Kinetics of Organic Transformations Under Mild Aqueous Conditions: Implications for the Origin of Life and Its Metabolism

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

2003-01-01

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction half-life at 50 C, and to reveal the effect of functional groups on reactivity. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable (i. e. acetate decarboxylation half-life was l0(exp 18) years at 50 C); whereas, organic substances containing two oxygenated groups in which one group was a beta-positioned carbonyl group were the most reactive (i. e. acetoacetate decarboxylation half-life was l0(exp-2) years at 50 C). Of all functional groups the beta-positioned carbonyl group (aldehyde or ketone) was the strongest activating group, giving rates of reaction that were up to 10(exp 24)-times faster than rates of similar molecules lacking the beta-carbonyl group. From this knowledge of organic reactivity and the inherent constraints of autocatalytic processes, we concluded that an origins-of-life process based on autocatalytic transformation of C,H,O-substrates was constrained to using the most reactive organic molecules that contain alpha- or beta-carbonyl groups, since small autocatalytic domains of plausible catalytic power that used less reactive substrates could not carry out chemical transformations fast enough to prevent catastrophic efflux (escape) of reaction intermediates. Knowledge of the kinetics of organic transformations is useful, not only in constraining the chemistry of the earliest autocatalytic process related to the origin of life, but also in establishing the relative reactivity of organic molecules on the early Earth and other planets that may or may not be related to the origin of life.

Comparison of functional group selective ion-molecule reactions of trimethyl borate in different ion trap mass spectrometers

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

Habicht, S C; Vinueza, Nelson R; Amundson, Lucas M

2011-02-01

We report here a comparison of the use of diagnostic ion–molecule reactions for the identification of oxygen-containing functional groups in Fourier-transform ion cyclotron resonance (FTICR) and linear quadrupole ion trap (LQIT) mass spectrometers. The ultimate goal of this research is to be able to identify functionalities in previously unknown analytes by using many different types of mass spectrometers. Previous work has focused on the reactions of various boron reagents with protonated oxygen-containing analytes in FTICR mass spectrometers. By using a LQIT modified to allow the introduction of neutral reagents into the helium buffer gas, this methodology has been successfully implementedmore » to this type of an ion trap instrument. The products obtained from the reactions of trimethyl borate (TMB) with various protonated analytes are compared for the two instruments. Finally, the ability to integrate these reactions into LC-MS experiments on the LQIT is demonstrated.« less

Plasma enhancement of in vitro attachment of rat bone-marrow-derived stem cells on cross-linked gelatin films.

PubMed

Prasertsung, I; Kanokpanont, S; Mongkolnavin, R; Wong, C S; Panpranot, J; Damrongsakkul, S

2012-01-01

In this work, nitrogen, oxygen and air glow discharges powered by 50 Hz AC power supply are used for the treatment of type-A gelatin film cross-linked by a dehydrothermal (DHT) process. The properties of cross-linked gelatin were characterized by contact angle measurement, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the water contact angle of gelatin films decrease with increasing plasma treatment time. The treatment of nitrogen, oxygen and air plasma up to 30 s had no effects on the surface roughness of the gelatin film as revealed by AFM results. The XPS analysis showed that the N-containing functional groups generated by nitrogen and air plasma, and O-containing functional groups generated by oxygen and air plasmas were incorporated onto the film surface, the functional groups were found to increase with increasing treatment time. An in vitro test using rat bone-marrow-mesenchym-derived stem cells (MSCs) revealed that the number of cells attached on plasma-treated gelatin films was significantly increased compared to untreated samples. The best enhancement of cell attachment was noticed when the film was treated with nitrogen plasma for 15-30 s, oxygen plasma for 3 s, and air plasma for 9 s. In addition, among the three types of plasmas used, nitrogen plasma treatment gave the best MSCs attachment on the gelatin surface. The results suggest that a type-A gelatin film with water contact angle of 27-28° and an O/N ratio of 1.4 is most suitable for MSCs attachment.

Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

DOE PAGES

Christ, J. M.; Neyerlin, K. C.; Wang, H.; ...

2014-10-30

The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

Mechanism of organic aerosol formation and aging: Role of the precursor carbon skeleton

NASA Astrophysics Data System (ADS)

Hunter, J. F.; Carrasquillo, A. J.; Daumit, K. E.; Cross, E. S.; Worsnop, D. R.; Kroll, J. H.

2012-12-01

Oxidative aging of organic aerosol consists of a complex set of reactions coupled with gas-particle partitioning processes. Functionalization reactions involve adding oxygen containing functional groups onto a molecule, leading to reduced vapor pressures and promoting aerosol formation. In fragmentation reactions carbon-carbon bonds are broken as oxygen containing functional groups are added, which generally splits the parent molecule into two smaller and more volatile products. The initial structure of an aerosol-forming precursor molecule may influence what chemistry will occur both by changing the branching between fragmentation and functionalization processes as well as changing the effects of those processes. The fate of early generation oxidation products upon further aging is dependent on this initial chemistry, leading to a persistent effect of the precursor carbon skeleton. Aging experiments have been conducted using a high NOx smog chamber based aging technique. Long residence times and modestly elevated OH concentrations lead to typical maximum OH exposure of 3e11 molecule*seconds/cc, approaching several days equivalent exposure to ambient OH concentrations. A broad set of linear, branched and cyclic aliphatic hydrocarbons has been oxidized to determine the effects of carbon skeleton on the relative importance of fragmentation and functionalization and impacts on aerosol formation chemistry. Relative degree of fragmentation and functionalization is constrained by mass spectrometry of both the gas and particle phase. Measurements of the aerosol oxygen content and mass yield are reported, and structural effects on these properties are determined. Degree of unsaturation is hypothesized to have a significant impact on the effect of fragmentation reactions and to promote additional aerosol formation, extended aging and more oxygenated aerosol.

The Effects of Direct Oxygen Supply During Static Cold Preservation of Rat Livers: An Experimental Study.

PubMed

Zumrutdal, Emin; Karateke, Faruk; Eser, Pınar Eylem; Turan, Umit; Ozyazici, Sefa; Sozutek, Alper; Gulkaya, Mustafa; Kunt, Mevlut

2016-12-01

We aimed to determine the biochemical and histopathologic effects of direct oxygen supply to the preservation fluid of static cold storage system with a simple method on rat livers. Sixteen rats were randomly divided into 2 groups: the control group, which contained Ringer's lactate as preservation fluid; and the oxygen group, which contained oxygen and Ringer's lactate for preservation. Each liver was placed in a bag containing 50 mL Ringer's lactate and placed in ice-filled storage containers. One hundred percent oxygen supplies were given via a simple, inexpensive system created in our laboratory, to the livers in oxygen group. We obtained samples for histopathologic evaluation in the 12th hour. In addition, 3 mL of preservation fluid was subjected to biochemical analysis at 0, sixth, and twelfth hours. Aspartate aminotransferase, alanine aminotransferase, lactate dehydrogenase, and pH levels were measured from the preservation fluid. In oxygen-supplemented group, the acceleration speed of increase in alanine aminotransferase and lactate dehydrogenase levels at sixth hour and lactate dehydrogenase, alanine aminotransferase, and lactate dehydrogenase levels at 12th hour were statistically significantly reduced. In histopathologic examination, all parameters except ballooning were statistically significantly better in the oxygen-supplemented group. This simple system for oxygenation of liver tissues during static cold storage was shown to be effective with good results in biochemical and histopathologic assessments. Because this is a simple, inexpensive, and easily available method, larger studies are warranted to evaluate its effects (especially in humans).

