an urgent concern for the society due to marked increase in weather related natural disasters and other negative consequences of global warming. CO2 is a highly stable molecule which does not readily interact with other neutral molecules. However it is more responsive to ions due to charge versus quadrupole interaction [1-2]. Ions can be created by dissolving a salt in water and then aerosolizing the solution. This approach gives CO2 molecules a chance to interact with the hydrated salt ions over the large surface area of the aerosol. Ion containing aerosols exist in nature, an example being sea spray particles generated by breaking waves. Such particles contain singly and doubly charged salt ions including Na+, Cl-, Mg++ and SO4--. Depending on the proximity of CO2 to the ion, interaction energy can be significantly higher than the thermal energy of the aerosol. For example, an interaction energy of 0.6 eV is obtained with the sulfate (SO4--) ion when CO2 is the nearest neighbor [2]. In this research interaction between CO2 and ions which carry higher charges are investigated. The molecules selected for the study are triply charged phosphate (PO4---) ions and quadruply charged silicate (SiO4----) ions. Examples of salts which contain such molecules are potassium phosphate (K3PO4) and sodium orthosilicate (Na4SiO4). The research has been carried out with first principle quantum mechanical calculations using the Density Functional Theory method with B3LYP functional and Pople type basis sets augmented with polarization and diffuse functions. Atomic models consist of the selected ions surrounded by water and CO2 molecules. Similar to the results obtained with singly and doubly charged ions [1-2], phosphate and silicate ions attract CO2 molecules. Energy of interaction between the ion and CO2 is 1.6 eV for the phosphate ion and 3.3 eV for the silicate ion. Hence one can expect that the selected ions would enhance the absorption of CO2 into the aerosol even more than the singly or doubly charged ions. Ion containing aerosols also help to catalyze reactions between water and CO2. Hydrated phosphate and silicate ions tend to attract hydrogen atoms from neighboring water molecules to reduce the charged state. When there is CO2 in the vicinity of the ion, the remainder of the water molecule which loses the hydrogen(s) reacts with CO2 to form carbonates. (PO4---) + H2O + CO2 -> (HPO3--) + (HCO3-) (SiO4----) + H2O + CO2 -> (HSiO4---) + (HCO3-) (SiO4----) + H2O + CO2 -> (H2SiO4--) + (CO3--) In conclusion, highly charged phosphate and silicate ions dissolved in water and aerosolized into small droplets can facilitate both the capture and the mineralization of CO2. This method would be especially effective in a CO2 rich environment such as the exhaust gas of a combustion process. [1] H. Gokturk, "Geoengineering with Charged Droplets," AGU Fall Meeting, San Francisco 2011 [2] H. Gokturk, "Atomistic Simulation of Sea Spray Particles," AGU Fall Meeting, San Francisco 2012

Automatic Nanodesign Using Evolutionary Techniques

NASA Technical Reports Server (NTRS)

Globus, Al; Saini, Subhash (Technical Monitor)

1998-01-01

Many problems associated with the development of nanotechnology require custom designed molecules. We use genetic graph software, a new development, to automatically evolve molecules of interest when only the requirements are known. Genetic graph software designs molecules, and potentially nanoelectronic circuits, given a fitness function that determines which of two molecules is better. A set of molecules, the first generation, is generated at random then tested with the fitness function, Subsequent generations are created by randomly choosing two parent molecules with a bias towards high scoring molecules, tearing each molecules in two at random, and mating parts from the mother and father to create two children. This procedure is repeated until a satisfactory molecule is found. An atom pair similarity test is currently used as the fitness function to evolve molecules similar to existing pharmaceuticals.

Normal coordinate analysis of the vibrational spectrum of benzil molecule

NASA Astrophysics Data System (ADS)

Volovšek, V.; Colombo, L.

1993-03-01

Normal coordinate analysis is performed for the benzil molecule. Force constants of phenyl rings are transferred from earlier studies on binuclear aromatic molecules. The existance of some low-frequency internal modes have been proved, thus eliminating the earlier explanations of the excess of the bands observed in the low-frequency Raman and FIR spectra of benzil crystal.

High-Resolution Electrospray Ionization/Ion Mobility Spectrometer for Detection of Abiotic Amino Acids

NASA Technical Reports Server (NTRS)

Beegle, L. W.; Terrell, C. A.; Kim, H.; Kanik, I.

2003-01-01

One of the primary goals of the current NASA thrust in Astrobiology is the detection and identification of organic molecules as part of an in-situ lander platform on the surface of Mars or Europa. The identification of these molecules should help determine whether indigenous organisms exist on the surface of Mars or in an undersea environment on Europa. In addition, a detailed organic chemical inventory of surface and near surface molecules will help elucidate the possibilities of life elsewhere in the Universe. Terrestrial life has, as its backbone, the family of molecules known as the amino acids (AA), and while AA can be found in the terrestrial environments as part of more complex molecules, such as peptides, and proteins, they also exist as individual molecules due to of the hydrolyses of biopolymers. In terrestrial biochemistry, there are 20 principal amino acids which are necessary for life. However, some forms of these molecules can be found in nature synthesized via abiotic process. For example, they are known to exist extraterrestrially as a component of carbonaceous meteorites. The idea that amino acids are readily created by abiotic means has been demonstrated by their positive identification in the Murchison CM2 meteorite, which fell in 1969. This meteorite was analyzed before contamination by terrestrial microbes could result. Three laboratories individually tested parts of the meteorite and concluded that the amino acids present in them were indigenous to the meteorite because, among other reasons, they had equal L- and D- enantiomers. Final identification of the constituents of the Murchison included 33 amino acids which have no known biotic source, 11 amino acids which have limited distribution and 8 (Glycine, Alanine, Valine, Proline, Leucine, Isoleucine, Aspartic Acid, and Glutamic Acid), which readily occur in terrestrial proteins.

No evidence for interstellar proteins

NASA Astrophysics Data System (ADS)

Koch, R. H.; Davies, R. E.

1984-03-01

The claim by Karim et al. (1983) that the broad interstellar feature near 280 nm suggests the existence of proteinaceous matter in the interstellar medium is addressed. From astronomical and biochemical arguments it is shown that no quantitative measures of optical depth can be derived from the published data and that there is a great wealth of organic molecules which have absorptions at or near this wavelength interval. The amino acid tryptophan is one such molecule but the deduced spectrum does not satisfy two other properties of its spectrum. In particular, the 280 nm absorption for tryptophan refers to an aqueous solution of the molecule, and no liquid water is expected to exist in the ISM.

Active colloidal molecules

NASA Astrophysics Data System (ADS)

Löwen, Hartmut

2018-03-01

Like ordinary molecules are composed of atoms, colloidal molecules consist of several species of colloidal particles tightly bound together. If one of these components is self-propelled or swimming, novel “active colloidal molecules” emerge. Active colloidal molecules exist on various levels such as “homonuclear”, “heteronuclear” and “polymeric” and possess a dynamical function moving as propellers, spinners or rotors. Self-assembly of such active complexes has been studied a lot recently and this perspective article summarizes recent progress and gives an outlook to future developments in the rapidly expanding field of active colloidal molecules.

Reducing Open Cell Landfill Methane Emissions with a Bioactive Alternative Daily

DOE Office of Scientific and Technical Information (OSTI.GOV)

Helene Hilger; James Oliver; Jean Bogner

2009-03-31

Methane and carbon dioxide are formed in landfills as wastes degrade. Molecule-for-molecule, methane is about 20 times more potent than carbon dioxide at trapping heat in the earth's atmosphere, and thus, it is the methane emissions from landfills that are scrutinized. For example, if emissions composed of 60% methane and 40% carbon dioxide were changed to a mix that was 40% methane and 60% carbon dioxide, a 30% reduction in the landfill's global warming potential would result. A 10% methane, 90% carbon dioxide ratio will result in a 75% reduction in global warming potential compared to the baseline. Gas collectionmore » from a closed landfill can reduce emissions, and it is sometimes combined with a biocover, an engineered system where methane oxidizing bacteria living in a medium such as compost, convert landfill methane to carbon dioxide and water. Although methane oxidizing bacteria merely convert one greenhouse gas (methane) to another (carbon dioxide), this conversion can offer significant reductions in the overall greenhouse gas contribution, or global warming potential, associated with the landfill. What has not been addressed to date is the fact that methane can also escape from a landfill when the active cell is being filled with waste. Federal regulations require that newly deposited solid waste to be covered daily with a 6 in layer of soil or an alternative daily cover (ADC), such as a canvas tarp. The aim of this study was to assess the feasibility of immobilizing methane oxidizing bacteria into a tarp-like matrix that could be used for alternative daily cover at open landfill cells to prevent methane emissions. A unique method of isolating methanotrophs from landfill cover soil was used to create a liquid culture of mixed methanotrophs. A variety of prospective immobilization techniques were used to affix the bacteria in a tarp-like matrix. Both gel encapsulation of methanotrophs and gels with liquid cores containing methanotrophs were readily made but prone to rapid desiccation. Bacterial adsorption onto foam padding, natural sponge, and geotextile was successful. The most important factor for success appeared to be water holding capacity. Prototype biotarps made with geotextiles plus adsorbed methane oxidizing bacteria were tested for their responses to temperature, intermittent starvation, and washing (to simulate rainfall). The prototypes were mesophilic, and methane oxidation activity remained strong after one cycle of starvation but then declined with repeated cycles. Many of the cells detached with vigorous washing, but at least 30% appeared resistant to sloughing. While laboratory landfill simulations showed that four-layer composite biotarps made with two different types of geotextile could remove up to 50% of influent methane introduced at a flux rate of 22 g m{sup -2} d{sup -1}, field experiments did not yield high activity levels. Tests revealed that there were high hour-to-hour flux variations in the field, which, together with frequent rainfall events, confounded the field testing. Overall, the findings suggest that a methanotroph embedded biotarp appears to be a feasible strategy to mitigate methane emission from landfill cells, although the performance of field-tested biotarps was not robust here. Tarps will likely be best suited for spring and summer use, although the methane oxidizer population may be able to shift and adapt to lower temperatures. The starvation cycling of the tarp may require the capacity for intermittent reinoculation of the cells, although it is also possible that a subpopulation will adapt to the cycling and become dominant. Rainfall is not expected to be a major factor, because a baseline biofilm will be present to repopulate the tarp. If strong performance can be achieved and documented, the biotarp concept could be extended to include interception of other compounds beyond methane, such as volatile aromatic hydrocarbons and chlorinated solvents.« less

CO2 diffusion in champagne wines: a molecular dynamics study.

PubMed

Perret, Alexandre; Bonhommeau, David A; Liger-Belair, Gérard; Cours, Thibaud; Alijah, Alexander

2014-02-20

Although diffusion is considered as the main physical process responsible for the nucleation and growth of carbon dioxide bubbles in sparkling beverages, the role of each type of molecule in the diffusion process remains unclear. In the present study, we have used the TIP5P and SPC/E water models to perform force field molecular dynamics simulations of CO2 molecules in water and in a water/ethanol mixture respecting Champagne wine proportions. CO2 diffusion coefficients were computed by applying the generalized Fick's law for the determination of multicomponent diffusion coefficients, a law that simplifies to the standard Fick's law in the case of champagnes. The CO2 diffusion coefficients obtained in pure water and water/ethanol mixtures composed of TIP5P water molecules were always found to exceed the coefficients obtained in mixtures composed of SPC/E water molecules, a trend that was attributed to a larger propensity of SPC/E water molecules to form hydrogen bonds. Despite the fact that the SPC/E model is more accurate than the TIP5P model to compute water self-diffusion and CO2 diffusion in pure water, the diffusion coefficients of CO2 molecules in the water/ethanol mixture are in much better agreement with the experimental values of 1.4 - 1.5 × 10(-9) m(2)/s obtained for Champagne wines when the TIP5P model is employed. This difference was deemed to rely on the larger propensity of SPC/E water molecules to maintain the hydrogen-bonded network between water molecules and form new hydrogen bonds with ethanol, although statistical issues cannot be completely excluded. The remarkable agreement between the theoretical CO2 diffusion coefficients obtained within the TIP5P water/ethanol mixture and the experimental data specific to Champagne wines makes us infer that the diffusion coefficient in these emblematic hydroalcoholic sparkling beverages is expected to remain roughly constant whathever their proportions in sugars, glycerol, or peptides.

Formation, structure, and evolution of boiling nucleus and interfacial tension between bulk liquid phase and nucleus

NASA Astrophysics Data System (ADS)

Wang, Xiao-Dong; Peng, Xiao-Feng; Tian, Yong; Wang, Bu-Xuan

2005-05-01

In this paper, the concept of the molecular free path is introduced to derive a criterion distinguishing active molecules from inactive molecules in liquid phase. A concept of the critical aggregation concentration (CAC) of active molecules is proposed to describe the physical configuration before the formation of a nucleus during vapor-liquid phase transition. All active molecules exist as monomers when the concentration of active molecules is lower than CAC, while the active molecules will generate aggregation once the concentration of the active molecules reaches CAC. However, these aggregates with aggregation number, N, smaller than five can steadily exist in bulk phase. The other excess active molecules can only produce infinite aggregation and form a critical nucleus of vapor-liquid phase transition. Without any outer perturbation the state point of CAC corresponds to the critical superheated or supercooled state. Meanwhile, a model of two-region structure of a nucleus is proposed to describe nucleus evolution. The interfacial tension between bulk liquid phase and nucleus is dependent of the density gradient in the transition region and varies with the structure change of the transition region. With the interfacial tension calculated using this model, the predicted nucleation rate is very close to the experimental measurement. Furthermore, this model and associated analysis provides solid theoretical evidences to clarify the definition of nucleation rate and understand nucleation phenomenon with the insight into the physical nature.

46 CFR 167.45-1 - Steam, carbon dioxide, Halon 1301, and clean agent fire extinguishing systems.

Code of Federal Regulations, 2014 CFR

2014-10-01

... holds, paint lockers, and similar spaces. However, although existing steam smothering systems may be... to each cargo-oil deep tank, lamp locker, oil room, and like compartments, which lamp locker, oil... lamp lockers, oil rooms, and like compartments may be taken from the nearest steam supply line...

46 CFR 167.45-1 - Steam, carbon dioxide, Halon 1301, and clean agent fire extinguishing systems.

Code of Federal Regulations, 2012 CFR

2012-10-01

... holds, paint lockers, and similar spaces. However, although existing steam smothering systems may be... to each cargo-oil deep tank, lamp locker, oil room, and like compartments, which lamp locker, oil... lamp lockers, oil rooms, and like compartments may be taken from the nearest steam supply line...

46 CFR 167.45-1 - Steam, carbon dioxide, Halon 1301, and clean agent fire extinguishing systems.

Code of Federal Regulations, 2013 CFR

2013-10-01

... holds, paint lockers, and similar spaces. However, although existing steam smothering systems may be... to each cargo-oil deep tank, lamp locker, oil room, and like compartments, which lamp locker, oil... lamp lockers, oil rooms, and like compartments may be taken from the nearest steam supply line...

75 FR 48860 - Approval and Promulgation of Air Quality Implementation Plans; New Mexico; Revisions to Emissions...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-12

... matter, and carbon monoxide. The revisions add new definitions; modify existing definitions; and require..., particulate matter, and sulfur dioxide. The SIP is a set of air pollution regulations, control strategies... to submit an annual report of sulfur input in tons per year, and added emission tracking requirements...

Managing the Future: Public Policy, Scientific Uncertainty, and Global Warming.

ERIC Educational Resources Information Center

Jamieson, Dale

Due to the injection of carbon dioxide and various other gasses into the atmosphere, the world of the 21st century may well have a climate that is beyond the parameters of human existence. Physical science produces information regarding the physical effects of increasing concentrations of "greenhouse" gasses. Once this information is…

Brownian dynamics simulation of a polymer chain in a solid-state nanopore attached to a molecular stop

NASA Astrophysics Data System (ADS)

Wells, Craig; Hulings, Zachery; Melnikov, Dmitriy; Gracheva, Maria

We study a nanopore inside a silicon dioxide membrane submerged in a KCl solution with a negatively charged polymer chain of varying lengths whose movement is described using Brownian dynamics. The polymer is attached to a molecule with a radius larger than that of the nanopore's which acts as a molecular stop, allowing the chain to thread the nanopore but preventing it from translocating. We found that the polymer chain's variation of movement along the nanopore decreased when increasing applied biases and chain lengths for portions of the chain closest to the molecular stop. The chain displacement within the pore is also compared to a freely translocating polymer where preliminary results show the free polymer having a greater variation in the radial direction. Overall, our preliminary results indicate that the radial direction of the polymer chain is dominated by the confinement in the narrow nanopore with restrictions imposed by the molecular stop and bias playing a lesser role. Understanding the interaction behavior of the polymer chain-stop molecule may lead to methods that decrease movement variation, facilitating an improvement on characterizing and identification of molecules. NSF DMR and CBET Grant No. 1352218.

First principles investigations of vinazene molecule and molecular crystal: a prospective candidate for organic photovoltaic applications.

PubMed

Mohamad, Mazmira; Ahmed, Rashid; Shaari, Amirudin; Goumri-Said, Souraya

2015-02-01

Escalating demand for sustainable energy resources, because of the rapid exhaustion of conventional energy resources as well as to maintain the environmental level of carbon dioxide (CO2) to avoid its adverse effect on the climate, has led to the exploitation of photovoltaic technology manifold more than ever. In this regard organic materials have attracted great attention on account of demonstrating their potential to harvest solar energy at an affordable rate for photovoltaic technology. 2-vinyl-4,5-dicyanoimidazole (vinazene) is considered as a suitable material over the fullerenes for photovoltaic applications because of its particular chemical and physical nature. In the present study, DFT approaches are employed to provide an exposition of optoelectronic properties of vinazene molecule and molecular crystal. To gain insight into its properties, different forms of exchange correlation energy functional/potential such as LDA, GGA, BLYP, and BL3YP are used. Calculated electronic structure of vinazene molecule has been displayed via HOMO-LUMO isosurfaces, whereas electronic structure of the vinazene molecular crystal, via electronic band structure, is presented. The calculated electronic and optical properties were analyzed and compared as well. Our results endorse vinazene as a suitable material for organic photovoltaic applications.

Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework.