Photoemission studies of fluorine functionalized porous graphitic carbon

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

Ganegoda, Hasitha; Olive, Daniel; Cheng, Lidens

2012-03-01

Porous graphitic carbon (PGC) has unique properties desirable for liquid chromatography applications when used as a stationary phase. The polar retention effect on graphite (PREG) allows efficient separation of polar and non-polar solutes. Perfluorinated hydrocarbons however lack polarizabilty and display strong lipo- and hydrophobicity, hence common lipophilic and hydrophilic analytes have low partition coefficiency in fluorinated stationary phases. Attractive interaction between fluorinated stationary phase and fluorinated analytes results in strong retention compared to non-fluorinated analytes. In order to change the selectivities of PGC, it is necessary to develop a bonded PGC stationary phase. In this study, we have synthesized perfluorinated,more » PGC using hepatadecafluoro-1-iodooctane, under different temperature conditions. Surface functionalization of the raw material was studied using photoelectron spectroscopy (PES). Results indicate the existence of fluorine containing functional groups, -CF, -CF{sub 2} along with an intercalated electron donor species. Multiple oxygen functional groups were also observed, likely due to the presence of oxygen in the starting material. These oxygen species may be responsible for significant modifications to planer and tetrahedral carbon ratios.« less

Oxygen-producing inert anodes for SOM process

DOEpatents

Pal, Uday B

2014-02-25

An electrolysis system for generating a metal and molecular oxygen includes a container for receiving a metal oxide containing a metallic species to be extracted, a cathode positioned to contact a metal oxide housed within the container; an oxygen-ion-conducting membrane positioned to contact a metal oxide housed within the container; an anode in contact with the oxygen-ion-conducting membrane and spaced apart from a metal oxide housed within the container, said anode selected from the group consisting of liquid metal silver, oxygen stable electronic oxides, oxygen stable crucible cermets, and stabilized zirconia composites with oxygen stable electronic oxides.

Selective adsorption for removal of nitrogen compounds from hydrocarbon streams over carbon-based adsorbents

NASA Astrophysics Data System (ADS)

Almarri, Masoud S.

The ultimate goal of this thesis is to develop a fundamental understanding of the role of surface oxygen functional groups on carbon-based adsorbents in the adsorption of nitrogen compounds that are known to be present in liquid fuels. N2 adsorption was used to characterize pore structures. The surface chemical properties of the adsorbents were characterized by X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) techniques with a mass spectrometer to identify and quantify the type and concentration of oxygen functional groups on the basis of CO2 and CO evolution profiles. It was found that although surface area and pore size distribution are important for the adsorption process, they are not primary factors in the adsorption of nitrogen compounds. On the other hand, both the type and concentration of surface oxygen-containing functional groups play an important role in determining adsorptive denitrogenation performance. Higher concentrations of the oxygen functional groups on the adsorbents resulted in a higher adsorption capacity for the nitrogen compounds. A fundamental insight was gained into the contributions of different oxygen functional groups by analyzing the changes in the monolayer maximum adsorption capacity, qm, and the adsorption constant, K, for nitrogen compounds on different activated carbons. Acidic functional groups such as carboxylic acids and carboxylic anhydrides appear to contribute more to the adsorption of quinoline, while the basic oxygen functional groups such as carbonyls and quinones enhance the adsorption of indole. Despite the high number of publications on the adsorptive desulfurization of liquid hydrocarbon fuels, these studies did not consider the presence of coexisting nitrogen compounds. It is well-known that, to achieve ultraclean diesel fuel, sulfur must be reduced to a very low level, where the concentrations of nitrogen and sulfur compounds are comparable. The adsorptive denitrogenation and desulfurization of model diesel fuel, which contains equimolar concentrations of nitrogen (i.e., quinoline and indole), sulfur (i.e., dibenzothiophene and 4,6-dimethyldibenzothiophene), and aromatic compounds (naphthalene, 1-methylnaphthalene, and fluorene), was examined. The results revealed that when both nitrogen and sulfur compounds coexist in the fuel, the type and density of oxygen functional groups on the surface of the activated carbon are crucial for selective adsorption of nitrogen compounds but have negligible positive effects for sulfur removal. The adsorption of quinoline and indole is largely governed by specific interactions. There is enough evidence to support the importance of dipole--dipole and acid-base-specific interactions for the adsorption of both quinoline and indole. Modified carbon is a promising material for the efficient removal of the nitrogen compounds from light cycle oil (LCO). Adsorptive denitrogenation of LCO significantly improved the hydrodesulfurization (HDS) performance, especially for the removal of the refractory sulfur compounds such as 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. An essential factor in applying activated carbon for adsorptive denitrogenation and desulfurization of liquid hydrocarbon streams is regeneration after saturation. The regeneration method of the saturated adsorbents consisted of toluene washing followed by heating to remove the remaining toluene. The results show that the spent activated carbon can be regenerated to completely recover the adsorption capacity. The high capacity and selectivity of activated carbon for nitrogen compounds, along with their ability to be regenerated, indicate that activated carbon is a promising adsorbent for the deep denitrogenation of liquid hydrocarbon streams.

Fabrication of hierarchical core-shell polydopamine@MgAl-LDHs composites for the efficient enrichment of radionuclides

NASA Astrophysics Data System (ADS)

Zhu, Kairuo; Lu, Songhua; Gao, Yang; Zhang, Rui; Tan, Xiaoli; Chen, Changlun

2017-02-01

Novel hierarchical core/shell structured polydopamine@MgAl-layered double hydroxides (PDA@MgAl-LDHs) composites involving MgAl-layered double hydroxide shells and PDA cores were fabricated thought one-pot coprecipitation assembly and methodically characterized by X-ray diffraction, Fourier transformed infrared spectroscopy, scanning/transmission electron microscopy, selected area electron diffraction, elemental mapping, thermogravimetric analysis and X-ray photoelectron spectroscopy technologies. U(VI) and Eu(III) sorption experiments showed that the PDA@MgAl-LDHs exhibited higher sorption ability with a maximum sorption capacity of 142.86 and 76.02 mg/g at 298 K and pH 4.5, respectively. More importantly, according to XPS analyses, U(VI) and Eu(III) were sorbed on PDA@MgAl-LDHs via oxygen-containing functional groups, and the chemical affinity of U(VI) by oxygen-containing functional groups is higher than that of Eu(III). These observations show great expectations in the enrichment of radionuclides from aquatic environments by PDA@MgAl-LDHs.

Surface Modification of Graphene Oxides by Plasma Techniques and Their Application for Environmental Pollution Cleanup.

PubMed

Wang, Xiangxue; Fan, Qiaohui; Chen, Zhongshan; Wang, Qi; Li, Jiaxing; Hobiny, Aatef; Alsaedi, Ahmed; Wang, Xiangke

2016-02-01

Graphene oxides (GOs) have come under intense multidisciplinary study because of their unique physicochemical properties and possible applications. The large amount of oxygen-containing functional groups on GOs leads to a high sorption capacity for the removal of various kinds of organic and inorganic pollutants from aqueous solutions in environmental pollution cleanup. However, the lack of selectivity results in difficulty in the selective removal of target pollutants from aqueous solutions in the presence of other coexisting pollutants. Herein, the surface grafting of GOs with special oxygen-containing functional groups using low-temperature plasma techniques and the application of the surface-modified GOs for the efficient removal of organic and inorganic pollutants in environmental pollution are reviewed. This paper gives an account of our research on the application of GO-based nanomaterials in environmental pollution cleanup, including: (1) the synthesis and surface grafting of functional groups on GOs, summarizing various types of low-temperature plasma techniques for the synthesis of graphene/GOs; and (2) the application of graphene/GOs and their composites for the efficient removal of organic and inorganic pollutants from aqueous solutions, including the interaction mechanism according to recently published results. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

**1**5N-NMR INVESTIGATION OF HYDROXYLAMINE DERIVATIZED HUMIC SUBSTANCES.

USGS Publications Warehouse

Thorn, Kevin A.; Arterburn, Jeffrey B.; Mikita, Michael A.

1986-01-01

Humic substances are the most abundant naturally occurring refactory organic compounds in soils and water. They have a broad range of physical, chemical and physiological properties. In soils, humic substances contribute to the cation exchange capacity, help maintain the physical structure, and play a role in plant growth and nutrition. In aquatic systems, humic substances serve to regulate the levels of inorganic constituents, yield trihalomethanes upon chlorination, and transport or concentrate organic and inorganic pollutants. The oxygen containing functional groups of humic and fulvic acids are believed to play a key role in the chemical properties of humic substances. This study was undertaken to gain additional information on the specific types of oxygen functionalities in humic substances. Since the analysis of hydroxyl moieties had been earlier established, we focused our attention on the analysis of ketone and aldehyde functional groups in humic substances.

Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2.

PubMed

Miner, Elise M; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dincă, Mircea

2016-03-08

Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units. Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. Such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications.

Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2

PubMed Central

Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dincă, Mircea

2016-01-01

Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units. Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. Such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications. PMID:26952523

Influence of surface oxides on the adsorption of naphthalene onto multiwalled carbon nanotubes.

PubMed

Cho, Hyun-Hee; Smith, Billy A; Wnuk, Joshua D; Fairbrother, D Howard; Ball, William P

2008-04-15

As greater quantities of carbon nanotubes (CNTs) enter the environment, they will have an increasingly important effect on the availability and transport of aqueous contaminants. As a consequence of purification, deliberate surface functionalization, and/or exposure to oxidizing agents after release to the environment, CNTs often contain surface oxides (i.e., oxygen containing functional groups). To probe the influence that surface oxides exert on CNT sorption properties, multiwalled CNTs (MWCNTs) with varying oxygen concentrations were studied with respect to their sorption properties toward naphthalene. For pristine (as-received) MWCNTs, the sorption capacity was intermediate between that of a natural char and a granular activated carbon. Sorption data also reveal that a linear relationship exists between the oxygen content of MWCNTs and their maximum adsorption capacity for naphthalene, with 10% surface oxygen concentration resulting in a roughly 70% decrease in maximum adsorption capacity. The relative distribution of sorption energies, as characterized by Freundlich isotherm exponents was, however, unaffected by oxidation. Thus, the data are consistent with the idea that incorporated surface oxides create polar regions that reduce the surface area available for naphthalene sorption. These results highlight the important role of surface chemistry in controlling the environmental properties of CNTs.

Graphene Oxide Catalyzed C-H Bond Activation: The Importance Oxygen Functional Groups for Biaryl Construction

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

Gao, Yongjun; Tang, Pei; Zhou, Hu

A heterogeneous, inexpensive and environment-friendly carbon catalytic system was developed for the C-H bond arylation of benzene resulting in the subsequent formation of biaryl compounds. The oxygen-containing groups on these graphene oxide sheets play an essential role in the observed catalytic activity. The catalytic results of model compounds and DFT calculations show that these functional groups promote this reaction by stabilization and activation of K ions at the same time of facilitating the leaving of I. And further mechanisms studies show that it is the charge induced capabilities of oxygen groups connected to specific carbon skeleton together with the giantmore » π-reaction platform provided by the π-domain of graphene that played the vital roles in the observed excellent catalytic activity. D. Mei acknowledges the support from the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory.« less

Investigation of Molecular Structure and Thermal Properties of Thermo-Oxidative Aged SBS in Blends and Their Relations

PubMed Central

Xu, Xiong; Yu, Jianying; Xue, Lihui; Zhang, Canlin; Zha, Yagang; Gu, Yi

2017-01-01

Tri-block copolymer styrene–butadiene (SBS) is extensively applied in bituminous highway construction due to its high elasticity and excellent weather resistance. With the extension of time, tri-block structural SBS automatically degrades into bi-block structural SB- with some terminal oxygen-containing groups under the comprehensive effects of light, heat, oxygen, etc. In this paper, the effects of aging temperature, aging time and oxygen concentration on the molecular structure of thermo-oxidative aged SBS were mainly investigated using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and the correlation between oxygen-containing groups and thermal properties (TG–DTG) was further discussed. The FTIR and XPS results show that rapid decomposition of SBS will occur with increments of aging temperature, aging time and oxygen concentration, and a large number of oxygen-containing groups such as –OH, C=O, –COOH, etc. will be formed during thermo-oxidative aging. In short-term aging, changes in aging temperature and oxygen concentration have a significant impact on the structural damage of SBS. However, in long-term aging, it has no further effect on the molecular structure of SBS or on increasing oxygen concentration. The TG and DTG results indicate that the concentration of substances with low molecular weight gradually increases with the improvement of the degree of aging of the SBS, while the initial decomposition rate increases at the beginning of thermal weightlessness and the decomposition rate slows down in comparison with neat SBS. From the relation between the XPS and TG results, it can be seen that the initial thermal stability of SBS rapidly reduces as the relative concentration of the oxygen-containing groups accumulates around 3%, while the maximum decomposition temperature slowly decreases when the relative concentration of the oxygen-containing groups is more than 3%, due to the difficult damage to strong bonds on the molecular structure of aged SBS. PMID:28773124

Investigation of Molecular Structure and Thermal Properties of Thermo-Oxidative Aged SBS in Blends and Their Relations.

PubMed

Xu, Xiong; Yu, Jianying; Xue, Lihui; Zhang, Canlin; Zha, Yagang; Gu, Yi

2017-07-07

Tri-block copolymer styrene-butadiene (SBS) is extensively applied in bituminous highway construction due to its high elasticity and excellent weather resistance. With the extension of time, tri-block structural SBS automatically degrades into bi-block structural SB- with some terminal oxygen-containing groups under the comprehensive effects of light, heat, oxygen, etc. In this paper, the effects of aging temperature, aging time and oxygen concentration on the molecular structure of thermo-oxidative aged SBS were mainly investigated using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and the correlation between oxygen-containing groups and thermal properties (TG-DTG) was further discussed. The FTIR and XPS results show that rapid decomposition of SBS will occur with increments of aging temperature, aging time and oxygen concentration, and a large number of oxygen-containing groups such as -OH, C=O, -COOH, etc. will be formed during thermo-oxidative aging. In short-term aging, changes in aging temperature and oxygen concentration have a significant impact on the structural damage of SBS. However, in long-term aging, it has no further effect on the molecular structure of SBS or on increasing oxygen concentration. The TG and DTG results indicate that the concentration of substances with low molecular weight gradually increases with the improvement of the degree of aging of the SBS, while the initial decomposition rate increases at the beginning of thermal weightlessness and the decomposition rate slows down in comparison with neat SBS. From the relation between the XPS and TG results, it can be seen that the initial thermal stability of SBS rapidly reduces as the relative concentration of the oxygen-containing groups accumulates around 3%, while the maximum decomposition temperature slowly decreases when the relative concentration of the oxygen-containing groups is more than 3%, due to the difficult damage to strong bonds on the molecular structure of aged SBS.