PubMed

Banerjee, Debasis; Wang, Hao; Plonka, Anna M; Emge, Thomas J; Parise, John B; Li, Jing

2016-08-08

Gate-opening is a unique and interesting phenomenon commonly observed in flexible porous frameworks, where the pore characteristics and/or crystal structures change in response to external stimuli such as adding or removing guest molecules. For gate-opening that is induced by gas adsorption, the pore-opening pressure often varies for different adsorbate molecules and, thus, can be applied to selectively separate a gas mixture. The detailed understanding of this phenomenon is of fundamental importance to the design of industrially applicable gas-selective sorbents, which remains under investigated due to the lack of direct structural evidence for such systems. We report a mechanistic study of gas-induced gate-opening process of a microporous metal-organic framework, [Mn(ina)2 ] (ina=isonicotinate) associated with commensurate adsorption, by a combination of several analytical techniques including single crystal X-ray diffraction, in situ powder X-ray diffraction coupled with differential scanning calorimetry (XRD-DSC), and gas adsorption-desorption methods. Our study reveals that the pronounced and reversible gate opening/closing phenomena observed in [Mn(ina)2 ] are coupled with a structural transition that involves rotation of the organic linker molecules as a result of interaction of the framework with adsorbed gas molecules including carbon dioxide and propane. The onset pressure to open the gate correlates with the extent of such interaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NASA Astrophysics Data System (ADS)

2017-11-01

To deal with these problems investigators usually rely on a calibration method that makes use of a substance with an accurately known set of interatomic distances. The procedure consists of carrying out a diffraction experiment on the chosen calibrating substance, determining the value of the distances with use of the nominal (meter) value of the voltage, and then correcting the nominal voltage by an amount that produces the distances in the calibration substance. Examples of gases that have been used for calibration are carbon dioxide, carbon tetrachloride, carbon disulfide, and benzene; solids such as zinc oxide smoke (powder) deposited on a screen or slit have also been used. The question implied by the use of any standard molecule is, how accurate are the interatomic distance values assigned to the standard? For example, a solid calibrant is subject to heating by the electron beam, possibly producing unknown changes in the lattice constants, and polyatomic gaseous molecules require corrections for vibrational averaging ("shrinkage") effects that are uncertain at best. It has lately been necessary for us to investigate this matter in connection with on-going studies of several molecules in which size is the most important issue. These studies indicated that our usual method for retrieval of data captured on film needed improvement. The following is an account of these two issues - the accuracy of the distances assigned to the chosen standard molecule, and the improvements in our methods of retrieving the scattered intensity data.

Relative impact of H 2 O and O 2 in the oxidation of UO 2 powders from 50 to 300 °C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donald, Scott B.; Davisson, M. Lee; Dai, Zurong

Here, we studied the reaction of water and molecular oxygen with stoichiometric uranium dioxide (i.e. UO 2) powder at elevated temperature by high-resolution x-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy, powder x-ray diffraction (XRD), and scanning electron microscopy (SEM). We observed and quatified oxidation resulting from the dissociative chemisorption of the adsorbing molecules and subsequent incorporation into the oxide lattice. Molecular oxygen was found to be a stronger oxidation agent than water at elevated temperatures but not at ambient.

Gas Sorption and Storage Properties of Calixarenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patil, Rahul S.; Banerjee, Debasis; Atwood, Jerry L.

2016-12-01

Calixarenes, a class of organic macrocyclic molecules have shown interesting gas sorption properties towards industrially important gases such as carbon di-oxide, hydrogen, methane and acetylene. These macrocycles are involved in weak van der Waals interaction to form multidimensional supramolecular frameworks. The gas-diffusion and subsequent sorption occurs due to a cooperative behavior between neighboring macrocycles. Furthermore, the flexibility at the upper rim functional group also plays a key role in the overall gas uptake of calixarene. In this book chapter, we give a brief account of interaction and diffusion of gases in calixarene and selected derivatives.

Insights into the mechanical properties of a silicone oil gel with a ‘latent’ gelator, 1-octadecylamine, and CO2 as an ‘activator’

PubMed Central

George, Mathew

2010-01-01

Summary A detailed study of the rheological properties of silicone oil gels, made from a low-molecular-mass organic gelator, a combination of 1-octadecylamine (a latent gelator) and carbon dioxide (an ‘activating’ molecule), is reported. Information gleaned from the mechanical measurements is used to characterize the gel networks and how they respond to temperature and strain. It is shown, for example, that very precise measurements of the gel-to-sol transitions can be obtained from plots of viscosity versus temperature. PMID:21085496

Methyl 4-eth-oxy-2-methyl-2H-1,2-benzothia-zine-3-carboxyl-ate 1,1-dioxide.

PubMed

Zia-Ur-Rehman, Muhammad; Choudary, Jamil Anwar; Elsegood, Mark R J; Akbar, Noshin; Latif Siddiqui, Hamid

2008-07-16

In the crystal structure of the title compound, C(13)H(15)NO(5)S, the mol-ecules exhibit weak S=O⋯H-C and C=O⋯H-C inter-molecular inter-actions and arrange themselves into centrosymmetric dimers by means of π-π inter-actions (ring centroids are separated by 3.619 Å, while the closest C⋯C contacts are 3.514 Å). 1,2-Benzothia-zines of this kind have a range of biological activities and are used as medicines in the treatment of inflammation and rheumatoid arthritis.

Relative impact of H2O and O2 in the oxidation of UO2 powders from 50 to 300 °C

NASA Astrophysics Data System (ADS)

Donald, Scott B.; Davisson, M. Lee; Dai, Zurong; Roberts, Sarah K.; Nelson, Art J.

2017-12-01

The reaction of water and molecular oxygen with stoichiometric uranium dioxide (i.e. UO2) powder at elevated temperature was studied by high-resolution x-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy, powder x-ray diffraction (XRD), and scanning electron microscopy (SEM). Oxidation resulting from the dissociative chemisorption of the adsorbing molecules and subsequent incorporation into the oxide lattice was observed and quantified. Molecular oxygen was found to be a stronger oxidation agent than water at elevated temperatures but not at ambient.

Relative impact of H 2 O and O 2 in the oxidation of UO 2 powders from 50 to 300 °C

DOE PAGES

Donald, Scott B.; Davisson, M. Lee; Dai, Zurong; ...

2017-10-04

Here, we studied the reaction of water and molecular oxygen with stoichiometric uranium dioxide (i.e. UO 2) powder at elevated temperature by high-resolution x-ray photoelectron spectroscopy (XPS), infrared (IR) spectroscopy, powder x-ray diffraction (XRD), and scanning electron microscopy (SEM). We observed and quatified oxidation resulting from the dissociative chemisorption of the adsorbing molecules and subsequent incorporation into the oxide lattice. Molecular oxygen was found to be a stronger oxidation agent than water at elevated temperatures but not at ambient.

The Interaction of Sorbitol with Caffeine in Aqueous Solution

PubMed Central

Tavagnacco, Letizia; Brady, John W.; Cesàro, Attilio

2013-01-01

Molecular dynamics simulations were carried out on a system of caffeine interacting with the sugar alcohol sorbitol. The system examined had a caffeine concentration 0.083 m and a sugar concentration 1.08 m. The trajectories of all molecules in the system were collected over a period of 80 ns and analyzed to determine whether there is any tendency for sorbitol to bind to caffeine, and if so, by what mechanism. The results show that the sorbitol molecules have an affinity for the caffeine molecules and that the binding occurred by the interaction of the aliphatic hydrophobic protons of the sugar with the caffeine face. This intermolecular association via face-to-face stacking, as suggested by simulation studies, is similar to that found for sucrose and for D-glucose, which overwhelmingly exists in the pyranose ring chair form in aqueous solution, as well as for caffeine-caffeine association. The sorbitol molecules, however, exist as relatively extended chains and are, therefore, topologically quite different from the sugars sucrose and glucose. The comparison of the average conformation of sorbitol molecules bound to caffeine with that of molecules in the free state shows a substantial similarity. PMID:24000279

The Interaction of Sorbitol with Caffeine in Aqueous Solution.

PubMed

Tavagnacco, Letizia; Brady, John W; Cesàro, Attilio

2013-09-01

Molecular dynamics simulations were carried out on a system of caffeine interacting with the sugar alcohol sorbitol. The system examined had a caffeine concentration 0.083 m and a sugar concentration 1.08 m. The trajectories of all molecules in the system were collected over a period of 80 ns and analyzed to determine whether there is any tendency for sorbitol to bind to caffeine, and if so, by what mechanism. The results show that the sorbitol molecules have an affinity for the caffeine molecules and that the binding occurred by the interaction of the aliphatic hydrophobic protons of the sugar with the caffeine face. This intermolecular association via face-to-face stacking, as suggested by simulation studies, is similar to that found for sucrose and for D-glucose, which overwhelmingly exists in the pyranose ring chair form in aqueous solution, as well as for caffeine-caffeine association. The sorbitol molecules, however, exist as relatively extended chains and are, therefore, topologically quite different from the sugars sucrose and glucose. The comparison of the average conformation of sorbitol molecules bound to caffeine with that of molecules in the free state shows a substantial similarity.

Nano-MnO2-mediated transformation of triclosan with humic molecules present: kinetics, products, and pathways.

PubMed

Sun, Kai; Li, Shunyao; Waigi, Michael Gatheru; Huang, Qingguo

2018-05-01

It has been shown that manganese dioxide (MnO 2 ) can mediate transformation of phenolic contaminants to form phenoxyl radical intermediates, and subsequently, these intermediates intercouple to form oligomers via covalent binding. However, the reaction kinetics and transformation mechanisms of phenolic contaminants with humic molecules present in nano-MnO 2 -mediated systems were still unclear. In this study, it was proven that nano-MnO 2 were effective in transforming triclosan under acidic conditions (pH 3.5-5.0) during manganese reduction, and the apparent pseudo first-order kinetics rate constants (k = 0.0599-1.5314 h -1 ) increased as the pH decreased. In particular, the transformation of triclosan by nano-MnO 2 was enhanced in the presence of low-concentration humic acid (1-10 mg L -1 ). The variation in the absorption of humic molecules at 275 nm supported possible covalent binding between humic molecules and triclosan in the nano-MnO 2 -mediated systems. A total of four main intermediate products were identified by high-resolution mass spectrometry (HRMS), regardless of humic molecules present in the systems or not. These products correspond to a suite of radical intercoupling reactions (dimers and trimers), ether cleavage (2,4-dichlorophenol), and oxidation to quinone-like products, triggered by electron transfer from triclosan molecules to nano-MnO 2 . A possible reaction pathway in humic acid solutions, including homo-coupling, decomposition, oxidation, and cross-coupling, was proposed. Our findings provide valuable information regarding the environmental fate and transformation mechanism of triclosan by nano-MnO 2 in complex water matrices.

Spectroscopic Investigation of the Primary Reaction Intermediates in the Oxidation of Levitated Droplets of Energetic Ionic Liquids.

PubMed

Brotton, Stephen J; Lucas, Michael; Chambreau, Steven D; Vaghjiani, Ghanshyam L; Yu, Jiang; Anderson, Scott L; Kaiser, Ralf I

2017-12-21

The production of the next generation of hypergolic, ionic-liquid-based fuels requires an understanding of the reaction mechanisms between the ionic liquid and oxidizer. We probed reactions between a levitated droplet of 1-methyl-4-amino-1,2,4-triazolium dicyanamide ([MAT][DCA]), with and without hydrogen-capped boron nanoparticles, and the nitrogen dioxide (NO 2 ) oxidizer. The apparatus exploits an ultrasonic levitator enclosed within a pressure-compatible process chamber equipped with complementary Raman, ultraviolet-visible, and Fourier-transform infrared (FTIR) spectroscopic probes. Vibrational modes were first assigned to the FTIR and Raman spectra of droplets levitated in argon. Spectra were subsequently collected for pure and boron-doped [MAT][DCA] exposed to nitrogen dioxide. By comparison with electronic structure calculations, some of the newly formed modes suggest that the N atom of the NO 2 molecule bonds to a terminal N on the dicyanamide anion yielding [O 2 N-NCNCN] - . This represents the first spectroscopic evidence of a key reaction intermediate in the oxidation of levitated ionic liquid droplets.

Unravelling Mechanistic Aspects of the Gas-Phase Ethanol Conversion: An Experimental and Computational Study on the Thermal Reactions of MO2 (+) (M=Mo, W) with Ethanol.

PubMed

González-Navarrete, Patricio; Schlangen, Maria; Wu, Xiao-Nan; Schwarz, Helmut

2016-02-24

The ion/molecule reactions of molybdenum and tungsten dioxide cations with ethanol have been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and density functional theory (DFT) calculations. Dehydration of ethanol has been found as the dominant reaction channel, while generation of the ethyl cation corresponds to a minor product. Cleary, the reactions are mainly governed by the Lewis acidity of the metal center. Computational results, together with isotopic labeling experiments, show that the dehydration of ethanol can proceed either through a conventional concerted [1,2]-elimination mechanism or a step-wise process; the latter occurs via a hydroxyethoxy intermediate. Formation of C2 H5 (+) takes place by transfer of OH(-) from ethanol to the metal center of MO2 (+) . The molybdenum and tungsten dioxide cations exhibit comparable reactivities toward ethanol, and this is reflected in similar reaction rate constants and branching ratios. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison and Analysis of Zinc and Cobalt-Based Systems as Catalytic Entities for the Hydration of Carbon Dioxide

PubMed Central

Lau, Edmond Y.; Wong, Sergio E.; Baker, Sarah E.; Bearinger, Jane P.; Koziol, Lucas; Valdez, Carlos A.; Satcher, Joseph H.; Aines, Roger D.; Lightstone, Felice C.

2013-01-01

In nature, the zinc metalloenzyme carbonic anhydrase II (CAII) efficiently catalyzes the conversion of carbon dioxide (CO2) to bicarbonate under physiological conditions. Many research efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolyl)phosphine, and tris(2-benzimidazolylmethyl)amine, in their complexed form either with the Zn2+ or the Co2+ ion and studied their reaction coordinate for CO2 hydration. These calculations demonstrated that the ability of the complex to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Furthermore, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts. PMID:23840420

Biotransformation of carbon dioxide in bioelectrochemical systems: State of the art and future prospects

NASA Astrophysics Data System (ADS)

Bajracharya, Suman; Srikanth, Sandipam; Mohanakrishna, Gunda; Zacharia, Renju; Strik, David PBTB; Pant, Deepak

2017-07-01

Carbon dioxide (CO2) utilization/recycling for the production of chemicals and gaseous/liquid energy-carriers is a way to moderate the rising CO2 in the atmosphere. One of the possible solutions for the CO2 sequestration is the electrochemical reduction of this stable molecule to useful fuel/products. Nevertheless, the surface chemistry of CO2 reduction is a challenge due to the presence of large energy barriers, requiring noticeable catalysis. The recent approach of microbial electrocatalysis of CO2 reduction has promising prospects to reduce the carbon level sustainably, taking full advantage of CO2-derived chemical commodities. We review the currently investigated bioelectrochemical approaches that could possibly be implemented to enable the handling of CO2 emissions. This review covers the most recent advances in the bioelectrochemical approaches of CO2 transformations in terms of biocatalysts development and process design. Furthermore, the extensive research on carbon fixation and conversion to different value added chemicals is reviewed. The review concludes by detailing the key challenges and future prospects that could enable economically feasible microbial electrosynthesis technology.

Light-driven carbon dioxide reduction to methane by nitrogenase in a photosynthetic bacterium

DOE PAGES

Fixen, Kathryn R.; Zheng, Yanning; Harris, Derek F.; ...

2016-08-22

Nitrogenase is an ATP-requiring enzyme capable of carrying out multielectron reductions of inert molecules. A purified remodeled nitrogenase containing two amino acid substitutions near the site of its FeMo cofactor was recently described as having the capacity to reduce carbon dioxide (CO 2) to methane (CH 4). Here, we developed the anoxygenic phototroph, Rhodopseudomonas palustris, as a biocatalyst capable of light-driven CO 2 reduction to CH 4 in vivo using this remodeled nitrogenase. Conversion of CO 2 to CH 4 by R. palustris required constitutive expression of nitrogenase, which was achieved by using a variant of the transcription factor NifAmore » that is able to activate expression of nitrogenase under all growth conditions. Also, light was required for generation of ATP by cyclic photophosphorylation. CH 4 production by R. palustris could be controlled by manipulating the distribution of electrons and energy available to nitrogenase. Furthermore, this work shows the feasibility of using microbes to generate hydrocarbons from CO 2 in one enzymatic step using light energy.« less

Comparison and analysis of zinc and cobalt-based systems as catalytic entities for the hydration of carbon dioxide

DOE PAGES

Lau, E. Y.; Wong, S. E.; Baker, S. E.; ...

2013-06-20

In nature, the zinc metalloenzyme carbonic anhydrase II (CAII) efficiently catalyzes the conversion of carbon dioxide (CO 2) to bicarbonate under physiological conditions. Efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolyl)phosphine, and tris(2-benzimidazolylmethyl)amine, in their complexed form either with the Zn 2+ or the Co 2+ ion and studied their reaction coordinate for CO 2 hydration. These calculations demonstrated that the ability of the complexmore » to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Moreover, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts.« less

H2 16O line list for the study of atmospheres of Venus and Mars

NASA Astrophysics Data System (ADS)

Lavrentieva, N. N.; Voronin, B. A.; Fedorova, A. A.

2015-01-01

IR spectroscopy is an important method of remote measurement of H2 16O content in planetary atmospheres with initial spectroscopic information from the HITRAN, GEISA, etc., databases adapted for studies in the Earth's atmosphere. Unlike the Earth, the atmospheres of Mars and Venus mainly consist of carbon dioxide with a CO2 content of about 95%. In this paper, the line list of H2 16O is obtained on the basis of the BT2 line list (R.J. Barber, J. Tennyson, G.J. Harris, et al., Mon. Not. R. Astron. Soc. 368, 1087 (2006)). The BT2 line list containing information on the centers, intensities, and quantum identification of lines is supplemented with the line contour parameters: the self-broadening and carbon dioxide broadening coefficients and the temperature dependence coefficient at 296 K in the range of 0.001-30000 cm-1. Transitions with intensity values 10-30, 10-32, and 10-35 cm/molecule, the total number of which is 323310, 753529, and 2011072, respectively, were chosen from the BT2 line list.

Differential Muon Tomography to Continuously Monitor Changes in the Composition of Subsurface Fluids

NASA Technical Reports Server (NTRS)

Coleman, Max; Kudryavtsev, Vitaly A.; Spooner, Neil J.; Fung, Cora; Gluyas, John

2013-01-01

Muon tomography has been used to seek hidden chambers in Egyptian pyramids and image subsurface features in volcanoes. It seemed likely that it could be used to image injected, supercritical carbon dioxide as it is emplaced in porous geological structures being used for carbon sequestration, and also to check on subsequent leakage. It should work equally well in any other application where there are two fluids of different densities, such as water and oil, or carbon dioxide and heavy oil in oil reservoirs. Continuous monitoring of movement of oil and/or flood fluid during enhanced oil recovery activities for managing injection is important for economic reasons. Checking on leakage for geological carbon storage is essential both for safety and for economic purposes. Current technology (for example, repeat 3D seismic surveys) is expensive and episodic. Muons are generated by high- energy cosmic rays resulting from supernova explosions, and interact with gas molecules in the atmosphere. This innovation has produced a theoretical model of muon attenuation in the thickness of rock above and within a typical sandstone reservoir at a depth of between 1.00 and 1.25 km. Because this first simulation was focused on carbon sequestration, the innovators chose depths sufficient for the pressure there to ensure that the carbon dioxide would be supercritical. This innovation demonstrates for the first time the feasibility of using the natural cosmic-ray muon flux to generate continuous tomographic images of carbon dioxide in a storage site. The muon flux is attenuated to an extent dependent on, amongst other things, the density of the materials through which it passes. The density of supercritical carbon dioxide is only three quarters that of the brine in the reservoir that it displaces. The first realistic simulations indicate that changes as small as 0.4% in the storage site bulk density could be detected (equivalent to 7% of the porosity, in this specific case). The initial muon flux is effectively constant at the surface of the Earth. Sensitivity of the method would be decreased with increasing depth. However, sensitivity can be improved by emplacing a greater array of particle detectors at the base of the reservoir.

Communication: Finding destructive interference features in molecular transport junctions.

PubMed

Reuter, Matthew G; Hansen, Thorsten

2014-11-14

Associating molecular structure with quantum interference features in electrode-molecule-electrode transport junctions has been difficult because existing guidelines for understanding interferences only apply to conjugated hydrocarbons. Herein we use linear algebra and the Landauer-Büttiker theory for electron transport to derive a general rule for predicting the existence and locations of interference features. Our analysis illustrates that interferences can be directly determined from the molecular Hamiltonian and the molecule-electrode couplings, and we demonstrate its utility with several examples.

Carbon Nanotube Devices Engineered by Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Prisbrey, Landon

This dissertation explores the engineering of carbon nanotube electronic devices using atomic force microscopy (AFM) based techniques. A possible application for such devices is an electronic interface with individual biological molecules. This single molecule biosensing application is explored both experimentally and with computational modeling. Scanning probe microscopy techniques, such as AFM, are ideal to study nanoscale electronics. These techniques employ a probe which is raster scanned above a sample while measuring probe-surface interactions as a function of position. In addition to topographical and electrostatic/magnetic surface characterization, the probe may also be used as a tool to manipulate and engineer at the nanoscale. Nanoelectronic devices built from carbon nanotubes exhibit many exciting properties including one-dimensional electron transport. A natural consequence of onedimensional transport is that a single perturbation along the conduction channel can have extremely large effects on the device's transport characteristics. This property may be exploited to produce electronic sensors with single-molecule resolution. Here we use AFM-based engineering to fabricate atomic-sized transistors from carbon nanotube network devices. This is done through the incorporation of point defects into the carbon nanotube sidewall using voltage pulses from an AFM probe. We find that the incorporation of an oxidative defect leads to a variety of possible electrical signatures including sudden switching events, resonant scattering, and breaking of the symmetry between electron and hole transport. We discuss the relationship between these different electronic signatures and the chemical structure/charge state of the defect. Tunneling through a defect-induced Coulomb barrier is modeled with numerical Verlet integration of Schrodinger's equation and compared with experimental results. Atomic-sized transistors are ideal for single-molecule applications due to their sensitivity to electric fields with very small detection volumes. In this work we demonstrate these devices as single-molecule sensors to detect individual N-(3-Dimethylaminopropyl)- N'-ethylcarbodiimide (EDC) molecules in an aqueous environment. An exciting application of these sensors is to study individual macromolecules participating in biological reactions, or undergoing conformational change. However, it is unknown whether the associated electrostatic signals exceed detection limits. We report calculations which reveal that enzymatic processes, such as substrate binding and internal protein dynamics, are detectable at the single-molecule level using existing atomic-sized transistors. Finally, we demonstrate the use of AFM-based engineering to control the function of nanoelectronic devices without creating a point defect in the sidewall of the nanotube. With a biased AFM probe we write charge patterns on a silicon dioxide surface in close proximity to a carbon nanotube device. The written charge induces image charges in the nearby electronics, and can modulate the Fermi level in a nanotube by +/-1 eV. We use this technique to induce a spatially controlled doping charge pattern in the conduction channel, and thereby reconfigure a field-effect transistor into a pn junction. Other simple charge patterns could be used to create other devices. The doping charge persists for days and can be erased and rewritten, offering a new tool for prototyping nanodevices and optimizing electrostatic doping profiles.

Visible light nitrogen dioxide spectrophotometer intercomparison: Mount Kobau, British Columbia, July 28 to August 10, 1991

NASA Technical Reports Server (NTRS)

Mcelroy, C. T.; Elokhov, A. S.; Elansky, N.; Frank, H.; Johnston, P.; Kerr, J. B.

1994-01-01

Under the auspices of the World Meteorological Organization, Environment Canada hosted an international comparison of visible light spectrophotometers at Mt. Kobau, British Columbia in August of 1991. Instruments from four countries were involved. The intercomparison results have indicated that some significant differences exist in the responses of the various instruments, and have provided a basis for the comparison of the historical data sets which currently exist as a result of the independent researches carried out in the past in the former Soviet Union, New Zealand, and Canada.

Optofluidic reactors for reverse combustion photocatalytic production of hydrocarbons (Conference Presentation)

NASA Astrophysics Data System (ADS)

Schein, Perry; Erickson, David

2017-03-01

In combustion, hydrocarbon fuels are burned with oxygen to release energy, carbon dioxide and water vapor. Here, we introduce a photocatalytic reactor for reversing this process, when carbon dioxide and water are combined and using optical and thermal energy from the sun hydrocarbons are produced and oxygen is released. This allows for the sustainable production of hydrocarbon products from non-fossil sources, allowing for the development of "green" hydrocarbon products. Our reactors take the form of modular cells of 10 x 10 x 10 cm scale where light is delivered to nanostructured catalysts through the evanescent field around dielectric slab waveguides. The light distribution is optimized through the use of engineered scattering sites to enhance field uniformity. This is combined with integrated fluidic architecture to deliver a stream rich in water and carbon dioxide (such as exhaust from a natural gas burning plant) to the nanostructured catalyst particles in a narrow channel. Exhaust streams rich in oxygen and hydrocarbon products are collected at the outlet of the reactor cell. The cell is heated using solar thermal energy and temperatures of up to 200°C are achieved, enhancing reaction efficiency. Hydrocarbon products produced include methanol as well as other potentially useful molecules for fuel production or precursors to the manufacture of plastics. These reactors can be coupled to solar collectors to take advantage of the sun as a free source of heat and light, and the modular nature of the cells enables scaling to larger deployments.

Preparation of Nonionic Vesicles Using the Supercritical Carbon Dioxide Reverse Phase Evaporation Method and Analysis of Their Solution Properties.

PubMed

Yamaguchi, Shunsuke; Tsuchiya, Koji; Sakai, Kenichi; Abe, Masahiko; Sakai, Hideki

2016-01-01

We have previously reported a new preparation method for liposomes using supercritical carbon dioxide (scCO2) as a solvent, referred to as the supercritical carbon dioxide reverse phase evaporation (scRPE) method. In our previous work, addition of ethanol to scCO2 as a co-solvent was needed, because lipid molecules had to be dissolved in scCO2 to form liposomes. In this new study, niosomes (nonionic surfactant vesicles) were prepared from various nonionic surfactants using the scRPE method. Among the nonionic surfactants tested were polyoxyethylene (6) stearylether (C18EO6), polyoxyethylene (5) phytosterolether (BPS-5), polyoxyethylene (6) sorbitan stearylester (TS-106V), and polyoxyethylene (4) sorbitan stearylester (Tween 61). All these surfactants have hydrophilic-lipophilic balance values (HLBs) around 9.5 to 9.9, and they can all form niosomes using the scRPE method even in the absence of ethanol. The high solubility of these surfactants in scCO2 was shown to be an important factor in yielding niosomes without ethanol addition. The niosomes prepared with the scRPE method had higher trapping efficiencies than those prepared using the conventional Bangham method, since the scRPE method gives a large number of unilamellar vesicles while the Bangham method gives multilamellar vesicles. Polyoxyethylene-type nonionic surfactants with HLB values from 9.5 to 9.9 were shown to be optimal for the preparation of niosomes with the scRPE method.

An ontology for major histocompatibility restriction.

PubMed

Vita, Randi; Overton, James A; Seymour, Emily; Sidney, John; Kaufman, Jim; Tallmadge, Rebecca L; Ellis, Shirley; Hammond, John; Butcher, Geoff W; Sette, Alessandro; Peters, Bjoern

2016-01-01

MHC molecules are a highly diverse family of proteins that play a key role in cellular immune recognition. Over time, different techniques and terminologies have been developed to identify the specific type(s) of MHC molecule involved in a specific immune recognition context. No consistent nomenclature exists across different vertebrate species. To correctly represent MHC related data in The Immune Epitope Database (IEDB), we built upon a previously established MHC ontology and created an ontology to represent MHC molecules as they relate to immunological experiments. This ontology models MHC protein chains from 16 species, deals with different approaches used to identify MHC, such as direct sequencing verses serotyping, relates engineered MHC molecules to naturally occurring ones, connects genetic loci, alleles, protein chains and multi-chain proteins, and establishes evidence codes for MHC restriction. Where available, this work is based on existing ontologies from the OBO foundry. Overall, representing MHC molecules provides a challenging and practically important test case for ontology building, and could serve as an example of how to integrate other ontology building efforts into web resources.

Ion mobility sensor

DOEpatents

Koo, Jackson C.; Yu, Conrad M.

2005-08-23

An ion mobility sensor which can detect both ion and molecules simultaneously. Thus, one can measure the relative arrival times between various ions and molecules. Different ions have different mobility in air, and the ion sensor enables measurement of ion mobility, from which one can identify the various ions and molecules. The ion mobility sensor which utilizes a pair of glow discharge devices may be designed for coupling with an existing gas chromatograph, where various gas molecules are already separated, but numbers of each kind of molecules are relatively small, and in such cases a conventional ion mobility sensor cannot be utilized.

The distribution of sulfur dioxide and other infrared absorbers on the surface of Io

USGS Publications Warehouse

Carlson, R.W.; Smythe, W.D.; Lopes-Gautier, R. M. C.; Davies, A.G.; Kamp, L.W.; Mosher, J.A.; Soderblom, L.A.; Leader, F.E.; Mehlman, R.; Clark, R.N.; Fanale, F.P.

1997-01-01

The Galileo Near Infrared Mapping Spectrometer was used to investigate the distribution and properties of sulfur dioxide over the surface of Io, and qualitative results for the anti-Jove hemisphere are presented here. SO2, existing as a frost, is found almost everywhere, but with spatially variable concentration. The exceptions are volcanic hot spots, where high surface temperatures promote rapid vaporization and can produce SO2-free areas. The pervasive frost, if fully covering the cold surface, has characteristic grain sizes of 30 to 100 Urn, or greater. Regions of greater sulfur dioxide concentrations are found. The equatorial Colchis Regio area exhibits extensive snowfields with large particles (250 to 500 ??m diameter, or greater) beneath smaller particles. A weak feature at 3.15 ??m is observed and is perhaps due to hydroxides, hydrates, or water. A broad absorption in the 1 ??m region, which could be caused by iron-containing minerals, shows a concentration in Io'S southern polar region, with an absence in the Pele plume deposition ring. Copyright 1997 by the American Geophysical Union.

Supercritical Carbon Dioxide and Its Potential as a Life-Sustaining Solvent in a Planetary Environment

PubMed Central

Budisa, Nediljko; Schulze-Makuch, Dirk

2014-01-01

Supercritical fluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercritical fluids. The special properties of supercritical fluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity) have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercritical fluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a “molecular memory”, i.e., the capacity to “remember” a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercritical fluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor), on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life. PMID:25370376

Supercritical carbon dioxide and its potential as a life-sustaining solvent in a planetary environment.

PubMed

Budisa, Nediljko; Schulze-Makuch, Dirk

2014-08-08

Supercritical fluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercritical fluids. The special properties of supercritical fluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity) have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercritical fluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a "molecular memory", i.e., the capacity to "remember" a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercritical fluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor), on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life.

Selective removal of dental composite using a rapidly scanned carbon dioxide laser

NASA Astrophysics Data System (ADS)

Chan, Kenneth H.; Fried, Daniel

2011-03-01

Dental restorative materials are color matched to the tooth and are difficult to remove by mechanical means without excessive removal or damage to peripheral enamel and dentin. Lasers are ideally suited for selective ablation to minimize healthy tissue loss when replacing existing restorations, sealants or removing composite adhesives such as residual composite left after debonding orthodontic brackets. In this study a carbon dioxide laser operating at high laser pulse repetition rates integrated with a galvanometer based scanner was used to selectively remove composite from tooth surfaces. A diode array spectrometer was used to measure the plume emission after each laser pulse and determine if the ablated material was tooth mineral or composite. The composite was placed on tooth buccal and occlusal surfaces and the carbon dioxide laser was scanned across the surface to selectively remove the composite without excessive damage to the underlying sound enamel. The residual composite and the damage to the underlying enamel was evaluated using optical microscopy. The laser was able to rapidly remove the composites rapidly from both surfaces with minimal damage to the underlying sound enamel.

Chemical markers of possible hot spots on Mars

NASA Astrophysics Data System (ADS)

Wong, Ah-San; Atreya, Sushil K.; Encrenaz, Thérèse

2003-04-01

Although there is no evidence of active volcanism on Mars today, ``localized'' outgassing sources, the hot spots, may not be ruled out. If outgassing does occur somewhere on Mars, water, carbon dioxide, sulfur species, methane, and to a lesser extent, halogens would be the likely molecules of outgassing, based on terrestrial analogs. The sulfur species, methane, and halogens have not been detected in the Martian atmosphere, but the observations were averaged over large areas, which could result in substantial dilution in abundances. If the interpretation of certain Mars Global Surveyor images indicating recent ground water seepage and surface runoff [Malin and Edgett, 2000] is correct, it may imply that Mars could still be active internally in some places from time to time, and outgassing of the abovementioned species may occur with or without the water seepage. Moreover, if the tentative detection of formaldehyde (CH2O) in the equatorial region of Mars [Korablev et al., 1993] is confirmed by future observations, it would imply at least local outgassing of methane, whose oxidation results in the formation of CH2O. Considering the possibility of outgassing from some localized hot spots, we have developed a one-dimensional photochemical model that includes methane (CH4), sulfur dioxide (SO2), and hydrogen sulfide (H2S), starting with their current ``global average'' upper limits of 0.02, 0.1, and 0.1 ppm at the surface, respectively, and then progressively increasing their abundances above possible hot spots. We find that the introduction of methane into the Martian atmosphere results in the formation of mainly formaldehyde, methyl alcohol (CH3OH), and ethane (C2H6), whereas the introduction of the sulfur species produces mainly sulfur monoxide (SO) and sulfuric acid (H2SO4). The effect of outgassed halogens on the Martian atmosphere is found to be negligible. Depending upon the flux of outgassed molecules from possible hot spots, some of these species and the resulting new molecules may be detectable locally, either by remote sensing or in situ measurements.

Distribution of Sulfur Dioxide Frost on Io

NASA Technical Reports Server (NTRS)

1997-01-01

Sulfur dioxide, normally a gas at room temperatures, is known to exist on Io's surface as a frost, condensing there from the hot gases emanating from the Io volcanoes. However, the deposition patterns and relation of the frost distribution to the volcanic activity is unknown, since prior measurements lacked the spatial resolution to accurately map the surface frost.

The Galileo Near Infrared Mapping Spectrometer (NIMS) obtained relatively high spatial and spectral resolution images during the C3 orbit, and the characteristic infrared absorptions of sulfur dioxide frost appearing in the spectra were used to produce the SO2 frost map shown on the right. The comparison image on the left (from 1979 Voyager measurements) shows the same view and indicates the surface brightness as seen in visible light.

The frost map shows maximum SO2 concentration as white, lesser amounts as blue coloration, and areas with little or no SO2 as black. The resolution of this map is about 120 km (75 miles), which spans the latitude range 120 W to 270 W.

It is interesting to compare this frost distribution with regions of volcanic activity. Volcanic hotspots identified from NIMS and SSI images occur in many of the dark - low SO2 - areas, a reasonable finding since sulfur dioxide would not condense on such hot regions. The Pele region (to the lower left), N. Colchis hot spots (upper center) and S. Volund (upper right) are good examples of hot spot areas depleted in sulfur dioxide. Much of the rest of this hemisphere of Io has varying amounts of sulfur dioxide present. The most sulfur dioxide-rich area is Colchis Regio, the white area to the right of center.

Of particular interest is the dark area to the south of Colchis Regio. From the study of other NIMS images, it is seen that this region does not have any large, obvious hotspots. However, it is depleted in sulfur dioxide.

The Jet Propulsion Laboratory, Pasadena, CA manages the mission for NASA's Office of Space Science, Washington, DC.

The Jet Propulsion Laboratory, Pasadena, CA manages the mission for NASA's Office of Space Science, Washington, DC.

This image and other images and data received from Galileo are posted on the World Wide Web, on the Galileo mission home page at URL http://galileo.jpl.nasa.gov.

Implications of global climate change for Southern forests: Can we separate fact from fiction?

Treesearch

Hermann Gucinski; Ron Neilson; Steve McNulty

2004-01-01

There is no scientific dispute regarding the existence of a greenhouse effect. There is no doubt that water vapor, carbon dioxide (CO2), and methane concentrations are greenhouse gases. The data showing increases in CO2 in the atmosphere are incontrovertible. Uncertainties arise when the Earth's biological responses to climate change are to...

The Greenhouse Effect and Built Environment Education.

ERIC Educational Resources Information Center

Greenall Gough, Annette; Gough, Noel

The greenhouse effect has always existed. Without the greenhouse effect, Earth could well have the oven-like environment of Venus or the deep-freeze environment of Mars. There is some debate about how much the Earth's surface temperature will rise given a certain amount of increase in the amount of greenhouse gases such as carbon dioxide, nitrous…

76 FR 18407 - Standards of Performance for New Stationary Sources and Emissions Guidelines for Existing Sources...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-04

... removing extraneous text from the hydrogen chloride emissions limit for large hospital/medical/infectious.../dibenzofurans, carbon monoxide, nitrogen oxides (NO X ), hydrogen chloride (HCl), and sulfur dioxide (SO 2...\\ dscf). Hydrogen chloride ppmv or percent 100 or 93% 100 or 93% 100 or 93% 3-run average (1- EPA...

NO to NO2 conversion rate analysis and implications for dispersion model chemistry methods using Las Vegas, Nevada near-road field measurements

EPA Science Inventory

Nitrogen dioxide/oxides of nitrogen (NO2/NOX) ratios are an important surrogate for nitric oxide (NO) NO-to-NO2 chemistry in dispersion models when estimating NOX emissions in a near-road environment. Existing dispersion models use different techniques and assumptions to represe...