Direct growth of high crystallinity graphene from water-soluble polymer powders

NASA Astrophysics Data System (ADS)

Chen, Qiao; Zhong, Yujia; Huang, Meirong; Zhao, Guoke; Zhen, Zhen; Zhu, Hongwei

2018-07-01

The use of solid-state carbon sources is effective to produce graphene by safe and low-cost chemical vapor deposition (CVD) process. Water-soluble polymers are generally environmentally friendly and have great potential on large-scale green production of graphene. Here, we systematically study the growth of graphene from water-soluble polymers on copper foils. Two different conversion ways are adopted to investigate the growth mechanism of graphene from water-soluble polymers. We find that the metal-binding functional group hydroxyl strongly influences the vaporization of water-soluble polymers on Cu foils, which hinders the formation of graphene films by rapid thermal treatment. In direct CVD process using water-soluble polymer powders as precursors, oxygenated functional groups in polymers can enhance the crystallinity of as-grown graphene in contrast to solid hydrocarbons without containing oxygen (e.g. polyethylene). Large and continuous graphene films of high quality are synthesized from polyvinyl alcohol and polyethylene glycol. Nitrogen doping in graphene can be easily realized by using nitrogen-containing water-soluble polymers (e.g. polyvinyl pyrrolidone).

Property Relationship in Organosilanes and Nanotubes Filled Polypropylene Hybrid Composites

PubMed Central

Monsiváis-Barrón, Alejandra J.; Bonilla-Rios, Jaime; Sánchez-Fernández, Antonio

2014-01-01

Polypropylene composites with different filler contents were prepared by creating a masterbatch containing 3 wt%. filler. A variety of silanol groups were used to synthetized three compounds in different media trough a sol-gel process with acetic acid, formic acid and ammonium hydroxide as catalysts. Besides, four different nanotubular fillers were also used to analyze their behavior and compare it with the effect caused by the silanol groups. These tubular structures comprise: unmodified halloysite, carbon nanotubes and functionalized halloysite and carbon nanotubes. Morphological characterization in SEM and STEM/TEM showed dispersion in the polypropylene matrix. According to TGA and DSC measurements thermal behavior remain similar for all the composites. Mechanical test in tension demonstrate that modulus of the composites increases for all samples with a major impact for materials containing silanol groups synthetized in formic acid. Rheological measurements show a significantly increment in viscosity for samples containing unmodified and modified carbon nanotubes. No difference was found for samples containing silanol groups and halloysite when compared to neat polypropylene. Finally, the oxygen transmission rate increased for all samples showing high barrier properties only for samples containing natural and functionalized halloysite nanotubes. PMID:28788233

Property Relationship in Organosilanes and Nanotubes Filled Polypropylene Hybrid Composites.

PubMed

Monsiváis-Barrón, Alejandra J; Bonilla-Rios, Jaime; Sánchez-Fernández, Antonio

2014-10-20

Polypropylene composites with different filler contents were prepared by creating a masterbatch containing 3 wt%. filler. A variety of silanol groups were used to synthetized three compounds in different media trough a sol-gel process with acetic acid, formic acid and ammonium hydroxide as catalysts. Besides, four different nanotubular fillers were also used to analyze their behavior and compare it with the effect caused by the silanol groups. These tubular structures comprise: unmodified halloysite, carbon nanotubes and functionalized halloysite and carbon nanotubes. Morphological characterization in SEM and STEM/TEM showed dispersion in the polypropylene matrix. According to TGA and DSC measurements thermal behavior remain similar for all the composites. Mechanical test in tension demonstrate that modulus of the composites increases for all samples with a major impact for materials containing silanol groups synthetized in formic acid. Rheological measurements show a significantly increment in viscosity for samples containing unmodified and modified carbon nanotubes. No difference was found for samples containing silanol groups and halloysite when compared to neat polypropylene. Finally, the oxygen transmission rate increased for all samples showing high barrier properties only for samples containing natural and functionalized halloysite nanotubes.

Theoretical study of interactions between cysteine and perfluoropropanoic acid in gas and aqueous phase

NASA Astrophysics Data System (ADS)

Holmes, Tiffani M.; Doskocz, Jacek; Wright, Terrance; Hill, Glake A.

The interaction of perfluoropropanoic acid (PFPA) with the amino acid cysteine was investigated using density functional theory. Previous studies suggest that the peroxisome proliferator chemical, perfluorooctanoic acid, is circulated throughout the body by way of sulfur-containing amino acids. We present conformational analysis of the interactions of PFPA, a small model of perfluorooctanoic acid, with the sulfur-containing amino acid which occur by the process of hydrogen bonding, in which the hydrogen of the sulfhydryl group interacts with the carboxyl oxygen, and the amino nitrogen forms a hydrogen bond with the hydrogen of the bond OH group of the fluorinated alkyl. We also show in our structures a recently characterized weak nonbonded interaction between divalent sulfur and a main chain carboxyl oxygen in proteins. B3LYP calculated free energies and interaction energies predict low-energy, high-interaction conformations for complex systems of perfluorinated fatty acid interactions with cysteine.

Synthesis and characterization of covalently bound benzocaine graphite oxide derivative

NASA Astrophysics Data System (ADS)

Kabbani, Ahmad; Kabbani, Mohamad; Safadi, Khadija

2015-09-01

Graphite oxide (GO) derived materials include chemically functionalize or reduced graphene oxide (exfoliated from GO) sheets, assembled paper-like forms , and graphene-based composites GO consists of intact graphitic regions interspersed with sp3-hybridized carbons containing hydroxyl and epoxide functional groups on the top and bottom surfaces of each sheet and sp2-hybridized carbons containing carboxyl and carbonyl groups mostly at the sheet edges. Hence, GO is hydrophilic and readily disperses in water to form stable colloidal suspensions Due to the attached oxygen functional groups, GO was used to prepare different derivatives which result in some physical and chemical properties that are dramatically different from their bulk counterparts .The present work discusses the covalent cross linking of graphite oxide to benzocaine or ethyl ester of para-aminobenzoic acid,structure I,used in many over-the-counter ointment drug.Synthesis is done via diazotization of the amino group.The product is characterized via IR,Raman, X-ray photoelectron spectroscopy as well as electron microscopy.

Micro-oxidation treatment to improve bonding strength of Sr and Na co-substituted hydroxyapatite coatings for carbon/carbon composites

NASA Astrophysics Data System (ADS)

Zhang, Leilei; Li, Hejun; Li, Kezhi; Zhang, Yulei; Liu, Shoujie; Guo, Qian; Li, Shaoxian

2016-08-01

To improve the bonding strength of Sr and Na co-substituted hydroxyapatite (SNH) coatings for carbon/carbon composites, carbon/carbon composites are surface modified by micro-oxidation treatment. The micro-oxidation treatment could generate large number of pores containing oxygenic functional groups on the surface of carbon/carbon composites. SNH is nucleated on the inwall of the pores and form a flaky shape coating with 10-50 nm in thickness and 200-900 nm in width. The bonding strength between SNH coating and carbon/carbon composites increases from 4.27 ± 0.26 MPa to 10.57 ± 0.38 MPa after the micro-oxidation treatment. The promotion of bonding strength is mainly attributed to the pinning effect caused by the pores and chemical bonding generated by the oxygenic functional groups.