Molecular approaches to the photocatalytic reduction of carbon dioxide for solar fuels.

PubMed

Morris, Amanda J; Meyer, Gerald J; Fujita, Etsuko

2009-12-21

The scientific community now agrees that the rise in atmospheric CO(2), the most abundant green house gas, comes from anthropogenic sources such as the burning of fossil fuels. This atmospheric rise in CO(2) results in global climate change. Therefore methods for photochemically transforming CO(2) into a source of fuel could offer an attractive way to decrease atmospheric concentrations. One way to accomplish this conversion is through the light-driven reduction of carbon dioxide to methane (CH(4(g))) or methanol (CH(3)OH((l))) with electrons and protons derived from water. Existing infrastructure already supports the delivery of natural gas and liquid fuels, which makes these possible CO(2) reduction products particularly appealing. This Account focuses on molecular approaches to photochemical CO(2) reduction in homogeneous solution. The reduction of CO(2) by one electron to form CO(2)(*-) is highly unfavorable, having a formal reduction potential of -2.14 V vs SCE. Rapid reduction requires an overpotential of up to 0.6 V, due at least in part to the kinetic restrictions imposed by the structural difference between linear CO(2) and bent CO(2)(*-). An alternative and more favorable pathway is to reduce CO(2) though proton-assisted multiple-electron transfer. The development of catalysts, redox mediators, or both that efficiently drive these reactions remains an important and active area of research. We divide these reactions into two class types. In Type I photocatalysis, a molecular light absorber and a transition metal catalyst work in concert. We also consider a special case of Type 1 photocatalysis, where a saturated hydrocarbon links the catalyst and the light absorber in a supramolecular compound. In Type II photocatalysis, the light absorber and the catalyst are the same molecule. In these reactions, transition-metal coordination compounds often serve as catalysts because they can absorb a significant portion of the solar spectrum and can promote activation of small molecules. This Account discusses four classes of transition-metal catalysts: (A) metal tetraaza-macrocyclic compounds; (B) supramolecular complexes; (C) metalloporphyrins and related metallomacrocycles; (D) Re(CO)(3)(bpy)X-based compounds where bpy = 2,2'-bipyridine. Carbon monoxide and formate are the primary CO(2) reduction products, and we also propose bicarbonate/carbonate production. For comprehensiveness, we briefly discuss hydrogen formation, a common side reaction that occurs concurrently with CO(2) reduction, though the details of that process are beyond the scope of this Account. It is our hope that drawing attention both to current mechanistic hypotheses and to the areas that are poorly understood will stimulate research that could one day provide an efficient solution to this global problem.

Carbon Dioxide Removal by Salty Aerosols

NASA Astrophysics Data System (ADS)

Gokturk, H.

2016-12-01

Aerosols consisting of salt ions dissolved in water are observed in nature as sea spray particles generated by breaking waves. Such aerosols can be also generated artificially by spraying seawater to the atmosphere to create clouds, which was suggested as a method of solar radiation management (SRM). Salty aerosols can be utilized not only for SRM, but also for carbon dioxide removal from the atmosphere, if salt ions carrying charges -2 or more negative are added to the seawater. CO2 is a very stable molecule where carbon to oxygen double bond has a bond strength of 8.3 eV (190 kcal/mol). Therefore the approach chosen here to modify CO2 is to further oxidize it to CO3. Quantum mechanical calculations indicate that CO2 reacts readily with hydroxyl minus ion (OH-) or oxygen double minus ion (O-) to form HCO3- or CO3-, respectively. What is studied in this paper is the utilization of hydrated negative salt ions to create OH- and possibly even O-. The negative ions chosen are chlorine minus ion (Cl-), sulfate double minus ion (SO4-), phosphate triple minus ion (PO4--) and silicate quadruple minus ion (SiO4--). The former two ions exist in seawater, but the latter two ions do not, though they are available as part of water soluble salts such as potassium phosphate. Using quantum mechanical calculations, following reactions were investigated: R1: (Cl-) + H2O => HCl + (OH-), R2: (SO4-) + H2O => (HSO4-) + (OH-), R3: (PO4--) + H2O => (HPO4-) + (OH-), R4: (SiO4--) + H2O => (HSiO4--) + (OH-), R5: (HPO4-) + H2O => (H2PO4-) + (OH-), R6: (HSiO4--) + H2O => (H2SiO4-) + (OH-), R7: (H2SiO4-) + H2O => (H3SiO4-) + (OH-), R8: (SiO4--) + H2O => (H2SiO4-) + (O-). Results indicate that singly charged negative salt ions, such as Cl- in R1, cannot create OH-. Doubly charged negative salt ions, such as SO4- in R2, can create OH-, though the amount of SO4- in seawater is relatively small. Triply or quadruply charged negative ions are even more favorable than doubly charged ions in creating OH- (R3, R4, R6). Quadruply charged negative ions can also create O- (R8), however in practice O- is likely to react with other water molecules to create more OH-. In conclusion, seawater fortified with highly charged negative salt ions and sprayed into the atmosphere has the potential to create aerosols containing OH- which can react with the CO2 and modify it to a carbonate.

Order from Force; A natural history of the vacuum

NASA Astrophysics Data System (ADS)

Williams, Jeffrey H.

2015-11-01

The laws of physics govern our lives, and the fundamental constants of Nature (for example, the mass and charge of the electron) define our very morphology. If a human body were totally dehydrated there would only remain about thirty kilograms of crystals and powder, after having removed about fifty litres of water. Yet the amazing machine that is our body functions because of the forces of interaction (attraction and repulsion) that exist between the molecules in that powder when fully hydrated. These forces of interaction are mediated and directed by the vast amount of water that is present. It is the precise orientation of one hydrated molecule with respect to another hydrated molecule, at a well-defined separation, in our central nervous systems that allows a nerve impulse to tunnel quantum-mechanically through the intermediate space between two nerve cells at a synapse. Thereby allowing us to observe our environment, and contemplate our existence. It is the arrangement of the water molecules along molecules of muscle proteins that allows one protein molecule to slide over neighbouring protein molecules, thereby allowing us to do exercise and work, or to hunt and to gather. The precise distances and orientations between the molecules of which our bodies are composed are determined by subtle intermolecular electrostatic forces, whose magnitude is determined by the various constants of Nature, and whose operation is dictated by the laws of physics. We are merely living representations of these immutable physical laws.

Characteristics of Hydrogen Sensors Based on Thin Tin Dioxide Films Modified with Gold

NASA Astrophysics Data System (ADS)

Almaev, A. V.; Gaman, V. I.

2017-11-01

Effect of hydrogen in the concentration range from 10 to 2000 ppm on the characteristics of sensors based on thin films of tin dioxide modified with gold (Au/SnO2:Sb, Au) is studied in the thermo-cyclic mode at temperatures from 623 to 773 K and absolute humidity from 2.5 to 20 g/m3. Experimental data are discussed using expressions obtained within the framework of a model that takes into account the presence of three types of adsorbed particles (O¯, OH, and OH¯) on the surface of SnO2 nanocrystals. The characteristics of the sensors based on thin Pt/Pd/SnO2:Sb films (the first series) are compared with those of Au/SnO2:Sb, Au films (the second series). It is found that the degree of dissociation of molecular hydrogen into atoms during adsorption on the sensor under interaction with Au particles on the SnO2 surface is 4 times greater than that under interaction with Pt/Pd particles. The degree of dissociation of H2O molecules into hydrogen atoms and hydroxyl groups in pure moist air on the surface of the sensors of the second series is 1.6 times greater than that for the sensors of the first series. Thus, gold is a more effective stimulator of the dissociation of H2 and H2O molecules than platinum and palladium. A formula is obtained that describes more accurately the dependence of the response of the sensors of both series to the effect of hydrogen on the concentration of this gas and on the temperature of the measuring devices.

Localization of intercellular adhesion molecule-1 (ICAM-1) in the lungs of silica-exposed mice.

PubMed Central

Nario, R C; Hubbard, A K

1997-01-01

Intercellular adhesion molecule-1 (ICAM-1) is expressed on a variety of cells including endothelial cells, alveolar epithelial cells, and alveolar macrophages. Endothelial/epithelial cell ICAM-1 participates in the migration of leukocytes out of the blood in response to pulmonary inflammation, whereas alveolar macrophage ICAM-1 may represent cell activation. Our previous studies have shown that there is increased expression of ICAM-1 in lung tissue during acute inflammation following intratracheal injection with silica particles (2 mg/mouse). This increased expression was shown to play a role, in part, in the migration of neutrophils from the circulation into the tissue parenchyma. The aim of the current work is to localize expression of ICAM-1 during acute inflammation in lungs of mice exposed to either silica or the nuisance dust, titanium dioxide. In silica-exposed mice, a significant increase in ICAM-1 was detected on day-1 and localized by immunohistochemistry to aggregates of pulmonary macrophages and to type II epithelial cells. Areas of the lung with increased ICAM-1 expression also showed increased tumor necrosis factor alpha expression. Immunocytochemical staining of bronchoalveolar lavage (BAL) cells demonstrated increased ICAM-1 expression associated with alveolar macrophages 3, 5, and 7 days following silica exposure. Finally, soluble ICAM-1 levels in the BAL fluid were significantly increased in mice exposed to silica on the same days. Titanium dioxide exposure elicited a minimal increase in expression of ICAM-1 in the lungs. These data demonstrate that exposure to the toxic particle silica specifically increases ICAM-1 expression localized to pulmonary macrophages and type II epithelial cells. Images Figure 2. B Figure 2. A Figure 2. D Figure 2. C Figure 3. A Figure 3. B Figure 5. B Figure 5. A Figure 5. C PMID:9400721

UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation.

PubMed

Luo, Feng; Yan, Changsheng; Dang, Lilong; Krishna, Rajamani; Zhou, Wei; Wu, Hui; Dong, Xinglong; Han, Yu; Hu, Tong-Liang; O'Keeffe, Michael; Wang, Lingling; Luo, Mingbiao; Lin, Rui-Biao; Chen, Banglin

2016-05-04

A new metal-organic framework Zn2(H2O)(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 Å. Unlike metal sites in the well-established MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn(2+) sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm(3)/cm(3)) to Zn-MOF-74. Interestingly, the accessible Zn(2+) sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm(3)/cm(3)) than Zn-MOF-74 (146 cm(3)/cm(3)) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result.

Interactions between CO2, minerals, and toxic ions: Implications for CO2 leakage from deep geological storage (Invited)

NASA Astrophysics Data System (ADS)

Renard, F.; Montes-Hernandez, G.

2013-12-01

The long-term injection of carbon dioxide into geological underground reservoirs may lead to leakage events that will enhance fluid-rock interactions and question the safety of these repositories. If injection of carbon dioxide into natural reservoirs has been shown to mobilize some species into the pore fluid, including heavy metals and other toxic ions, the detailed interactions remain still debated because two main processes could interact and modify fluid composition: on the one hand dissolution/precipitation reactions may release/incorporate trace elements, and on the other hand adsorption/desorption reactions on existing mineral surfaces may also mobilize or trap these elements. We analyze here, through laboratory experiments, a scenario of a carbon dioxide reservoir that leaks into a fresh water aquifer through a localized leakage zone such as a permeable fault zone localized in the caprock and enhance toxic ions mobilization. Our main goal is to evaluate the potential risks on potable water quality. In a series of experiments, we have injected carbon dioxide into a fresh water aquifer-like medium that contained carbonate and/or iron oxide particles, pure water, and various concentrations of trace elements (copper, arsenic, cadmium, and selenium, in various states of oxidation). This analogue and simplified medium has been chosen because it contains two minerals (calcite, goethite) widespread found in freshwater aquifers. The surface charge of these minerals may vary with pH and therefore control how trace elements are adsorbed or desorbed, depending on fluid composition. Our experiments show that these minerals could successfully prevent the remobilization of adsorbed Cu(II), Cd(II), Se(IV), and As(V) if carbon dioxide is intruded into a drinking water aquifer. Furthermore, a decrease in pH resulting from carbon dioxide intrusion could reactivate the adsorption of Se(IV) and As(V) if goethite and calcite are sufficiently available in the aquifer. Our results also suggest that adsorption of cadmium and copper could be promoted by calcite dissolution. These ions adsorbed on calcite are not remobilized when carbon dioxide is intruded into the system, even if calcite dissolution is intensified. On the other hand, arsenite As(III), significantly adsorbed on goethite, is partially remobilized by carbon dioxide intrusion. These results show that carbon dioxide may, in some case remobilize some toxic ions in the pore fluid, but the pH effect may also enhance adsorption of other toxic ione on calcite and goethite particles.

Electron Paramagnetic Resonance Spectroscopic Study on Nonequilibrium Reaction Pathways in the Photolysis of Solid Nitromethane (CH3NO2) and D3-Nitromethane (CD3NO2).

PubMed

Tsegaw, Yetsedaw Andargie; Sander, Wolfram; Kaiser, Ralf I

2016-03-10

Thin films of nitromethane (CH3NO2) along with its isotopically labeled counterpart D3-nitromethane (CD3NO2) were photolyzed at discrete wavelength between 266 nm (4.7 eV) and 121 nm (10.2 eV) to explore the underlying mechanisms involved in the decomposition of model compounds of energetic materials in the condensed phase at 5 K. The chemical modifications of the ices were traced in situ via electron paramagnetic resonance, thus focusing on the detection of (hitherto elusive) reaction intermediates and products with unpaired electrons. These studies revealed the formation of two carbon-centered radicals [methyl (CH3), nitromethyl (CH2NO2)], one oxygen-centered radical [methoxy (CH3O)], two nitrogen-centered radicals [nitrogen monoxide (NO), nitrogen dioxide (NO2)], as well as atomic hydrogen (H). The decomposition products of these channels and the carbon-centered nitromethyl (CH2NO2) radical in particular represent crucial reaction intermediates leading via sequential molecular mass growth processes in the exposed nitromethane samples to complex organic molecules as predicted previously by dynamics calculations. The detection of the nitromethyl (CH2NO2) radical along with atomic hydrogen (H) demonstrated the existence of a high-energy decomposition pathway, which is closed under collisionless conditions in the gas phase.

The Three Forms of Molecular Oxygen.

ERIC Educational Resources Information Center

Laing, Michael

1989-01-01

Finds that a logical application of the simple rules of the molecular orbital bonding theory for diatomic molecules predicted the existence of three spin isomers of the oxygen molecule: one triplet form with two unpaired electrons and two singlet forms with all electrons paired. (MVL)

CO/sub 2/ line design needs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Recht, D.L.

Large volumes of carbon dioxide are required for tertiary oil recovery projects that utilize the carbon dioxide miscible flooding method. Carbon dioxide can be successfully transported as a supercritical fluid through a pipeline designed and operated similar to a natural gas pipeline, with careful consideration given to specific differences in design and materials of construction. Carbon dioxide is a colorless, odorless, nonflammable, non-toxic substance that may exist as a gas, as a liquid, as a solid, or in all three forms at its triple point. The critical pressure and temperature of CO/sub 2/ are 1,070 psia and 88/sup 0/F, respectively.more » It is present in the normal atmosphere in a concentration of approximately 330 ppm, and somewhat higher concentrations may occur in occupied buildings. Air in lungs contains approximately 5.5% (55,000 ppm) of CO/sub 2/. Although it is non-toxic, air containing 10% to 20% CO/sub 2/ concentrations by volume is immediately hazardous to life by causing unconsciousness, failure of respiratory muscles, and a change in the pH of the blood stream. Carbon dioxide is commonly used for carbonated beverages, aerosol propellants, fire extinguishers, enrichment of air in greenhouses, fracturing and acidizing of oil wells, as a shielding gas for welding, and as dry ice for refrigeration. In tertiary recovery projects of suitable oil reservoirs, CO/sub 2/ is injected into the formation where it dissolves in the oil, swells the oil, reduces the oil's viscosity, exerts an acidic effect on the reservoir rock (in some cases), and vaporizes some of the oil. As a rough rule of thumb, approximately 6 to 10 mcf of CO/sub 2/ are required to be injected for recovery of 1 bbl of oil. Carbon dioxide miscible flooding will recover approximately 10% to 15% of the oil remaining in place after a waterflood program.« less

A new process for converting SO2 to sulfur without generating secondary pollutants through reactions involving CaS and CaSO4.

PubMed

Sohn, H Y; Kim, Byung-Su

2002-07-01

Nonferrous smelters and coal gasification processes generate environmentally harmful sulfur dioxide streams, most of which are treated to produce sulfuric acid with the accompanying problems of market shortage and transportation difficulties. Some sulfur dioxide streams are scrubbed with an alkali solution or a solid substance such as limestone or dolomite, which in turn generates wastes that pose other pollution problems. While the conversion of sulfur dioxide to elemental sulfur has many environmental advantages, no processes exist that are environmentally acceptable and economically viable. A new method for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium sulfide and calcium sulfate without generating solid wastes has been developed. In this process, calcium sulfate pellets as the starting raw material are reduced by a suitable reducing agent such as hydrogen to produce calcium sulfide pellets, which are used to reduce sulfur dioxide producing elemental sulfur vapor and calcium sulfate. The latter is then reduced to regenerate calcium sulfide. Thermodynamic analysis and experimental results indicated that the CaS-SO2 reaction produces mainly sulfur vapor and solid calcium sulfate and that the gaseous product from the CaSO4-H2 reaction is mainly water vapor. The rates of the two reactions are reasonably rapid in the temperature range 1000-1100 K, and, importantly, the physical strengths and reactivities of the pellets are maintained largely unchanged up to the tenth cycle, the last cycle tested in this work. Sulfur dioxide-containing streams from certain sources, such as the regenerator off-gas from an integrated gasification combined cycle desulfurization unit and new sulfide smelting plants, contain much higher partial pressures of SO2. In these cases, the rate of the first reaction is expected to be proportionally higher than in the test conditions reported in this paper.

[Sulfur dioxide limit standard and residues in Chinese medicinal materials].

PubMed

Kang, Chuan-Zhi; Yang, Wan-Zhen; Mo, Ge; Zhou, Li; Jiang, Jing-Yi; Lv, Chao-Geng; Wang, Sheng; Zhou, Tao; Yang, Ye; Guo, Lan-Ping

2018-01-01

The traditional sulfur fumigation processing method has been widely used in the initial processing and storage of traditional Chinese medicinal materials due to its economy, efficiency, convenience, high operability and effect on mold and insect prevention. However, excessive sulfur fumigation of traditional Chinese medicinal materials would lead to the changes in chemical compositions, and even endanger human health. This study showed that traditional Chinese medicinal materials were sulfur fumigated directly after being harvested for quick drying, or fumigated after being weted in the storage process for preventing mold and insects. We found that the sulfur dioxide limits for traditional Chinese medicinal materials were stricter than those for foods. Based on the existing limit standards, we obtained the data of sulfur dioxide residues for 35 types of traditional Chinese medicinal materials in a total of 862 batches. According to the limit standard in the Chinese Pharmacopoeia (150， 400 mg·kg⁻¹), the average over-standard rate of sulfur dioxide was as high as 52.43%, but it was reduced to 29.47% if calculated based on the limit for vegetable additive standard (500 mg·kg⁻¹). Sulfur fumigation issue shall be considered correctly: sulfur dioxide is a type of low toxic substance and less dangerous than aflatoxin and other highly toxic substances, and a small amount of residue would not increase the toxicity of traditional Chinese medicinal materials. However, sulfur fumigation might change the content of chemical substances and affect the quality of traditional Chinese medicinal materials. Furthermore, the exposure hazards of toxic substances are comprehensively correlated with exposure cycle, exposure frequency, and application method. In conclusion, it is suggested to strengthen the studies on the limit standard of traditional Chinese medicinal materials, formulate practical and feasible limit standard for sulfur dioxide residues in traditional Chinese medicinal materials that are consistent with the medication characteristics of traditional Chinese medicinal materials and can guarantee people's demand for safe medication. Copyright© by the Chinese Pharmaceutical Association.

Electrocatalytic Production of C3-C4 Compounds by Conversion of CO2 on a Chloride-Induced Bi-Phasic Cu2O-Cu Catalyst.

PubMed

Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung

2015-12-01

Electrocatalytic conversion of carbon dioxide (CO2) has recently received considerable attention as one of the most feasible CO2 utilization techniques. In particular, copper and copper-derived catalysts have exhibited the ability to produce a number of organic molecules from CO2. Herein, we report a chloride (Cl)-induced bi-phasic cuprous oxide (Cu2O) and metallic copper (Cu) electrode (Cu2OCl) as an efficient catalyst for the formation of high-carbon organic molecules by CO2 conversion, and identify the origin of electroselectivity toward the formation of high-carbon organic compounds. The Cu2OCl electrocatalyst results in the preferential formation of multi-carbon fuels, including n-propanol and n-butane C3-C4 compounds. We propose that the remarkable electrocatalytic conversion behavior is due to the favorable affinity between the reaction intermediates and the catalytic surface. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

LETTER TO THE EDITOR: Differential electron scattering from the (010) excited vibrational mode of N2O

NASA Astrophysics Data System (ADS)

Akther, P.; Johnstone, W. M.; El-Zein, A. A. A.; Campbell, L.; Teubner, P. J. O.; Brunger, M. J.; Newell, W. R.

2002-11-01

In this letter we report differential superelastic, elastic and inelastic electron scattering measurements from nitrous oxide (N2O) in its (010)* excited vibrational quantum. The incident electron energy was 2.5 eV and the scattered electron angular range was 10°- 40°. Unlike our previous results (1999 J. Phys. B: At. Mol. Opt. Phys. 32 5779) with the isoelectronic molecule carbon dioxide (CO2), where the elastic differential cross sections (DCSs) for scattering from the (010)* mode were 2.3 times larger than those for elastic scattering from the ground (000) state, in N2O the corresponding (010)* elastic cross sections are usually only a fraction of those for the ground state. To the best of our knowledge, the present data are the first DCSs which have been reported in the literature for electron scattering from an excited vibrational level of the N2O molecule.

Simultaneous photodegradation of VOC mixture by TiO2 powders.

PubMed

Stucchi, Marta; Galli, Federico; Bianchi, Claudia L; Pirola, Carlo; Boffito, Daria C; Biasioli, Franco; Capucci, Valentino

2018-02-01

Volatile and semi volatile organic compounds' concentration have dramatically increased in indoor environments in recent years. UV light promotes titanium dioxide, which oxidises various molecules; however, most of the studies report the degradation of a single VOC. Here, we investigate the photo-oxidation of 17 molecules in mixture to have a realistic test of TiO 2 efficacy. We compare P25, a nanometric catalyst, and 1077, a micrometric sample, that poses less health concerns. A proton-transfer-reaction mass spectrometer measured online the concentration of all the pollutants simultaneously. Aldehydes compete for the adsorption on both the catalyst's active sites and thus they degrade 70% and 55% with P25 and 1077 respectively. Considering the single pollutant oxidation, instead, aldehydes fully oxidize. Even though benzene is recalcitrant to degradation, P25 and 1077 reduced toluene's concentration to 97% and 96% in 55 min, respectively. Acetonitrile is refractory to photocatalysis. Copyright © 2017. Published by Elsevier Ltd.

Field Tests of a Gas-Filter Imaging Radiometer for Methane, CH4,: A Prototype for Geostationary Remote Infrared Pollution Sounder, GRIPS

NASA Astrophysics Data System (ADS)

Dickerson, R. R.; Fish, C. S.; Brent, L. C.; Burrows, J. P.; Fuentes, J. D.; Gordley, L. L.; Jacob, D. J.; Schoeberl, M. R.; Salawitch, R. J.; Ren, X.; Thompson, A. M.

2013-12-01

Gas filter radiometry is a powerful tool for measuring infrared active trace gases. Methane (CH4) is the second most important greenhouse gas and is more potent molecule for molecule than carbon dioxide (CO2). Unconventional natural gas recovery has the potential to show great environmental benefits relative to coal, but only if fugitive leakage is held below 3% and leak rates remain highly uncertain. We present design specifications and initial field/aircraft test results for an imaging remote sensing device to measure column content of methane. The instrument is compared to in situ altitude profiles measured with cavity ring-down. This device is an airborne prototype for the Geostationary Remote Infrared Pollution Sounder, GRIPS, a satellite instrument designed to monitor CH4, CO2, CO, N2O and AOD from geostationary orbit, with capabilities for great advances in air quality and climate research. GRIPS: The Geostationary Remote Infrared Pollution Sounder

Carbocation/Polyol Systems as Efficient Organic Catalysts for the Preparation of Cyclic Carbonates.

PubMed

Rulev, Yuri A; Gugkaeva, Zalina T; Lokutova, Anastasia V; Maleev, Victor I; Peregudov, Alexander S; Wu, Xiao; North, Michael; Belokon, Yuri N

2017-03-22

Carbocation/polyol systems are shown to be highly efficient catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide at 50 °C and 5 MPa CO 2 pressure. The best activity was shown by the combination of crystal violet and 1,1'-bi-2-naphthol (BINOL), which could be recycled five times with no loss of activity. The presence of specific interactions between the amino groups of the carbocation and the hydroxyl protons was confirmed by NMR experiments. The Job plots for the crystal violet iodide/BINOL and brilliant green iodide/BINOL systems showed that the catalytic systems consist of one molecule of the carbocation and one molecule of BINOL. Mechanistic studies using a deuterated epoxide indicate that there was some loss of epoxide stereochemistry during the reaction, but predominant retention of stereochemistry is observed. On this basis, a catalytic cycle is proposed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of the sodium phenytoin effect on the formation of sol-gel SiO 2 nanotubes by TEM

NASA Astrophysics Data System (ADS)

López, T.; Asomoza, M.; Picquart, M.; Castillo-Ocampo, P.; Manjarrez, J.; Vázquez, A.; Ascencio, J. A.

2005-04-01

Microencapsulation is a versatile technology that allows controlling the release of different active molecules. Recently the sol-gel process has emerged like a promising method to immobilization and stabilization of biologically active compounds like enzymes, antigens, microorganisms and drugs. Porous silica and titanium dioxide materials made by low temperature sol-gel processes are promising host matrixes for encapsulation of biological molecules. The preparation of a low-temperature silica sol followed by gelation to neutral pH with water for injection containing the antiepileptic drug is reported here. The structure is very important so the analysis of the new developed material is also reported. Particularly interesting is the presence of nanotubes and microtubes, produced in the inorganic matrix in the presence of the sodium phenytoin. The use of transmission electron microscopy and quantum mechanics molecular simulation allows determining a micelle-like effect during the synthesis of these materials, which controls the size, structure and stability of them.

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates.

PubMed

Qiao, Zhen-An; Chai, Song-Hai; Nelson, Kimberly; Bi, Zhonghe; Chen, Jihua; Mahurin, Shannon M; Zhu, Xiang; Dai, Sheng

2014-04-16

High-performance polymeric membranes for gas separation are attractive for molecular-level separations in industrial-scale chemical, energy and environmental processes. Molecular sieving materials are widely regarded as the next-generation membranes to simultaneously achieve high permeability and selectivity. However, most polymeric molecular sieve membranes are based on a few solution-processable polymers such as polymers of intrinsic microporosity. Here we report an in situ cross-linking strategy for the preparation of polymeric molecular sieve membranes with hierarchical and tailorable porosity. These membranes demonstrate exceptional performance as molecular sieves with high gas permeabilities and selectivities for smaller gas molecules, such as carbon dioxide and oxygen, over larger molecules such as nitrogen. Hence, these membranes have potential for large-scale gas separations of commercial and environmental relevance. Moreover, this strategy could provide a possible alternative to 'classical' methods for the preparation of porous membranes and, in some cases, the only viable synthetic route towards certain membranes.

Effects of hydrogen bonding between pyrrole-2-carboxaldehyde and nearest polar and nonpolar environment

NASA Astrophysics Data System (ADS)

Rana, Meenakshi; Chowdhury, Papia

2017-10-01

The present paper represents dominant effects of hydrogen bonding on the existence of different molecular aggregates in one of the heterocyclic pyrrole system: pyrrole-2-carboxaldehyde (PCL). Theoretical and experimental Raman spectral evidence verifies the existence of different molecular aggregates like dimeric, monomeric, hydrated complex states in PCL. Atoms in molecules (AIMs) analysis and fluorescence decay profile provide a strong signature of intermolecular hydrogen bonding (IerHB) as the possible reason for the existence of cis form of dimeric (X) molecular aggregates. The high remnant polarization of 3.13 μCcm- 2 and smaller dielectric loss in solid form of PCL arise due to in X by ordering of dipoles as a result of IerHB. A remarkable high ferroelectric response in solid phase makes PCL a desirable candidate to be used as raw material for energy storage devices. For solution phase, in presence of external hydroxylic environment, PCL reacts with external water molecules through weak IerHB and creates different hydrated PCL/(H2O)n complexes by creating water bridge with number of water molecules from 1 to n. An increasing number of water molecules helps to form stronger hydrated complex by separation of charges by lowering the transferring energy barrier.

Excited Negative Ions and Molecules and Negative Ion Production

DTIC Science & Technology

1992-01-01

theoretically to have negative electron affinities, analogous to the rare gases. Then, Froese Fischer et al.I found theoretically that Ca- exists...AD-A247 017 Final Report - January 1992 EXCITED NEGATIVE IONS AND MOLECULES AND NEGATIVE ION PRODUCTION OTIC James R. Peterson, Senior Staff...Vice President 92-05594Physical Sciences Division1111111111II fuii 1111 ii 92 3 ’ Final Report . January 1992 EXCITED NEGATIVE IONS AND MOLECULES AND

On the metal-insulator-transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Jovaini, Azita; Fujita, Shigeji; Godoy, Salvador; Suzuki, Akira

2012-02-01

Vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340 K with the structural change from tetragonal to monoclinic crystal. The conductivity σ drops at MIT by four orders of magnitude. The low temperature monoclinic phase is known to have a lower ground-state energy. The existence of the k-vector k is prerequisite for the conduction since the k appears in the semiclassical equation of motion for the conduction electron (wave packet). The tetragonal (VO2)3 unit is periodic along the crystal's x-, y-, and z-axes, and hence there is a three-dimensional k-vector. There is a one-dimensional k for a monoclinic crystal. We believe this difference in the dimensionality of the k-vector is the cause of the conductivity drop.

[Effects of air pollution on human health and their importance in Mexico City].

PubMed

Vallejo, Maite; Jáuregui-Renaud, Kathrine; Hermosillo, Antonio G; Márquez, Manlio F; Cárdenas, Manuel

2003-01-01

The impact of air pollution on human health is a complicated problem. In this review, we describe the main health effects of exposure to ozone, carbon monoxide, sulfur dioxide, nitrogen dioxide, lead and particulate matter. Geographical characteristics of the metropolitan area of Mexico City that favor pollutant persistence with adverse effects on the population are described; the use of the Indice Metropolitano de la Calidad del Aire (IMECA), current norms, and present programs to diminish this problem are discussed. Evidence shows that through these actions, air quality has improved. However, some pollutants such as ozone and particulate matter, still exceed the standard. To further improve air quality in the city, existing programs should continue and multidisciplinary research, both basic and applied, is required.

Volcanic recycling of carbonates on Mars

NASA Technical Reports Server (NTRS)

Schaefer, M. W.

1993-01-01

Thermal erosion of carbonate deposits by turbulently-flowing lava is investigated as a means of recycling carbon dioxide back into the atmosphere of Mars. Erosion rates of several meters/day are found, implying that up to hundreds of meters of carbonate could be removed over the lifetime of a flow. A large fraction of the northern plains and other parts of Mars were covered by lava during the Hesperian, and may have released the carbon dioxide trapped in carbonate deposits. This period of time, several times 10 exp 8 yrs, is comparable to that for the redeposition of such carbonate deposits. Therefore, there could have existed a relatively dense atmosphere, and enhanced weathering and erosion, after the Noachian era. This may help explain the apparent observational evidence for late fluvial and lacustrine activity on Mars.

Systems biology, adverse outcome pathways, and ecotoxicology in the 21st century

EPA Science Inventory

While many definitions of systems biology exist, the majority of these contain most (if not all) of the following elements: global measurements of biological molecules to the extent technically feasible, dynamic measurements of key biological molecules to establish quantitative r...

A simple diagnostic test to confirm correct intravascular placement of peripheral catheters in order to avoid extravasation.

PubMed

Keidan, Ilan; Sidi, Avner; Ben-Menachem, Erez; Derazne, Estela; Berkenstadt, Haim

2015-11-01

Intravenous catheters are ubiquitous among modern medical management of patients, yet misplaced or tissued cannulas can result in serious iatrogenic injury due to infiltration or extravasation of injectate. Prevention is difficult, and currently few reliable tests exist to confirm intravascular placement of catheters in awake spontaneously breathing patients. Twenty conscious spontaneously breathing healthy volunteers were injected with 50 mL normal saline and 50 mL 4.2%, or 50 mL 2.1%, or 20 mL 4.2% sodium bicarbonate in a random order. A blinded anesthetist observed continuous sampling of exhaled carbon dioxide and was asked to differentiate between the sodium bicarbonate and saline injections. Peak increase in measured exhaled carbon dioxide was also calculated. Exhaled carbon dioxide increased significantly in participants injected with intravenous sodium bicarbonate. Mean peak increase was 7.4 mm Hg (±2.1 mm Hg) for 50 mL 4.2% sodium bicarbonate, 4.7 mm Hg (±2.5 mm Hg) for 20 mL 4.2% sodium bicarbonate, and 3.5 mm Hg (±1. 8 mm Hg) for 50 mL 2.1% sodium bicarbonate. The blinded observer correctly identified the injection as sodium bicarbonate or normal saline in every instance. Intravenous injection of dilute sodium bicarbonate with exhaled carbon dioxide monitoring reliably confirms correct intravascular placement of a catheter. A transient increase of exhaled carbon dioxide by 10% or more is an objective and reliable confirmation of intravascular location of the catheter. We recommend using 20 mL of 4.2% sodium bicarbonate to minimize the mEq dose of sodium bicarbonate required. Copyright © 2015 Elsevier Inc. All rights reserved.

Sorption Behavior of Compressed CO2 and CH4 on Ultrathin Hybrid Poly(POSS-imide) Layers.

PubMed

Raaijmakers, Michiel J T; Ogieglo, Wojciech; Wiese, Martin; Wessling, Matthias; Nijmeijer, Arian; Benes, Nieck E

2015-12-09

Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally accompanied by dilation, or swelling, of the polymer material. In turn, this dilation can result in penetrant induced plasticization and physical aging that affect the nonequilibrium status of the polymer. Here, we investigate the dilation and sorption behavior of ultrathin membrane layers of a hybrid inorganic-organic network material that consists of alternating polyhedral oligomeric silsesquioxane and imide groups, upon exposure to compressed carbon dioxide and methane. The imide precursor contains fluoroalkene groups that provide affinity toward carbon dioxide, while the octa-functionalized silsesquioxane provides a high degree of cross-linking. This combination allows for extremely high sorption capacities, while structural rearrangements of the network are hindered. We study the simultaneous uptake of gases and dilation of the thin films at high pressures using spectroscopic ellipsometry measurements. Ellipsometry provides the changes in both the refractive index and the film thickness, and allows for accurate quantification of sorption and swelling. In contrast, gravimetric and volumetric measurements only provide a single parameter; this does not allow an accurate correction for, for instance, the changes in buoyancy because of the extensive geometrical changes of highly swelling films. The sorption behavior of the ultrathin hybrid layers depends on the fluoroalkene group content. At low pressure, the apparent molar volume of the gases is low compared to the liquid molar volume of carbon dioxide and methane, respectively. At high gas concentrations in the polymer film, the apparent molar volume of carbon dioxide and methane exceeds that of the liquid molar volume, and approaches that of the gas phase. The high sorption capacity and reversible dilation characteristics of the presented materials provide new directions for applications including gas sensors and gas separation membranes.

The influence of dissolved H2O content in supercritical carbon dioxide to the inclusion complexes formation of ketoprofen/β-cyclodextrin

NASA Astrophysics Data System (ADS)

Goenawan, Joshua; Trisanti, P. N.; Sumarno

2015-12-01

This work studies the relation between dissolved H2O content in supercritical carbon dioxide (SC-CO2) with the formation of ketoprofen (KP)/β-cyclodextrin(CD) inclusion complexes. The process involves a physical mixture of these two compounds into contact with the supercritical carbon dioxide which had been previously saturated with H2O over a certain duration. The pressure used for saturation process is 130 bar and saturation temperature was ranged between 30 °C to 50 °C. The inclusion process was achieved by keeping it for 2 hours at 160 bar and 200 bar with inclusion temperature of 50 °C. The results enable us to suggest explanations for the inclusion formation. The inclusion complexes can be formed by contacting the dissolved H2O in SC-CO2 to the physical mixture of KP and CD. An increase in the temperature of saturation process resulted in an increase of dissolved H2O content in the supercritical carbon dioxide. The increasing levels of this water soluble resulted an increase in the inclusion complexes that has been formed. The formation of inclusion complexes includes the water molecules enhancing the emptying of the CD cavities and being replaced by KP, towards a more stable energy state. The drug release used for analyzing the dissolution rate of the KP/CD complexes. The results vary from 79,85% to 99,98% after 45 minutes which is above the rate that has been assigned by Farmakope Indonesia at 70% dissolution rate for KP. The use of SC-CO2 offers a new methods for increasing the rate of dissolution of drugs that are hydrophobic such as KP. CO2 used as a supercritical fluid because of its relatively low cost, easily obtainable supercritical conditions, and lack of toxicity. The material samples were characterized by DSC and Spectrophotometer UV-vis technique.