Optimization and application of atmospheric pressure chemical and photoionization hydrogen-deuterium exchange mass spectrometry for speciation of oxygen-containing compounds.

PubMed

Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Jin, Jang Mi; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

2016-05-01

This paper presents a detailed investigation of the feasibility of optimized positive and negative atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and atmospheric pressure photoionization (APPI) MS coupled to hydrogen-deuterium exchange (HDX) for structural assignment of diverse oxygen-containing compounds. The important parameters for optimization of HDX MS were characterized. The optimized techniques employed in the positive and negative modes showed satisfactory HDX product ions for the model compounds when dichloromethane and toluene were employed as a co-solvent in APCI- and APPI-HDX, respectively. The evaluation of the mass spectra obtained from 38 oxygen-containing compounds demonstrated that the extent of the HDX of the ions was structure-dependent. The combination of information provided by different ionization techniques could be used for better speciation of oxygen-containing compounds. For example, (+) APPI-HDX is sensitive to compounds with alcohol, ketone, or aldehyde substituents, while (-) APPI-HDX is sensitive to compounds with carboxylic functional groups. In addition, the compounds with alcohol can be distinguished from other compounds by the presence of exchanged peaks. The combined information was applied to study chemical compositions of degraded oils. The HDX pattern, double bond equivalent (DBE) distribution, and previously reported oxidation products were combined to predict structures of the compounds produced from oxidation of oil. Overall, this study shows that APCI- and APPI-HDX MS are useful experimental techniques that can be applied for the structural analysis of oxygen-containing compounds.

Catalytic biomass conversion methods, catalysts, and methods of making the same

DOEpatents

Delgass, William Nicholas; Agrawal, Rakesh; Ribeiro, Fabio Henrique; Saha, Basudeb; Yohe, Sara Lynn; Abu-Omar, Mahdi M; Parsell, Trenton; Dietrich, Paul James; Klein, Ian Michael

2017-10-10

Described herein are processes for one-step delignification and hydrodeoxygenation of lignin fraction a biomass feedstock. The lignin feedstock is derived from by-products of paper production and biorefineries. Additionally described is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function. Finally, also described herein is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function.

Biochar production method and composition therefrom

DOEpatents

Lee, James W; Buchanan, III, Archibald C; Evans, Barbara R; Kidder, Michelle K

2014-04-29

The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

Biochar production method and composition therefrom

DOEpatents

Lee, James W.; Buchanan, III, Archibald C.; Evans, Barbara R.; Kidder, Michelle K.

2013-03-19

The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

Graphene oxide papers with high water adsorption capacity for air dehumidification.

PubMed

Liu, Renlong; Gong, Tao; Zhang, Kan; Lee, Changgu

2017-08-29

Graphene oxide (GO) has shown a high potential to adsorb and store water molecules due to the oxygen-containing functional groups on its hydrophilic surface. In this study, we characterized the water absorbing properties of graphene oxide in the form of papers. We fabricated three kinds of graphene oxide papers, two with rich oxygen functional groups and one with partial chemical reduction, to vary the oxygen/carbon ratio and found that the paper with high oxygen content has higher moisture adsorption capability. For the GO paper with reduction, the overall moisture absorbance was reduced. However, the absorbance at high humidity was significantly improved due to direct formation of multilayer water vapor in the system, which derived from the weak interaction between the adsorbent and the adsorbate. To demonstrate one application of GO papers as a desiccant, we tested grape fruits with and without GO paper. The fruits with a GO paper exhibited longer-term preservation with delayed mold gathering because of desiccation effect from the paper. Our results suggest that GO will find numerous practical applications as a desiccant and is a promising material for moisture desiccation and food preservation.

Comparison on graphite, graphene oxide and reduced graphene oxide: Synthesis and characterization

NASA Astrophysics Data System (ADS)

Hidayah, N. M. S.; Liu, Wei-Wen; Lai, Chin-Wei; Noriman, N. Z.; Khe, Cheng-Seong; Hashim, U.; Lee, H. Cheun

2017-10-01

Graphene oxide (GO) and reduced graphene oxide (RGO) are known to have superior properties for various applications. This work compares the properties of GO and RGO with graphite. GO was prepared by using Improved Hummer's method whereas the produced GO was subjected to chemical reduction with the use of hydrazine hydrate. Graphite, GO and RGO had different morphologies, quality, functionalized groups, UV-Vis absorption peaks and crystallinity. With the removal of oxygen-containing functional group during reduction for RGO, the quality of samples was decreased due to higher intensity of D band than G band was seen in Raman results. In addition, platelet-like surface can be observed on the surface of graphite as compared to GO and RGO where wrinkled and layered flakes, and crumpled thin sheets were observed on GO and RGO surface respectively. Fourier Transform Infra-Red (FTIR) analysis showed the presence of abundant oxygen-containing functional groups in GO as compared to RGO and graphite. The characteristic peaks at 26.62°, 9.03° and 24.10° for graphite, GO and RGO, respectively, can be detected from X-Ray diffraction (XRD). Furthermore, the reduction also caused red shift at 279nm from 238nm, as obtained from ultraviolet visible (UV-Vis) analysis. The results proved that GO was successfully oxidized from graphite whereas RGO was effectively reduced from GO.

Role of oxygen-containing functional groups in forest fire-generated and pyrolytic chars for immobilization of copper and nickel.

PubMed

Esfandbod, Maryam; Merritt, Christopher R; Rashti, Mehran Rezaei; Singh, Balwant; Boyd, Sue E; Srivastava, Prashant; Brown, Christopher L; Butler, Orpheus M; Kookana, Rai S; Chen, Chengrong

2017-01-01

Char as a carbon-rich material, can be produced under pyrolytic conditions, wildfires or prescribed burn offs for fire management. The objective of this study was to elucidate mechanistic interactions of copper (Cu 2+ ) and nickel (Ni 2+ ) with different chars produced by pyrolysis (green waste, GW; blue-Mallee, BM) and forest fires (fresh-burnt by prescribed fire, FC; aged char produced by wild fire, AC). The pyrolytic chars were more effective sorbents of Cu 2+ (∼11 times) and Ni 2+ (∼5 times) compared with the forest fire chars. Both cross-polarization (CPMAS-NMR) and Bloch decay (BDMAS-NMR) 13 C NMR spectroscopies showed that forest fire chars have higher woody components (aromatic functional groups) and lower polar groups (e.g. O-alkyl C) compared with the pyrolytic chars. The polarity index was greater in the pyrolytic chars (0.99-1.34) than in the fire-generated chars (0.98-1.15), while aromaticity was lower in the former than in the latter. Fourier transform infrared (FTIR) and Raman spectroscopies indicated the binding of carbonate and phosphate with both Cu 2+ and Ni 2+ in all chars, but with a greater extent in pyrolytic than forest fire-generated chars. These findings have demonstrated the key role of char's oxygen-containing functional groups in determining their sorption capacity for the Cu 2+ and Ni 2+ in contaminated lands. Copyright © 2016 Elsevier Ltd. All rights reserved.

Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase.

PubMed

Bohli, Thouraya; Ouederni, Abdelmottaleb

2016-08-01

Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O3) and in liquid phase using nitric acid (HNO3). The activated carbon samples were characterized using N2 adsorption-desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m(2)/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich-Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO3), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.

Microwave assisted synthesis of camellia oleifera shell-derived porous carbon with rich oxygen functionalities and superior supercapacitor performance

NASA Astrophysics Data System (ADS)

Liang, Jiyuan; Qu, Tingting; Kun, Xiang; Zhang, Yu; Chen, Shanyong; Cao, Yuan-Cheng; Xie, Mingjiang; Guo, Xuefeng

2018-04-01

Biomass-derived carbon (BDCs) materials are receiving extensive attention as electrode materials for energy storage because of the considerable economic value offering possibility for practical applications, but the electrochemical capacitance of BDCs are usually relatively low resulted from limited electric double layer capacitance. Herein, an oxygen-rich porous carbon (KMAC) was fabricated through a rapid and convenient microwave assisted carbonization and KOH activation of camellia oleifera shell. The obtained KMAC possesses three-dimensional porous architecture, large surface area (1229 m2/g) and rich oxygen functionalities (C/O ratio of 1.66). As the electrode materials for supercapacitor, KMAC exhibits superior supercapacitive performances as compared to the activated carbon (KAC) derived from direct carbonization/KOH activation method in 2.0 M H2SO4 (315 F/g vs. 202 F/g) and 6.0 M KOH (251 F/g vs. 214 F/g) electrolyte due to the rich oxygen-containing functional groups on the surface of porous carbon resulted from the developed microwave-assisted carbonization/activation approach.

Macroevolutionary trends of atomic composition and related functional group proportion in eukaryotic and prokaryotic proteins.

PubMed

Zhang, Yu-Juan; Yang, Chun-Lin; Hao, You-Jin; Li, Ying; Chen, Bin; Wen, Jian-Fan

2014-01-25

To fully explore the trends of atomic composition during the macroevolution from prokaryote to eukaryote, five atoms (oxygen, sulfur, nitrogen, carbon, hydrogen) and related functional groups in prokaryotic and eukaryotic proteins were surveyed and compared. Genome-wide analysis showed that eukaryotic proteins have more oxygen, sulfur and nitrogen atoms than prokaryotes do. Clusters of Orthologous Groups (COG) analysis revealed that oxygen, sulfur, carbon and hydrogen frequencies are higher in eukaryotic proteins than in their prokaryotic orthologs. Furthermore, functional group analysis demonstrated that eukaryotic proteins tend to have higher proportions of sulfhydryl, hydroxyl and acylamino, but lower of sulfide and carboxyl. Taken together, an apparent trend of increase was observed for oxygen and sulfur atoms in the macroevolution; the variation of oxygen and sulfur compositions and their related functional groups in macroevolution made eukaryotic proteins carry more useful functional groups. These results will be helpful for better understanding the functional significances of atomic composition evolution. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of atmospheric plasma on physicochemical properties of vapor-grown graphite nanofibers.

PubMed

Seo, Min-Kang; Park, Soo-Jin; Lee, Sang-Kwan

2005-05-01

Vapor-grown graphite nanofibers (GNFs) were modified by plasma treatments using low-pressure plasmas with different gases (Ar gas only and/or Ar/O2 gases), flow rates, pressures, and powers. Surface characterizations and morphologies of the GNFs after plasma treatment were investigated by X-ray photoelectron spectroscopy (XPS), contact angle, titration, and transmission electron microscopy (TEM) measurements. Also, the investigation of thermomechanical behavior and impact strengths of the GNFs/epoxy composites was performed by dynamic-mechanical thermal analysis (DMTA) and Izod impact testing, respectively. The plasma treatment of the fibers changed the surface morphologies by forming a layer with a thickness on the order of 1 nm, mainly consisting of oxygen functional groups such as hydroxyl, carbonyl, and carboxyl groups. After functionalization of the complete surfaces, further plasma treatment did not enhance the superficial oxygen content but slightly changed the portions of the functional groups. Also, the composites with plasma-treated GNFs showed an increase in T(g) and impact strength compared to the composites containing the same amount of plasma-untreated GNFs.

Carefully designed oxygen-containing functional groups and defects of porous carbon spheres with UV-O3 treatment and their enhanced catalytic performance

NASA Astrophysics Data System (ADS)

Han, Weiliang; Huang, Xiaosheng; Lu, Gongxuan; Tang, Zhicheng

2018-04-01

In this paper, the support surface properties (surface oxygen-containing functional groups and structure defects) of porous carbon spheres (PCSs) were carefully designed by as UV assisted O3 technology. CO catalytic oxidation reactions performed over the supported Pd-Ce catalysts on modified porous carbon spheres. Results illustrated that the Pd-Ce/PCSs catalysts exhibited high CO catalytic activity, which were increased at first, and then decreased with UV assistant-O3 treatment time. The Pd-Ce/PCSs-30 catalyst exhibited superior activity and T100 was only 15 °C. Moreover, the Pd-Ce/PCSs-30 catalyst obtained an excellent stability, and 100% CO conversion could be maintained as the time on stream evolutes up to 16h in the presence of H2O in the feed. Based on characterization results, there were two main factors: (a) the surface area and pore volume were decreased with UV-O3 treatment, leading to the enhancement of Pd-Ce particle size, and the decrease of Pd-Ce nanoparticle dispersion and mass transfer efficiency, as well as the decrease of catalytic activity of Pd-Ce/PCSs, (b) the surface oxygen content and defect sites of PCSs were raised by UV-O3 treatment, which could improve surface loading of Pd, Ce and enhance Pdsbnd Osbnd Ce bonding interactions, thereby increasing the activity of Pd-Ce/PCSs.

Effect of pre-pyrolysis mode on simultaneous introduction of nitrogen/oxygen-containing functional groups into the structure of bagasse-based mesoporous carbon and its influence on Cu(II) adsorption.

PubMed

Wan, Zeqing; Li, Kunquan

2018-03-01

A convenient effective microwave pre-pyrolysis treatment to synthesize biomass-based mesoporous carbon with higher nitrogen/oxygen-chelating adsorption for Cu(II) is reported here, in which phosphoric acid impregnated bagasse was used as a microwave absorber and porogen. For comparison, conventional electric-heating pyrolyzed carbon was prepared and doped with nitrogen/oxygen groups. Nitrogen adsorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS) and batch adsorption were employed to investigate the effects of the two pre-pyrolysis modes on the sample physicochemical and Cu(II) adsorptive properties. The 22-min-microwave-pyrolyzed bagasse mesoporous activated carbon (MBAC, 85.32% mesoporosity) contained 10.52% O, which is 3.94% more than electric-heating pyrolyzed mesoporous activated carbon (89.52% mesoporosity). After electrophilic aromatic substitutions of N/O doping, the former possessed more N (5.83%) and more O (21.40%), confirming that time-saving energy-efficient microwave pyrolysis favors the formation of defective C/O atoms in or at the edges of the graphite layer of MBAC, which are highly active and tend to act as preferred reactive positions for the doping of N/O-containing groups simultaneously compared with conventional electric-heating pyrolysis. These N and O species existed mainly as COOH, OH, NH and NH 2 functional groups, and were confirmed by XPS to be active sites for metal binding via electrostatic attraction, hydrogen bonding, a chelate effect and complexation, resulting in the great enhancement of Cu(II) adsorption. Langmuir isotherm and pseudo-second-order kinetic fitting further proved that Cu(II) adsorption by N/O-doped MBAC is ascribed mainly to chemisorption. Therefore, rapid microwave pre-pyrolysis provides a promising route to prepare excellent-performance N/O-doped carbon adsorbents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Plasma surface modification of polypropylene track-etched membrane to improve its performance properties

NASA Astrophysics Data System (ADS)

Kravets, L. I.; Elinson, V. M.; Ibragimov, R. G.; Mitu, B.; Dinescu, G.