Understanding the Phase Behavior of Tetrahydrofuran + Carbon Dioxide, + Methane, and + Water Binary Mixtures from the SAFT-VR Approach.

PubMed

Míguez, J M; Piñeiro, M M; Algaba, J; Mendiboure, B; Torré, J P; Blas, F J

2015-11-05

The high-pressure phase diagrams of the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) mixtures are examined using the SAFT-VR approach. Carbon dioxide molecule is modeled as two spherical segments tangentially bonded, water is modeled as a spherical segment with four associating sites to represent the hydrogen bonding, methane is represented as an isolated sphere, and tetrahydrofuran is represented as a chain of m tangentially bonded spherical segments. Dispersive interactions are modeled using the square-well intermolecular potential. In addition, two different molecular model mixtures are developed to take into account the subtle balance between water-tetrahydrofuran hydrogen-bonding interactions. The polar and quadrupolar interactions present in water, tetrahydrofuran, and carbon dioxide are treated in an effective way via square-well potentials of variable range. The optimized intermolecular parameters are taken from the works of Giner et al. (Fluid Phase Equil. 2007, 255, 200), Galindo and Blas (J. Phys. Chem. B 2002, 106, 4503), Patel et al. (Ind. Eng. Chem. Res. 2003, 42, 3809), and Clark et al. (Mol. Phys. 2006, 104, 3561) for tetrahydrofuran, carbon dioxide, methane, and water, respectively. The phase diagrams of the binary mixtures exhibit different types of phase behavior according to the classification of van Konynenburg and Scott, ranging from types I, III, and VI phase behavior for the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) binary mixtures, respectively. This last type is characterized by the presence of a Bancroft point, positive azeotropy, and the so-called closed-loop curves that represent regions of liquid-liquid immiscibility in the phase diagram. The system exhibits lower critical solution temperatures (LCSTs), which denote the lower limit of immiscibility together with upper critical solution temperatures (UCSTs). This behavior is explained in terms of competition between the incompatibility with the alkyl parts of the tetrahydrofuran ring chain and the hydrogen bonding between water and the ether group. A minimum number of unlike interaction parameters are fitted to give the optimal representation of the most representative features of the binary phase diagrams. In the particular case of tetrahydrofuran(1) + water(2), two sets of intermolecular potential model parameters are proposed to describe accurately either the hypercritical point associated with the closed-loop liquid-liquid immiscibility region or the location of the mixture lower- and upper-critical end-points. The theory is not only able to predict the type of phase behavior of each mixture, but also provides a reasonably good description of the global phase behavior whenever experimental data are available.

The missing organic molecules on Mars

NASA Technical Reports Server (NTRS)

Benner, S. A.; Devine, K. G.; Matveeva, L. N.; Powell, D. H.

2000-01-01

GC-MS on the Viking 1976 Mars missions did not detect organic molecules on the Martian surface, even those expected from meteorite bombardment. This result suggested that the Martian regolith might hold a potent oxidant that converts all organic molecules to carbon dioxide rapidly relative to the rate at which they arrive. This conclusion is influencing the design of Mars missions. We reexamine this conclusion in light of what is known about the oxidation of organic compounds generally and the nature of organics likely to come to Mars via meteorite. We conclude that nonvolatile salts of benzenecarboxylic acids, and perhaps oxalic and acetic acid, should be metastable intermediates of meteoritic organics under oxidizing conditions. Salts of these organic acids would have been largely invisible to GC-MS. Experiments show that one of these, benzenehexacarboxylic acid (mellitic acid), is generated by oxidation of organic matter known to come to Mars, is rather stable to further oxidation, and would not have been easily detected by the Viking experiments. Approximately 2 kg of meteorite-derived mellitic acid may have been generated per m(2) of Martian surface over 3 billion years. How much remains depends on decomposition rates under Martian conditions. As available data do not require that the surface of Mars be very strongly oxidizing, some organic molecules might be found near the surface of Mars, perhaps in amounts sufficient to be a resource. Missions should seek these and recognize that these complicate the search for organics from entirely hypothetical Martian life.

The missing organic molecules on Mars

PubMed Central

Benner, Steven A.; Devine, Kevin G.; Matveeva, Lidia N.; Powell, David H.

2000-01-01

GC-MS on the Viking 1976 Mars missions did not detect organic molecules on the Martian surface, even those expected from meteorite bombardment. This result suggested that the Martian regolith might hold a potent oxidant that converts all organic molecules to carbon dioxide rapidly relative to the rate at which they arrive. This conclusion is influencing the design of Mars missions. We reexamine this conclusion in light of what is known about the oxidation of organic compounds generally and the nature of organics likely to come to Mars via meteorite. We conclude that nonvolatile salts of benzenecarboxylic acids, and perhaps oxalic and acetic acid, should be metastable intermediates of meteoritic organics under oxidizing conditions. Salts of these organic acids would have been largely invisible to GC-MS. Experiments show that one of these, benzenehexacarboxylic acid (mellitic acid), is generated by oxidation of organic matter known to come to Mars, is rather stable to further oxidation, and would not have been easily detected by the Viking experiments. Approximately 2 kg of meteorite-derived mellitic acid may have been generated per m2 of Martian surface over 3 billion years. How much remains depends on decomposition rates under Martian conditions. As available data do not require that the surface of Mars be very strongly oxidizing, some organic molecules might be found near the surface of Mars, perhaps in amounts sufficient to be a resource. Missions should seek these and recognize that these complicate the search for organics from entirely hypothetical Martian life. PMID:10706606

The missing organic molecules on Mars.

PubMed

Benner, S A; Devine, K G; Matveeva, L N; Powell, D H

2000-03-14

GC-MS on the Viking 1976 Mars missions did not detect organic molecules on the Martian surface, even those expected from meteorite bombardment. This result suggested that the Martian regolith might hold a potent oxidant that converts all organic molecules to carbon dioxide rapidly relative to the rate at which they arrive. This conclusion is influencing the design of Mars missions. We reexamine this conclusion in light of what is known about the oxidation of organic compounds generally and the nature of organics likely to come to Mars via meteorite. We conclude that nonvolatile salts of benzenecarboxylic acids, and perhaps oxalic and acetic acid, should be metastable intermediates of meteoritic organics under oxidizing conditions. Salts of these organic acids would have been largely invisible to GC-MS. Experiments show that one of these, benzenehexacarboxylic acid (mellitic acid), is generated by oxidation of organic matter known to come to Mars, is rather stable to further oxidation, and would not have been easily detected by the Viking experiments. Approximately 2 kg of meteorite-derived mellitic acid may have been generated per m(2) of Martian surface over 3 billion years. How much remains depends on decomposition rates under Martian conditions. As available data do not require that the surface of Mars be very strongly oxidizing, some organic molecules might be found near the surface of Mars, perhaps in amounts sufficient to be a resource. Missions should seek these and recognize that these complicate the search for organics from entirely hypothetical Martian life.

N-(3,4-Dimethyl-phen-yl)-4-hydr-oxy-2-methyl-2H-1,2-benzothia-zine-3-carboxamide 1,1-dioxide.

PubMed

Siddiqui, Waseeq Ahmad; Ali, Muhammad; Zia-Ur-Rehman, Muhammad; Sharif, Saima; Tizzard, Graham John

2009-03-28

1,2-Benzothia-zines similar to the title compound, C(18)H(18)N(2)O(4)S, are well known in the literature for their biological activities and are used as medicines in the treatment of inflammation and rheumatoid arthritis. The thia-zine ring adopts a distorted half-chair conformation. The enolic H atom is involved in an intra-molecular O-H⋯O hydrogen bond, forming a six-membered ring. In the crystal, mol-ecules arrange themselves into centrosymmetric dimers by means of pairs of weak inter-molecular N-H⋯O hydrogen bonds.

The physics and chemistry behind the bubbling properties of champagne and sparkling wines: a state-of-the-art review.

PubMed

Liger-Belair, Gérard

2005-04-20

In this review, the latest results about the chemical physics behind the bubbling properties of Champagne and sparkling wines are collected and fully illustrated. The chemistry of carbon dioxide molecules dissolved into the liquid matrix (section 2) is presented, as are the three main steps of a fleeting bubble's life, that is, the bubble nucleation on tiny particles stuck on the glass wall (section 3), the bubble ascent and growth through the liquid matrix (section 4), and the bursting of bubbles at the liquid surface (section 5), which constitutes the most intriguing, functional, and visually appealing step.

The Amazing Molecule Race: A WebQuest for 8th Grade Science

NASA Astrophysics Data System (ADS)

Soehl, Diana; Moats, S. J.; Langston, G. I.

2009-01-01

Did you ever wonder if life exists beyond Earth? The molecules that helped make up you and your friends are the same floating in outer space! The Race is ON to discover as many molecules in space as possible and to find the most important molecules for life: amino acids, DNA and RNA! As aspiring astronomers and astrobiologists, you will explore how these molecules are detected on Earth and in space. The `Search for Life’ is a pretty big task considering the size of the Universe. By learning how to find evidence of life forming molecules you will be able to provide conclusions that will shape policy regarding space missions, funding and technology development during your lifetime.

Analyzing the efficacy of subtropical urban forests in offsetting carbon emissions from cities

Treesearch

Francisco Escobedo; Sebastian Varela; Min Zhao; John E. Wagner; Wayne Zipperer

2010-01-01

Urban forest management and policies have been promoted as a tool to mitigate carbon dioxide (CO2) emissions. This study used existing CO2 reduction measures from subtropical Miami-Dade and Gainesville, USA and modeled carbon storage and sequestration by trees to analyze policies that use urban forests to offset carbon emissions. Field data were analyzed, modeled, and...

The combined toxicological effects of titanium dioxide nanoparticles and bisphenol A on zebrafish embryos

PubMed Central

2014-01-01

Environmental pollutants co-exist and exhibit interaction effects that are different from those associated with a single pollutant. As one of the more commonly manufactured nanomaterials, titanium dioxide nanoparticles (TiO2-NPs) are most likely to bind to other contaminants in water. In this paper, we aimed to study the combined toxicological effects of TiO2-NPs and bisphenol A (BPA) on organism. First, in vitro adsorption experiments were conducted to determine the adsorptive interaction between TiO2-NPs and BPA. Second, zebrafish embryo toxicity tests were performed to monitor for changes in the toxicological effects associated with the two chemicals. The study results demonstrated that adsorptive interactions exist between the two chemicals and increased toxicity effects which included an advanced toxicological effect time, decreased survival, increased morphological abnormalities, and delayed embryo hatching. Also, we suggest that the mode of combined action has a synergistic effect. Based on this, we postulate that concomitant exposure to TiO2-NPs and BPA increased BPA bioavailability and uptake into cells and organisms. Further studies are required to understand the mechanisms of interactions of this mixture. PMID:25177222

Derivatives of cysteine related to the thiosulfate metabolism of sulfur bacteria by the multi-enzyme complex "Sox"-studied by B3LYP-PCM and G3X(MP2) calculations.

PubMed

Steudel, Ralf; Steudel, Yana

2010-01-21

Certain sulfur bacteria oxidize thiosulfate enzymatically to sulfate, and derivatives of the amino acid cysteine play an important role as intermediates in this process. Since some of the proposed intermediates have so far been of hypothetical nature, we have investigated the structures and thermodynamic properties of more than 60 related derivatives of cysteine (CysH) by high-level quantum chemical calculations both in the gas phase and in a polarizable continuum using the PCM method to simulate an aqueous solution. Most of these molecules and anions were studied for the first time. Especially for the smaller species several conformational isomers of similar energy were identified; their relative stabilities are mainly determined by intramolecular hydrogen bonds. In contrast to the thiolate ion [Cys](-), the gaseous anions [CysS](-), [CysSO(2)](-), [CysSO(3)](-) and [CysSSO(3)](-) are most stable as zwitterions containing an NH(3) rather than an NH(2) group. This result also holds for the polarizable continuum. On the other hand, the related neutral molecules CysH, CysSH and CysSO(2)H are predicted to exist as NH(2) derivatives rather than zwitterions in the gas phase and this connectivity is predicted for CysH and CysSH also in the polarizable continuum. A model molecule of composition C(4)H(7)N(2)O(2)SH (abbreviated as RSH) simulating the structural environment of a cysteine residue within the peptide chain near the corresponding reaction center of the thiosulfate oxidizing enzyme complex "Sox" was used to elucidate the geometry of the proposed reaction intermediates as well as their thermodynamic properties. In the polarizable phase, the S-sulfonate ions [CysSO(3)](-) and [RSSO(3)](-) are predicted to react exothermically with water to the corresponding thiol and hydrogensulfate ions. These results support the proposed mechanism for enzymatic thiosulfate metabolism. Sulfur dioxide and hydrogensulfite anions are predicted to react exothermically and exergonically with thiolate and persulfide anions to give the corresponding S-sulfinate species [RSSO(2)](-) and [RSSSO(2)](-), respectively. The latter ions help to explain the inhibition of certain thiolate based enzymes by aqueous sulfite, disulfite and dithionite anions in sulfur oxidizing microorganisms.

Optical and electronic properties of SO2 molecule adsorbed on Si-doped (8, 0) boron nitride nanotube

NASA Astrophysics Data System (ADS)

Guo, Shuang-Shuang; Wei, Xiu-Mei; Zhang, Jian-Min; Zhu, Gang-Qiang; Guo, Wan-Jin

2016-09-01

The study of the optical properties of pristine BNNT, Si-doped BNNTs and SO2 molecule adsorption on Si-doped BNNTs is that, to our knowledge, few relevant research have ever been found. In this paper, the adsorption behaviors of Sulfur dioxide (SO2) molecule on Si-doped Boron nitride nanotubes (BNNTs) are investigated applying the first-principles calculations. The main contribution of this paper is that the foremost investigation for the optical properties of the pristine BNNT, Si-doped BNNTs and SO2 adsorption on Si-doped BNNTs. Additionally, the electronic properties and the structural properties are also presented. In our calculations of optical properties, the dielectric constant, the refractive index and the absorption coefficient are obtained. Comparing the pristine BNNT, our results indicate that, the blue-shifts (in the main peaks of the dielectric constant of SiB -BNNT and SO2-SiB -BNNT), and the red-shifts (in the main peaks of the refractive index of SiN -BNNT and SO2-SiN -BNNT) are appeared. Under these conditions, Si-doped BNNT and Si-doped BNNT with SO2 adsorption, the gaps are reduced both for the speculated optical band gaps and the electronic structure band gaps.

Catalytic water dissociation by greigite Fe3S4 surfaces: density functional theory study

PubMed Central

Roldan, A.; de Leeuw, N. H.

2016-01-01

The iron sulfide mineral greigite, Fe3S4, has shown promising capability as a hydrogenating catalyst, in particular in the reduction of carbon dioxide to produce small organic molecules under mild conditions. We employed density functional theory calculations to investigate the {001},{011} and {111} surfaces of this iron thiospinel material, as well as the production of hydrogen ad-atoms from the dissociation of water molecules on the surfaces. We systematically analysed the adsorption geometries and the electronic structure of both bare and hydroxylated surfaces. The sulfide surfaces presented a higher flexibility than the isomorphic oxide magnetite, Fe3O4, allowing perpendicular movement of the cations above or below the top atomic sulfur layer. We considered both molecular and dissociative water adsorption processes, and have shown that molecular adsorption is the predominant state on these surfaces from both a thermodynamic and kinetic point of view. We considered a second molecule of water which stabilizes the system mainly by H-bonds, although the dissociation process remains thermodynamically unfavourable. We noted, however, synergistic adsorption effects on the Fe3S4{001} owing to the presence of hydroxyl groups. We concluded that, in contrast to Fe3O4, molecular adsorption of water is clearly preferred on greigite surfaces. PMID:27274698

Public health impacts of city policies to reduce climate change: findings from the URGENCHE EU-China project.

PubMed

Sabel, Clive E; Hiscock, Rosemary; Asikainen, Arja; Bi, Jun; Depledge, Mike; van den Elshout, Sef; Friedrich, Rainer; Huang, Ganlin; Hurley, Fintan; Jantunen, Matti; Karakitsios, Spyros P; Keuken, Menno; Kingham, Simon; Kontoroupis, Periklis; Kuenzli, Nino; Liu, Miaomiao; Martuzzi, Marco; Morton, Katie; Mudu, Pierpaolo; Niittynen, Marjo; Perez, Laura; Sarigiannis, Denis; Stahl-Timmins, Will; Tobollik, Myriam; Tuomisto, Jouni; Willers, Saskia

2016-03-08

Climate change is a global threat to health and wellbeing. Here we provide findings of an international research project investigating the health and wellbeing impacts of policies to reduce greenhouse gas emissions in urban environments. Five European and two Chinese city authorities and partner academic organisations formed the project consortium. The methodology involved modelling the impact of adopted urban climate-change mitigation transport, buildings and energy policy scenarios, usually for the year 2020 and comparing them with business as usual (BAU) scenarios (where policies had not been adopted). Carbon dioxide emissions, health impacting exposures (air pollution, noise and physical activity), health (cardiovascular, respiratory, cancer and leukaemia) and wellbeing (including noise related wellbeing, overall wellbeing, economic wellbeing and inequalities) were modelled. The scenarios were developed from corresponding known levels in 2010 and pre-existing exposure response functions. Additionally there were literature reviews, three longitudinal observational studies and two cross sectional surveys. There are four key findings. Firstly introduction of electric cars may confer some small health benefits but it would be unwise for a city to invest in electric vehicles unless their power generation fuel mix generates fewer emissions than petrol and diesel. Second, adopting policies to reduce private car use may have benefits for carbon dioxide reduction and positive health impacts through reduced noise and increased physical activity. Third, the benefits of carbon dioxide reduction from increasing housing efficiency are likely to be minor and co-benefits for health and wellbeing are dependent on good air exchange. Fourthly, although heating dwellings by in-home biomass burning may reduce carbon dioxide emissions, consequences for health and wellbeing were negative with the technology in use in the cities studied. The climate-change reduction policies reduced CO2 emissions (the most common greenhouse gas) from cities but impact on global emissions of CO2 would be more limited due to some displacement of emissions. The health and wellbeing impacts varied and were often limited reflecting existing relatively high quality of life and environmental standards in most of the participating cities; the greatest potential for future health benefit occurs in less developed or developing countries.