2018-02-01

The surface and electrochemical properties of polypropylene track-etched membrane treated by plasma of nitrogen, air and oxygen are studied. The effect of the plasma-forming gas composition on the surface morphology is considered. It has been found that the micro-relief of the membrane surface formed under the gas-discharge etching, changes. Moreover, the effect of the non-polymerizing gas plasma leads to formation of oxygen-containing functional groups, mostly carbonyl and carboxyl. It is shown that due to the formation of polar groups on the surface and its higher roughness, the wettability of the plasma-modified membranes improves. In addition, the presence of polar groups on the membrane surface layer modifies its electrochemical properties so that conductivity of plasma-treated membranes increase.

Tailoring properties of reduced graphene oxide by oxygen plasma treatment

NASA Astrophysics Data System (ADS)

Kondratowicz, Izabela; Nadolska, Małgorzata; Şahin, Samet; Łapiński, Marcin; Prześniak-Welenc, Marta; Sawczak, Mirosław; Yu, Eileen H.; Sadowski, Wojciech; Żelechowska, Kamila

2018-05-01

We report an easily controllable, eco-friendly method for tailoring the properties of reduced graphene oxide (rGO) by means of oxygen plasma. The effect of oxygen plasma treatment time (1, 5 and 10 min) on the surface properties of rGO was evaluated. Physicochemical characterization using microscopic, spectroscopic and thermal techniques was performed. The results revealed that different oxygen-containing groups (e.g. carboxyl, hydroxyl) were introduced on the rGO surface enhancing its wettability. Furthermore, upon longer treatment time, other functionalities were created (e.g. quinones, lactones). Moreover, external surface of rGO was partially etched resulting in an increase of the material surface area and porosity. Finally, the oxygen plasma-treated rGO electrodes with bilirubin oxidase were tested for oxygen reduction reaction. The study showed that rGO treated for 10 min exhibited twofold higher current density than untreated rGO. The oxygen plasma treatment may improve the enzyme adsorption on rGO electrodes by introduction of oxygen moieties and increasing the porosity.

Sorption mechanism of enrofloxacin on humic acids extracted from Brazilian soils.

PubMed

Martínez-Mejía, Mónica J; Sato, Isabela; Rath, Susanne

2017-07-01

Veterinary antimicrobials are emerging environmental contaminants of concern. In this study, the sorption of enrofloxacin (ENR) onto humic acids (HAs) extracted from three Brazilian soils was evaluated. HAs were characterized by elemental analysis and solid 13 C nuclear magnetic resonance spectroscopy. The sorption of ENR onto HAs was at least 20-fold higher than onto the soils from which they were separated. Ionic and cation bridging are the primary interactions involved. The interactions driven by cation exchange are predominant on HAs, which appear to have abundant carboxylic groups and a relatively high proportion of H-bond donor moieties with carbohydrate-like structures. Interactions explained by cation bridging and/or surface complexation on HAs are facilitated by moieties containing conjugated ligands, significant content of oxygen-containing functional groups, such as phenolic-OH or lignin-like structures. HAs containing electron-donating phenolic moieties and carboxylic acid ligand groups exhibit a sorption mechanism that is primarily driven by strong metal binding, favoring the formation of ternary complexes between functional groups of the organic matter and drugs.

Electrochemical oxygen reduction catalysed by Ni 3(hexaiminotriphenylene) 2

DOE PAGES

Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; ...

2016-03-08

Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni 3(HITP) 2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni 3(HITP) 2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N 4 sites are structurally reminiscent of the highly active and widely studied non-platinum groupmore » metal electrocatalysts containing M-N 4 units. Ni 3(HITP) 2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. As a result, such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications.« less

Cation Radical Accelerated Nucleophilic Aromatic Substitution via Organic Photoredox Catalysis.

PubMed

Tay, Nicholas E S; Nicewicz, David A

2017-11-15

Nucleophilic aromatic substitution (S N Ar) is a direct method for arene functionalization; however, it can be hampered by low reactivity of arene substrates and their availability. Herein we describe a cation radical-accelerated nucleophilic aromatic substitution using methoxy- and benzyloxy-groups as nucleofuges. In particular, lignin-derived aromatics containing guaiacol and veratrole motifs were competent substrates for functionalization. We also demonstrate an example of site-selective substitutive oxygenation with trifluoroethanol to afford the desired trifluoromethylaryl ether.

Pyrolysis temperature influences ameliorating effects of biochars on acidic soil.

PubMed

Wan, Qing; Yuan, Jin-Hua; Xu, Ren-Kou; Li, Xing-Hui

2014-02-01

The biochars were prepared from straws of canola, corn, soybean, and peanut at different temperatures of 300, 500, and 700 °C by means of oxygen-limited pyrolysis.Amelioration effects of these biochars on an acidic Ultisol were investigated with incubation experiments, and application rate of biochars was 10 g/kg. The incorporation of these biochars induced the increase in soil pH, soil exchangeable base cations, base saturation, and cation exchange capacity and the decrease in soil exchangeable acidity and exchangeable Al. The ameliorating effects of biochars on acidic soil increased with increase in their pyrolysis temperature. The contribution of oxygen-containing functional groups on the biochars to their ameliorating effects on the acidic soil decreased with the rise in pyrolysis temperature, while the contribution from carbonates in the biochars changed oppositely. The incorporation of the biochars led to the decrease in soil reactive Al extracted by 0.5mol/L CuCl2, and the content of reactive Al was decreased with the increase in pyrolysis temperature of incorporated biochars. The biochars generated at 300 °C increased soil organically complexed Al due to ample quantity of oxygen-containing functional groups such as carboxylic and phenolic groups on the biochars, while the biochars generated at 500 and 700 °C accelerated the transformation of soil exchangeable Al to hydroxyl-Al polymers due to hydrolysis of Al at higher pH. Therefore, the crop straw-derived biochars can be used as amendments for acidic soils and the biochars generated at relatively high temperature have great ameliorating effects on the soils.

A Novel Study of Methane-Rich Gas Reforming to Syngas and Its Kinetics over Semicoke Catalyst

PubMed Central

Zhang, Guojie; Su, Aiting; Qu, Jiangwen; Du, Yannian

2014-01-01

A small-size gasification unit is improved through process optimization to simulate industrial United Gas Improvement Company gasification. It finds that the reaction temperature has important impacts on semicoke catalyzed methane gas mixture. The addition of water vapor can enhance the catalytic activity of reforming, which is due to the fact that addition of water vapor not only removes carbon deposit produced in the reforming and gasification reaction processes, but also participates in gasification reaction with semicoke to generate some active oxygen-containing functional groups. The active oxygen-containing functional groups provide active sites for carbon dioxide reforming of methane, promoting the reforming reaction. It also finds that the addition of different proportions of methane-rich gas can yield synthesis gas with different H2/CO ratio. The kinetics study shows that the semicoke can reduce the activation energy of the reforming reaction and promote the occurrence of the reforming reaction. The kinetics model of methane reforming under the conditions of steam gasification over semicoke is as follows: k-=5.02×103·pCH40.71·pH20.26·exp(−74200/RT). PMID:24959620

Kinetics of organic transformations under mild aqueous conditions: implications for the origin of life and its metabolism

NASA Technical Reports Server (NTRS)

Weber, Arthur L.