Persistence length of collagen molecules based on nonlocal viscoelastic model.

PubMed

Ghavanloo, Esmaeal

2017-12-01

Persistence length is one of the most interesting properties of a molecular chain, which is used to describe the stiffness of a molecule. The experimentally measured values of the persistence length of the collagen molecule are widely scattered from 14 to 180 nm. Therefore, an alternative approach is highly desirable to predict the persistence length of a molecule and also to explain the experimental results. In this paper, a nonlocal viscoelastic model is developed to obtain the persistence length of the collagen molecules in solvent. A new explicit formula is proposed for the persistence length of the molecule with the consideration of the small-scale effect, viscoelastic properties of the molecule, loading frequency, and viscosity of the solvent. The presented model indicates that there exists a range of molecule lengths in which the persistence length strongly depends on the frequency and spatial mode of applied loads, small-scale effect, and viscoelastic properties of the collagen.

Bosch Reactor Development for High Percentage Oxygen Recovery from Carbon Dioxide

NASA Technical Reports Server (NTRS)

Howard, David; Abney, Morgan

2015-01-01

This next Generation Life Support Project entails the development and demonstration of Bosch reaction technologies to improve oxygen recovery from metabolically generated oxygen and/or space environments. A primary focus was placed on alternate carbon formation reactor concepts to improve useful catalyst life for space vehicle applications, and make use of in situ catalyst resources for non-terrestrial surface missions. Current state-of-the-art oxygen recovery systems onboard the International Space Station are able to effectively recover approximately 45 percent of the oxygen consumed by humans and exhausted in the form of carbon dioxide (CO2). Excess CO2 is vented overboard and the oxygen contained in the molecules is lost. For long-duration missions beyond the reaches of Earth for resupply, it will be necessary to recover greater amounts of constituents such as oxygen that are necessary for sustaining life. Bosch technologies theoretically recover 100 percent of the oxygen from CO2, producing pure carbon as the sole waste product. Challenges with this technology revolve around the carbon product fouling catalyst materials, drastically limiting catalyst life. This project successfully demonstrated techniques to extend catalyst surface area exposure times to improve catalyst life for vehicle applications, and demonstrated the use of Martian and lunar regolith as viable catalyst Bosch Reactor Development for High Percentage Oxygen Recovery From Carbon Dioxide materials for surface missions. The Bosch process generates carbon nanotube formation within the regolith, which has been shown to improve mechanical properties of building materials. Production of bricks from post reaction regolith for building and radiation shielding applications were also explored.

Constraints on water vapor and sulfur dioxide at Ceres: Exploiting the sensitivity of the Hubble Space Telescope

NASA Astrophysics Data System (ADS)

Roth, Lorenz

2018-05-01

Far-ultraviolet observations of dwarf-planet (1) Ceres were obtained on several occasions in 2015 and 2016 by the Cosmic Origins Spectrograph (COS) and the Space Telescope Imaging Spectrograph (STIS), both on board the Hubble Space Telescope (HST). We report a search for neutral gas emissions at hydrogen, oxygen and sulfur lines around Ceres from a potential teneous exosphere. No detectable exosphere emissions are present in any of the analyzed HST observations. We apply analytical models to relate the derived upper limits for the atomic species to a water exosphere (for H and O) and a sulfur dioxide exosphere (for S and O), respectively. The H and O upper limits constrain the H2O production rate at the surface to (2 - 4) ×1026 molecules s-1 or lower, similar to or slightly larger than previous detections and upper limits. With low fluxes of energetic protons measured in the solar wind prior to the HST observations and the obtained non-detections, an assessment of the recently suggested sputter-generated water exosphere during solar energetic particle events is not possible. Investigating a sulfur dioxide-based exosphere, we find that the O and S upper limits constrain the SO2 density at the surface to values ∼ 1010 times lower than the equilibrium vapor pressure density. This result implies that SO2 is not present on Ceres' sunlit surface, contrary to previous findings in HST ultraviolet reflectance spectra but in agreement with the absence of SO2 infrared spectral features as observed by the Dawn spacecraft.

Strategy to discover diverse optimal molecules in the small molecule universe.

PubMed

Rupakheti, Chetan; Virshup, Aaron; Yang, Weitao; Beratan, David N

2015-03-23

The small molecule universe (SMU) is defined as a set of over 10(60) synthetically feasible organic molecules with molecular weight less than ∼500 Da. Exhaustive enumerations and evaluation of all SMU molecules for the purpose of discovering favorable structures is impossible. We take a stochastic approach and extend the ACSESS framework ( Virshup et al. J. Am. Chem. Soc. 2013 , 135 , 7296 - 7303 ) to develop diversity oriented molecular libraries that can generate a set of compounds that is representative of the small molecule universe and that also biases the library toward favorable physical property values. We show that the approach is efficient compared to exhaustive enumeration and to existing evolutionary algorithms for generating such libraries by testing in the NKp fitness landscape model and in the fully enumerated GDB-9 chemical universe containing 3 × 10(5) molecules.

Strategy To Discover Diverse Optimal Molecules in the Small Molecule Universe

PubMed Central

2015-01-01

The small molecule universe (SMU) is defined as a set of over 1060 synthetically feasible organic molecules with molecular weight less than ∼500 Da. Exhaustive enumerations and evaluation of all SMU molecules for the purpose of discovering favorable structures is impossible. We take a stochastic approach and extend the ACSESS framework (Virshup et al. J. Am. Chem. Soc.2013, 135, 7296–730323548177) to develop diversity oriented molecular libraries that can generate a set of compounds that is representative of the small molecule universe and that also biases the library toward favorable physical property values. We show that the approach is efficient compared to exhaustive enumeration and to existing evolutionary algorithms for generating such libraries by testing in the NKp fitness landscape model and in the fully enumerated GDB-9 chemical universe containing 3 × 105 molecules. PMID:25594586

The future of small molecule inhibitors in lymphoma.

PubMed

Gerecitano, John

2009-09-01

For the many patients with lymphoma that has relapsed after and/or has become refractory to existing treatments, the development of novel therapeutics is imperative. Investigation into intracellular processes that are dysregulated during lymphomagenesis has uncovered several new potential targets for anticancer agents. Although monoclonal antibodies and other immunotherapeutics have led to dramatic advances in the treatment of patients with lymphoma, the parallel development of small molecule inhibitors has been equally exciting. These agents, whose small size allows direct entry into tumor cells, can target distinct proteins or complexes, thereby disrupting molecular processes on which neoplastic cells depend for survival and growth. This review surveys the published literature on many of these new targeted molecules, focusing on some of the most promising agents for which phase 2 data currently exist. It also explores the potential for incorporating these agents into broader multidrug regimens.

Does a network structure exist in molecular liquid SnI4 and GeI4?

NASA Astrophysics Data System (ADS)

Sakagami, Takahiro; Fuchizaki, Kazuhiro

2017-04-01

The existence of a network structure consisting of electrically neutral tetrahedral molecules in liquid SnI4 and GeI4 at ambient pressure was examined. The liquid structures employed for the examination were obtained from a reverse Monte Carlo analysis. The structures were physically interpreted by introducing an appropriate intermolecular interaction. A ‘bond’ was then defined as an intermolecular connection that minimizes the energy of intermolecular interaction. However, their ‘bond’ energy is too weak for the ‘bond’ and the resulting network structure to be defined statically. The vertex-to-edge orientation between the nearest molecules is so ubiquitous that almost all of the molecules in the system can take part in the network, which is reflected in the appearance of a prepeak in the structure factor.

Effects of concentration on the microwave dielectric spectra of aqueous urea solutions

NASA Astrophysics Data System (ADS)

Lyashchenko, A. K.; Dunyashev, V. S.; Zasetsky, A. Yu.

2017-05-01

Several models of relaxation for the dielectric spectra of aqueous urea solutions in the microwave region are compared. The spectra are shown to contain two main Debye components arising from the rotational motions of urea and water molecules. Two essentially different concentration regions in urea solutions are identified. The first is characterized by a small increase in the mobility of water molecules (τ1 = 7.8 ps) and the existence of hydrated urea molecules (τ2 = 19 ps). Due to the aggregation of urea molecules, the relaxation times for the latter process grow considerably in highly concentrated solutions. At the same time, faster molecular motions (τ3 = 6 ps) are observed for water molecules.

Sensitivity of the Palaeocene-Eocene Thermal Maximum climate to cloud properties.

PubMed

Kiehl, Jeffrey T; Shields, Christine A

2013-10-28

The Palaeocene-Eocene Thermal Maximum (PETM) was a significant global warming event in the Earth's history (approx. 55 Ma). The cause for this warming event has been linked to increases in greenhouse gases, specifically carbon dioxide and methane. This rapid warming took place in the presence of the existing Early Eocene warm climate. Given that projected business-as-usual levels of atmospheric carbon dioxide reach concentrations of 800-1100 ppmv by 2100, it is of interest to study past climates where atmospheric carbon dioxide was higher than present. This is especially the case given the difficulty of climate models in simulating past warm climates. This study explores the sensitivity of the simulated pre-PETM and PETM periods to change in cloud condensation nuclei (CCN) and microphysical properties of liquid water clouds. Assuming lower levels of CCN for both of these periods leads to significant warming, especially at high latitudes. The study indicates that past differences in cloud properties may be an important factor in accurately simulating past warm climates. Importantly, additional shortwave warming from such a mechanism would imply lower required atmospheric CO2 concentrations for simulated surface temperatures to be in reasonable agreement with proxy data for the Eocene.

A Risk-Based Framework for Assessing the Effectiveness of Stratospheric Aerosol Geoengineering

PubMed Central

Ferraro, Angus J.; Charlton-Perez, Andrew J.; Highwood, Eleanor J.

2014-01-01

Geoengineering by stratospheric aerosol injection has been proposed as a policy response to warming from human emissions of greenhouse gases, but it may produce unequal regional impacts. We present a simple, intuitive risk-based framework for classifying these impacts according to whether geoengineering increases or decreases the risk of substantial climate change, with further classification by the level of existing risk from climate change from increasing carbon dioxide concentrations. This framework is applied to two climate model simulations of geoengineering counterbalancing the surface warming produced by a quadrupling of carbon dioxide concentrations, with one using a layer of sulphate aerosol in the lower stratosphere, and the other a reduction in total solar irradiance. The solar dimming model simulation shows less regional inequality of impacts compared with the aerosol geoengineering simulation. In the solar dimming simulation, 10% of the Earth's surface area, containing 10% of its population and 11% of its gross domestic product, experiences greater risk of substantial precipitation changes under geoengineering than under enhanced carbon dioxide concentrations. In the aerosol geoengineering simulation the increased risk of substantial precipitation change is experienced by 42% of Earth's surface area, containing 36% of its population and 60% of its gross domestic product. PMID:24533155

Axial Colocalization of Single Molecules with Nanometer Accuracy Using Metal-Induced Energy Transfer.

PubMed

Isbaner, Sebastian; Karedla, Narain; Kaminska, Izabela; Ruhlandt, Daja; Raab, Mario; Bohlen, Johann; Chizhik, Alexey; Gregor, Ingo; Tinnefeld, Philip; Enderlein, Jörg; Tsukanov, Roman

2018-04-11

Single-molecule localization based super-resolution microscopy has revolutionized optical microscopy and routinely allows for resolving structural details down to a few nanometers. However, there exists a rather large discrepancy between lateral and axial localization accuracy, the latter typically three to five times worse than the former. Here, we use single-molecule metal-induced energy transfer (smMIET) to localize single molecules along the optical axis, and to measure their axial distance with an accuracy of 5 nm. smMIET relies only on fluorescence lifetime measurements and does not require additional complex optical setups.

Patterning of Functional Antibodies and Other Proteins by Photolithography of Silane Monolayers

NASA Astrophysics Data System (ADS)

Mooney, J. F.; Hunt, A. J.; McIntosh, J. R.; Liberko, C. A.; Walba, D. M.; Rogers, C. T.

1996-10-01

We have demonstrated the assembly of two-dimensional patterns of functional antibodies on a surface. In particular, we have selectively adsorbed micrometer-scale regions of biotinylated immunoglobulin that exhibit specific antigen binding after adsorption. The advantage of this technique is its potential adaptability to adsorbing arbitrary proteins in tightly packed monolayers while retaining functionality. The procedure begins with the formation of a self-assembled monolayer of n-octadecyltrimethoxysilane (OTMS) on a silicon dioxide surface. This monolayer can then be selectively removed by UV photolithography. Under appropriate solution conditions, the OTMS regions will adsorb a monolayer of bovine serum albumin (BSA), while the silicon dioxide regions where the OTMS has been removed by UV light will adsorb less than 2% of a monolayer, thus creating high contrast patterned adsorption of BSA. The attachment of the molecule biotin to the BSA allows the pattern to be replicated in a layer of streptavidin, which bonds to the biotinylated BSA and in turn will bond an additional layer of an arbitrary biotinylated protein. In our test case, functionality of the biotinylated goat antibodies raised against mouse immunoglobulin was demonstrated by the specific binding of fluorescently labeled mouse IgG.

Dendrimer-based Nanoparticle for Dye Sensitized Solar Cells with Improved Efficiency.

PubMed

Ghann, William; Kang, Hyeonggon; Uddin, Jamal; Gonawala, Sunalee J; Mahatabuddin, Sheikh; Ali, Meser M

2018-01-01

Dye sensitized solar cells were fabricated with DyLight680 (DL680) dye and its corresponding europium conjugated dendrimer, DL680-Eu-G5PAMAM, to study the effect of europium on the current and voltage characteristics of the DL680 dye sensitized solar cell. The dye samples were characterized by using Absorption Spectroscopy, Emission Spectroscopy, Fluorescence lifetime and Fourier Transform Infrared measurements. Transmission electron microscopy imaging was carried out on the DL680-Eu-G5PAMAM dye and DL680-Eu-G5PAMAM dye sensitized titanium dioxide nanoparticles to analyze the size of the dye molecules and examine the interaction of the dye with titanium dioxide nanoparticles. The DL680-Eu-G5PAMAM dye sensitized solar cells demonstrated an enhanced solar-to-electric energy conversion of 0.32% under full light illumination (100 mWcm -2 , AM 1.5 Global) in comparison with that of DL680 dye sensitized cells which recorded an average solar-to-electric energy conversion of only 0.19%. The improvement of the efficiency could be due to the presence of the europium that enhances the propensity of dye to absorb sunlight.

Habitats for life in the Venusian Environment? Can the VENUS EXPRESS payload answer?

NASA Astrophysics Data System (ADS)

Muller, C.

2003-04-01

The Venusian conditions are unique in the solar system. Venus abounds in molecules which could feed a life form except that the usual missing factor, energy, is present in excessive amounts from both active geothermic phenomena and from the nearby solar radiation trapped in a dense carbon dioxide atmosphere. Its surface conditions are hotter than the best practiced in hospital sterilisation; volcanism injects highly toxic gases which in the absence of water can accumulate in the atmosphere. Its upper atmosphere lays bare to solar radiation with only carbon dioxide to act as a confirmed EUV filter, so any consideration of life might seem excessive compared to what was known from life on earth before extremophile bacterias were discovered in dark undersea high temperature sulphur rich volcanic vents. However, some regions of the atmosphere might show conditions similar to the earth surface and could be a habitat of earth like microbial life. A synergy between the different atmospheric instruments of the VENUS-Express payload: SPICAM, VIRTIS and PFS can provide the way to probe the actual environmental conditions of this region and to check its capabilities of preserving an extant life or providing nutrients to a new one.

Diffusive counter dispersion of mass in bubbly media.

PubMed

Goldobin, Denis S; Brilliantov, Nikolai V

2011-11-01

We consider a liquid bearing gas bubbles in a porous medium. When gas bubbles are immovably trapped in a porous matrix by surface-tension forces, the dominant mechanism of transfer of gas mass becomes the diffusion of gas molecules through the liquid. Essentially, the gas solution is in local thermodynamic equilibrium with vapor phase all over the system, i.e., the solute concentration equals the solubility. When temperature and/or pressure gradients are applied, diffusion fluxes appear and these fluxes are faithfully determined by the temperature and pressure fields, not by the local solute concentration, which is enslaved by the former. We derive the equations governing such systems, accounting for thermodiffusion and gravitational segregation effects, which are shown not to be neglected for geological systems-marine sediments, terrestrial aquifers, etc. The results are applied for the treatment of non-high-pressure systems and real geological systems bearing methane or carbon dioxide, where we find a potential possibility of the formation of gaseous horizons deep below a porous medium surface. The reported effects are of particular importance for natural methane hydrate deposits and the problem of burial of industrial production of carbon dioxide in deep aquifers.

Final Report: Room Temperature Electrochemical Upgrading of Methane to Oxygenate Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mustain, William E.

The overall objective of this project is to discover the nature of the electrochemically active sites and to uncover the mechanisms for the electrocatalytic transformation of small organic molecules to oxygenate products such as methanol, formaldehyde, carbon monoxide and acetylene. Among the feedstocks of interest in this study are: methane, carbon dioxide, and acetic acid. Methane is an incredibly attractive potential feedstock because of the recent discovery of large shale deposits; carbon dioxide is potentially a very available feedstock from carbon capture technologies; acetic acid (as well as CH 4 and CO 2 and ethanol) has potential as a bio-derivedmore » feedstock. This report summarizes the major results to date regarding the electrochemical transformation of CH 4, CO 2 and acetic acid to chemicals and fuels – with a primary focus on methane. Finer details are available in each of the projects annual reports. In addition to the primary objective, the work in this project has led to synergistic discoveries that are advantageous to other fields including: catalyst layer deposition, anion exchange membrane fuel cells, CO 2 capture and li-ion batteries. Those are very briefly discussed as well.« less

Influence of porous texture and surface chemistry on the CO₂ adsorption capacity of porous carbons: acidic and basic site interactions.

PubMed

Sánchez-Sánchez, Angela; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M D

2014-12-10

Doped porous carbons exhibiting highly developed porosity and rich surface chemistry have been prepared and subsequently applied to clarify the influence of both factors on carbon dioxide capture. Nanocasting was selected as synthetic route, in which a polyaramide precursor (3-aminobenzoic acid) was thermally polymerized inside the porosity of an SBA-15 template in the presence of different H3PO4 concentrations. The surface chemistry and the porous texture of the carbons could be easily modulated by varying the H3PO4 concentration and carbonization temperature. Porous texture was found to be the determinant factor on carbon dioxide adsorption at 0 °C, while surface chemistry played an important role at higher adsorption temperatures. We proved that nitrogen functionalities acted as basic sites and oxygen and phosphorus groups as acidic ones toward adsorption of CO2 molecules. Among the nitrogen functional groups, pyrrolic groups exhibited the highest influence, while the positive effect of pyridinic and quaternary functionalities was smaller. Finally, some of these N-doped carbons exhibit CO2 heats of adsorption higher than 42 kJ/mol, which make them excellent candidates for CO2 capture.

Structure of the Cyanuric Acid Hydrolase TrzD Reveals Product Exit Channel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bera, Asim K.; Aukema, Kelly G.; Elias, Mikael

Cyanuric acid hydrolases are of industrial importance because of their use in aquatic recreational facilities to remove cyanuric acid, a stabilizer for the chlorine. Degradation of excess cyanuric acid is necessary to maintain chlorine disinfection in the waters. Cyanuric acid hydrolase opens the cyanuric acid ring hydrolytically and subsequent decarboxylation produces carbon dioxide and biuret. In the present study, we report the X-ray structure of TrzD, a cyanuric acid hydrolase from Acidovorax citrulli. The crystal structure at 2.19 Å resolution shows a large displacement of the catalytic lysine (Lys163) in domain 2 away from the active site core, whereas themore » two other active site lysines from the two other domains are not able to move. The lysine displacement is proposed here to open up a channel for product release. Consistent with that, the structure also showed two molecules of the co-product, carbon dioxide, one in the active site and another trapped in the proposed exit channel. Previous data indicated that the domain 2 lysine residue plays a role in activating an adjacent serine residue carrying out nucleophilic attack, opening the cyanuric acid ring, and the mobile lysine guides products through the exit channel.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Springston, Stephen R.

The Sulfur Dioxide Analyzer measures sulfur dioxide based on absorbance of UV light at one wavelength by SO 2 molecules which then decay to a lower energy state by emitting UV light at a longer wavelength. Specifically, SO 2 + hυ1 →SO 2 *→SO 2 + hυ2 The emitted light is proportional to the concentration of SO 2 in the optical cell. External communication with the analyzer is available through an Ethernet port configured through the instrument network of the AOS systems. The Model 43i-TLE is part of the i-series of Thermo Scientific instruments. The i-series instruments are designed tomore » interface with external computers through the proprietary Thermo Scientific iPort Software. However, this software is somewhat cumbersome and inflexible. Brookhaven National Laboratory (BNL) has written an interface program in National Instruments LabView that both controls the Model 43i-TLE Analyzer AND queries the unit for all measurement and housekeeping data. The LabView vi (the software program written by BNL) ingests all raw data from the instrument and outputs raw data files in a uniform data format similar to other instruments in the AOS and described more fully in Section 6.0 below.« less

Electrochemical Capture and Release of CO2 in Aqueous Electrolytes Using an Organic Semiconductor Electrode

PubMed Central

2017-01-01

Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g–1. This is on par with the best solution-phase amine chemical capture technologies available today. PMID:28378994

Sulfur dioxide retrievals from OMI and GOME-2 in preparation of TROPOMI

NASA Astrophysics Data System (ADS)

Theys, Nicolas; De Smedt, Isabelle; Danckaert, Thomas; Yu, Huan; van Gent, Jeroen; Van Roozendael, Michel

2016-04-01

The TROPOspheric Monitoring Instrument (TROPOMI) will be launched in 2016 onboard the ESA Sentinel-5 Precursor (S5P) platform and will provide global observations of atmospheric trace gases, with unprecedented spatial resolution. Sulfur dioxide (SO2) measurements from S5P will significantly improve the current capabilities for anthropogenic and volcanic emissions monitoring, and will extend the long-term datasets from past and existing UV sensors (TOMS, GOME, SCIAMACHY, OMI, GOME-2, OMPS). This work presents the SO2 retrieval schemes performed at BIRA-IASB as part of level-2 algorithm prototyping activities for S5P and tested on OMI and GOME-2. With a focus on anthropogenic sources, we show comparisons between OMI and GOME-2 as well as ground-based measurements, and discuss the possible reasons for the differences.

An advanced analysis and modelling the air pollutant concentration temporal dynamics in atmosphere of the industrial cities: Odessa city

NASA Astrophysics Data System (ADS)

Buyadzhi, V. V.; Glushkov, A. V.; Khetselius, O. Yu; Ternovsky, V. B.; Serga, I. N.; Bykowszczenko, N.

2017-10-01

Results of analysis and modelling the air pollutant (dioxide of nitrogen) concentration temporal dynamics in atmosphere of the industrial city Odessa are presented for the first time and based on computing by nonlinear methods of the chaos and dynamical systems theories. A chaotic behaviour is discovered and investigated. To reconstruct the corresponding strange chaotic attractor, the time delay and embedding dimension are computed. The former is determined by the methods of autocorrelation function and average mutual information, and the latter is calculated by means of correlation dimension method and algorithm of false nearest neighbours. It is shown that low-dimensional chaos exists in the nitrogen dioxide concentration time series under investigation. Further, the Lyapunov’s exponents spectrum, Kaplan-Yorke dimension and Kolmogorov entropy are computed.

hCG, the wonder of today's science

PubMed Central

2012-01-01

Background hCG is a wonder. Firstly, because hCG is such an extreme molecule. hCG is the most acidic glycoprotein containing the highest proportion of sugars. Secondly, hCG exists in 5 common forms. Finally, it has so many functions ranging from control of human pregnancy to human cancer. This review examines these molecules in detail. Content These 5 molecules, hCG, sulfated hCG, hyperglycosylated hCG, hCG free beta and hyperglycosylated free beta are produced by placental syncytiotrophoblast cells and pituitary gonadotrope cells (group 1), and by placental cytotrophoblast cells and human malignancies (group 2). Group 1 molecules are both hormones that act on the hCG/LH receptor. These molecules are central to human menstrual cycle and human pregnancy. Group 2 molecules are autocrines, that act by antagonizing a TGF beta receptor. These molecules are critical to all advanced malignancies. Conclusions The hCG groups are molecules critical to both the molecules of pregnancy or human life, and to the advancement of cancer, or human death. PMID:22455390

Determining the influence and effects of manufacturing variables on sulfur dioxide cells

NASA Technical Reports Server (NTRS)

Zajac, W. V.; Thomas, M. A.; Barnes, J. A.; Bis, R., F.; Davis, P. B.; Debold, F. C.; Gemmill, G. W.; Kowalchik, L. A.

1986-01-01

A survey of the Li/SO2 manufacturing community was conducted to determine where variability exists in processing. The upper and lower limits of these processing variables might, by themselves or by interacting with other variables, influence safety, performance, and reliability. A number of important variables were identified and a comprehensive design experiment is being proposed to make the proper determinations.

Treatment-Induced Autophagy Associated with Tumor Dormancy and Relapse

DTIC Science & Technology

2015-07-01

Food Sciences, Sultan Zainal Abidin University, Tembila Campus, 22200 Besut, Terengganu, Malaysia , 71Planet Biotechnologies Inc, St Albert, Canada...characterization results and/or relevant low-dose research evidence that might exist. The term ‘low dose’ was defined using the European Food Safety...redox signaling (193,221). Titanium dioxide nanoparticles are also common in many consumer prod- ucts and foods and have been reported to disrupt

A quantum spin-probe molecular microscope

NASA Astrophysics Data System (ADS)

Perunicic, V. S.; Hill, C. D.; Hall, L. T.; Hollenberg, L. C. L.

2016-10-01

Imaging the atomic structure of a single biomolecule is an important challenge in the physical biosciences. Whilst existing techniques all rely on averaging over large ensembles of molecules, the single-molecule realm remains unsolved. Here we present a protocol for 3D magnetic resonance imaging of a single molecule using a quantum spin probe acting simultaneously as the magnetic resonance sensor and source of magnetic field gradient. Signals corresponding to specific regions of the molecule's nuclear spin density are encoded on the quantum state of the probe, which is used to produce a 3D image of the molecular structure. Quantum simulations of the protocol applied to the rapamycin molecule (C51H79NO13) show that the hydrogen and carbon substructure can be imaged at the angstrom level using current spin-probe technology. With prospects for scaling to large molecules and/or fast dynamic conformation mapping using spin labels, this method provides a realistic pathway for single-molecule microscopy.

SLOW-NEUTRON SCATTERING BY MOLECULES OF LIQUID METHANE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rogalska, Z.

1962-10-01

The total slow neutron scattering cross section of liquid methane molecules as a function of neutron energy was measured. Agreement between experimental results and the theoretical curve, calculated on the basis of the Krieger and Nelkin theory for gaseous methane, was found. The most reasonable interpretation of this agreement was attributed to the fact that there exists a free rotation of molecules in liquid methane. It might be concluded that a free rotation is maintained at the transition from gas to liquid. (auth)

Spectroscopy and reactions of molecules important in chemical evolution

NASA Technical Reports Server (NTRS)

Becker, R. S.

1974-01-01

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Nature of bonding and cooperativity in linear DMSO clusters: A DFT, AIM and NCI analysis.

PubMed

Venkataramanan, Natarajan Sathiyamoorthy; Suvitha, Ambigapathy

2018-05-01

This study aims to cast light on the nature of interactions and cooperativity that exists in linear dimethyl sulfoxide (DMSO) clusters using dispersion corrected density functional theory. In the linear DMSO, DMSO molecules in the middle of the clusters are bound strongly than at the terminal. The plot of the total binding energy of the clusters vs the cluster size and mean polarizabilities vs cluster size shows an excellent linearity demonstrating the presence of cooperativity effect. The computed incremental binding energy of the clusters remains nearly constant, implying that DMSO addition at the terminal site can happen to form an infinite chain. In the linear clusters, two σ-hole at the terminal DMSO molecules were found and the value on it was found to increase with the increase in cluster size. The quantum theory of atoms in molecules topography shows the existence of hydrogen and SO⋯S type in linear tetramer and larger clusters. In the dimer and trimer SO⋯OS type of interaction exists. In 2D non-covalent interactions plot, additional peaks in the regions which contribute to the stabilization of the clusters were observed and it splits in the trimer and intensifies in the larger clusters. In the trimer and larger clusters in addition to the blue patches due to hydrogen bonds, additional, light blue patches were seen between the hydrogen atom of the methyl groups and the sulphur atom of the nearby DMSO molecule. Thus, in addition to the strong H-bonds, strong electrostatic interactions between the sulphur atom and methyl hydrogens exists in the linear clusters. Copyright © 2018 Elsevier Inc. All rights reserved.

Benzene construction via organocatalytic formal [3+3] cycloaddition reaction.

PubMed

Zhu, Tingshun; Zheng, Pengcheng; Mou, Chengli; Yang, Song; Song, Bao-An; Chi, Yonggui Robin

2014-09-25

The benzene unit, in its substituted forms, is a most common scaffold in natural products, bioactive molecules and polymer materials. Nearly 80% of the 200 best selling small molecule drugs contain at least one benzene moiety. Not surprisingly, the synthesis of substituted benzenes receives constant attentions. At present, the dominant methods use pre-existing benzene framework to install substituents by using conventional functional group manipulations or transition metal-catalyzed carbon-hydrogen bond activations. These otherwise impressive approaches require multiple synthetic steps and are ineffective from both economic and environmental perspectives. Here we report an efficient method for the synthesis of substituted benzene molecules. Instead of relying on pre-existing aromatic rings, here we construct the benzene core through a carbene-catalyzed formal [3+3] reaction. Given the simplicity and high efficiency, we expect this strategy to be of wide use especially for large scale preparation of biomedicals and functional materials.

Concentration profiles of actin-binding molecules in lamellipodia

NASA Astrophysics Data System (ADS)

Falcke, Martin

2016-04-01

Motile cells form lamellipodia in the direction of motion, which are flat membrane protrusions containing an actin filament network. The network flows rearward relative to the leading edge of the lamellipodium due to actin polymerization at the front. Thus, actin binding molecules are subject to transport towards the rear of the cell in the bound state and diffuse freely in the unbound state. We analyze this reaction-diffusion-advection process with respect to the concentration profiles of these species and provide an analytic approximation for them. Network flow may cause a depletion zone of actin binding molecules close to the leading edge. The existence of such zone depends on the free molecule concentration in the cell body, on the ratio of the diffusion length to the distance bound molecules travel rearward with the flow before dissociating, and the ratio of the diffusion length to the width of the region with network flow and actin binding. Our calculations suggest the existence of depletion zones for the F-actin cross-linkers filamin and α-actinin in fish keratocytes (and other cell types), which is in line with the small elastic moduli of the F-actin network close to the leading edge found in measurements of the force motile cells are able to exert.

Exploiting single photon vacuum ultraviolet photoionization to unravel the synthesis of complex organic molecules in interstellar ices

NASA Astrophysics Data System (ADS)

Abplanalp, Matthew J.; Förstel, Marko; Kaiser, Ralf I.

2016-01-01

Complex organic molecules (COM) such as aldehydes, ketones, carboxylic acids, esters, and amides are ubiquitous in the interstellar medium, but traditional gas phase astrochemical models cannot explain their formation routes. By systematically exploiting on line and in situ vacuum ultraviolet photoionization coupled with reflectron time of flight mass spectrometry (PI-ReTOF-MS) and combining these data with infrared spectroscopy (FTIR), we reveal that complex organic molecules can be synthesized within interstellar ices that are condensed on interstellar grains via non-equilibrium reactions involving suprathermal hydrogen atoms at temperatures as low as 5 K. By probing for the first time specific structural isomers without their degradation (fragment-free), the incorporation of tunable vacuum ultraviolet photoionization allows for a much greater understanding of reaction mechanisms that exist in interstellar ices compared to traditional methods, thus eliminating the significant gap between observational and laboratory data that existed for the last decades. With the commission of the Atacama Large Millimeter/Submillimeter Array (ALMA), the number of detections of more complex organic molecules in space will continue to grow ⿿ including biorelevant molecules connected to the Origins of Life theme ⿿ and an understanding of these data will rely on future advances in sophisticated physical chemistry laboratory experiments.

Analyzing Single-Molecule Time Series via Nonparametric Bayesian Inference

PubMed Central

Hines, Keegan E.; Bankston, John R.; Aldrich, Richard W.

2015-01-01

The ability to measure the properties of proteins at the single-molecule level offers an unparalleled glimpse into biological systems at the molecular scale. The interpretation of single-molecule time series has often been rooted in statistical mechanics and the theory of Markov processes. While existing analysis methods have been useful, they are not without significant limitations including problems of model selection and parameter nonidentifiability. To address these challenges, we introduce the use of nonparametric Bayesian inference for the analysis of single-molecule time series. These methods provide a flexible way to extract structure from data instead of assuming models beforehand. We demonstrate these methods with applications to several diverse settings in single-molecule biophysics. This approach provides a well-constrained and rigorously grounded method for determining the number of biophysical states underlying single-molecule data. PMID:25650922

Expanding Biosensing Abilities through Computer-Aided Design of Metabolic Pathways.

PubMed

Libis, Vincent; Delépine, Baudoin; Faulon, Jean-Loup

2016-10-21

Detection of chemical signals is critical for cells in nature as well as in synthetic biology, where they serve as inputs for designer circuits. Important progress has been made in the design of signal processing circuits triggering complex biological behaviors, but the range of small molecules recognized by sensors as inputs is limited. The ability to detect new molecules will increase the number of synthetic biology applications, but direct engineering of tailor-made sensors takes time. Here we describe a way to immediately expand the range of biologically detectable molecules by systematically designing metabolic pathways that transform nondetectable molecules into molecules for which sensors already exist. We leveraged computer-aided design to predict such sensing-enabling metabolic pathways, and we built several new whole-cell biosensors for molecules such as cocaine, parathion, hippuric acid, and nitroglycerin.

Controlling molecular condensation/diffusion of copper phthalocyanine by local electric field induced with scanning tunneling microscope tip

NASA Astrophysics Data System (ADS)

Nagaoka, Katsumi; Yaginuma, Shin; Nakayama, Tomonobu

2018-02-01

We have discovered the condensation/diffusion phenomena of copper phthalocyanine (CuPc) molecules controlled with a pulsed electric field induced by the scanning tunneling microscope tip. This behavior is not explained by the conventional induced dipole model. In order to understand the mechanism, we have measured the electronic structure of the molecule by tunneling spectroscopy and also performed theoretical calculations on molecular orbitals. These data clearly indicate that the molecule is positively charged owing to charge transfer to the substrate, and that hydrogen bonding exists between CuPc molecules, which makes the molecular island stable.

A quasi-hexagonal prism-shaped carbon nitride for photoreduction of carbon dioxide under visible light.

PubMed

He, Zhiqiao; Wang, Danfen; Tang, Juntao; Song, Shuang; Chen, Jianmeng; Tao, Xinyong

2017-03-01

A quasi-hexagonal prism-shaped carbon nitride (H-C 3 N 4 ) was synthesized from urea-derived C 3 N 4 (U-C 3 N 4 ) using an alkaline hydrothermal process. U-C 3 N 4 decomposition followed by hydrogen bond rearrangement of hydrolyzed products leads to the formation of a quasi-hexagonal prism-shaped structure. The H-C 3 N 4 catalysts displayed superior activity in the photoreduction of CO 2 with H 2 O compared to U-C 3 N 4 . The enhanced photocatalytic activities can be attributed to the promotion of incompletely coordinated nitrogen atom formation in the C 3 N 4 molecules. Graphical abstract ᅟ.

Non-equilibrium vibrational and chemical kinetics in shock heated carbon dioxide

NASA Astrophysics Data System (ADS)

Kosareva, A. A.

2018-05-01

The flows of CO2/CO/O2/O/C and CO2/CO/O mixtures behind shock waves are studied in the three-temperature, two-temperature and one-temperature approximations. The influence of the vibrational relaxation and chemical reactions on the flow composition, temperature and velocity is investigated. It is shown that the vibrational non-equilibrium has a significant effect on the macroscopic parameters of the flow near the front of the shock wave. It was found that the composition of the mixture has the greatest effect on the numerical density of CO molecules and O atoms. Also, significant differences between the values of the vibrational temperature of the asymmetric regime have been revealed.

N-(2,3-Dimethyl-phen-yl)-4-hydr-oxy-2-methyl-2H-1,2-benzothia-zine-3-carboxamide 1,1-dioxide.

PubMed

Siddiqui, Waseeq Ahmad; Bukahari, Iftikhar Hussain; Zia-Ur-Rehman, Muhammad; Khan, Islam Ullah; Tizzard, Graham John

2009-02-28

In the crystal structure of the title compound, C(18)H(18)N(2)O(4)S, the thia-zine ring adopts a distorted half-chair conformation. 1,2-Benzothia-zines of this kind have a wide range of biological activities and are mainly used as medicines in the treatment of inflammation and rheumatoid arthritis. The enolic H atom is involved in an intra-molecular O-H⋯O hydrogen bond, forming a six-membered ring. The mol-ecules arrange themselves into centrosymmetric dimers by means of inter-molecular N-H⋯O hydrogen bonds. A weak inter-molcular C-H⋯O inter-action is also present.