2004-01-01

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction of half-lifes at 50 degrees C. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable; whereas organic substances containing two oxygenated groups in which one group was an alpha- or beta-positioned carbonyl group were the most reactive. Compounds with an alpha- or beta-positioned carbonyl group (aldehyde or ketone) had rates of reaction that were up to 10(24)-times faster than rates of similar molecules lacking the carbonyl group. This survey of organic reactivity, together with estimates of the molecular containment properties of lipid vesicles and liquid spherules, indicates that an origins process in a small domain that used C,H,O-intermediates had to be catalytic and use the most reactive organic molecules to prevent escape of its reaction intermediates.

Conformation-dependent chemical reaction of formic acid with an oxygen atom.

PubMed

Khriachtchev, Leonid; Domanskaya, Alexandra; Marushkevich, Kseniya; Räsänen, Markku; Grigorenko, Bella; Ermilov, Alexander; Andrijchenko, Natalya; Nemukhin, Alexander

2009-07-23

Conformation dictates many physical and chemical properties of molecules. The importance of conformation in the selectivity and function of biologically active molecules is widely accepted. However, clear examples of conformation-dependent bimolecular chemical reactions are lacking. Here we consider a case of formic acid (HCOOH) that is a valuable model system containing the -COOH carboxyl functional group, similar to many biomolecules including the standard amino acids. We have found a strong case of conformation-dependent reaction between formic acid and atomic oxygen obtained in cryogenic matrices. The reaction surprisingly leads to peroxyformic acid only from the ground-state trans conformer of formic acid, and it results in the hydrogen-bonded complex for the higher-energy cis conformer.

Effect of Oxygen-containing Functional Groups on Protein Stability in Ionic Liquid Solutions

NASA Technical Reports Server (NTRS)

Turner, Megan B.; Holbrey, John D.; Spear, Scott K.; Pusey, Marc L.; Rogers, Robin D.

2004-01-01

The ability of functionalized ionic liquids (ILs) to provide an environment of increased stability for biomolecules has been studied. Serum albumin is an inexpensive, widely available protein that contributes to the overall colloid osmotic blood pressure within the vascular system. Albumin is used in the present study as a marker of biomolecular stability in the presence of various ILs in a range of concentrations. The incorporation of hydroxyl functionality into the methylimidazolium-based cation leads to increased protein stability detected by fluorescence spectroscopy and circular dichroic (CD) spectrometry.

Physical origins of weak H 2 binding on carbon nanostructures: Insight from ab initio studies of chemically functionalized graphene nanoribbons

DOE PAGES

Ulman, Kanchan; Bhaumik, Debarati; Wood, Brandon C.; ...

2014-05-05

Here, we have performed ab initio density functional theory calculations, incorporating London dispersion corrections, to study the absorption of molecular hydrogen on zigzag graphene nanoribbons whose edges have been functionalized by OH, NH 2, COOH, NO 2, or H 2PO 3. We find that hydrogen molecules always preferentially bind at or near the functionalized edge, and display induced dipole moments. Binding is generally enhanced by the presence of polar functional groups. Furthermore, the largest gains are observed for groups with oxygen lone pairs that can facilitate local charge reorganization, with the biggest single enhancement in adsorption energy found for “strongmore » functionalization” by H 2PO 3 (115 meV/H 2 versus 52 meV/H 2 on bare graphene). We show that for binding on the “outer edge” near the functional group, the presence of the group can introduce appreciable contributions from Debye interactions and higher-order multipole electrostatic terms, in addition to the dominant London dispersion interactions. For those functional groups that contain the OH moiety, the adsorption energy is linearly proportional to the number of lone pairs on oxygen atoms. Mixed functionalization with two different functional groups on a graphene edge can also have a synergistic effect, particularly when electron-donating and electron-withdrawing groups are combined. For binding on the “inner edge” somewhat farther from the functional group, most of the binding again arises from London interactions; however, there is also significant charge redistribution in the π manifold, which directly reflects the electron donating or withdrawing capacity of the functional group. These results offer insight into the specific origins of weak binding of gas molecules on graphene, and suggest that edge functionalization could perhaps be used in combination with other strategies to increase the uptake of hydrogen in graphene. They also have relevance for the storage of hydrogen in porous carbon materials, such as activated carbons.« less

Tuning of electronic properties and dynamical stability of graphene oxide with different functional groups

NASA Astrophysics Data System (ADS)

Dabhi, Shweta D.; Jha, Prafulla K.

2017-09-01

The structural, electronic and vibrational properties of graphene oxide (GO) with varying proportion of epoxy and hydroxyl functional groups have been studied using density functional theory. The functional groups and oxygen density have an obvious influence on the electronic and vibrational properties. The dependence of band gap on associated functional groups and oxygen density shows a possibility of tuning the band gap of graphene by varying the functional groups as well as oxidation level. The absorption of high oxygen content in graphene leads to the gap opening and resulting in a transition from semimetal to semiconductor. Phonon dispersion curves show no imaginary frequency or no softening of any phonon mode throughout the Brillouin zone which confirms the dynamical stability of all considered GO models. Different groups and different oxygen density result into the varying characteristics of phonon modes. The computed results show good agreement with the experimental observations. Our results present interesting possibilities for engineering the electronic properties of graphene and GO and impact the fabrication of new electronics.

Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation

NASA Astrophysics Data System (ADS)

Hill, Christopher K.; Hartwig, John F.

2017-12-01

Polyoxygenated hydrocarbons that bear one or more hydroxyl groups comprise a large set of natural and synthetic compounds, often with potent biological activity. In synthetic chemistry, alcohols are important precursors to carbonyl groups, which then can be converted into a wide range of oxygen- or nitrogen-based functionality. Therefore, the selective conversion of a single hydroxyl group in natural products into a ketone would enable the selective introduction of unnatural functionality. However, the methods known to convert a simple alcohol, or even an alcohol in a molecule that contains multiple protected functional groups, are not suitable for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or reversible oxidation and reduction.

Functionalization of Single-Wall Carbon Nanotubes by Photo-Oxidation

NASA Technical Reports Server (NTRS)

Lebron-Colon, Marisabel; Meador, Michael A.

2010-01-01

new technique for carbon nanotube oxidation was developed based upon the photo-oxidation of organic compounds. The resulting method is more benign than conventional oxidation approaches and produces single-wall carbon nanotubes (SWCNTs) with higher levels of oxidation. In this procedure, an oxygen saturated suspension of SWNTs in a suitable solvent containing a singlet oxygen sensitizer, such as Rose Bengal, is irradiated with ultraviolet light. The resulting oxidized tubes are recovered by filtering the suspension, followed by washing to remove any adsorbed solvent and sensitizer, and drying in a vacuum oven. Chemical analysis by FT-infrared and x-ray photoelectron spectroscopy revealed that the oxygen content of the photo-oxidized SWCNT was 11.3 atomic % compared to 6.7 atomic % for SWCNT that had been oxidized by standard treatment in refluxing acid. The photo-oxidized SWCNT produced by this method can be used directly in various polymer matrixes, or can be further modified by chemical reactions at the oxygen functional groups and then used as additives. This method may also be suitable for use in oxidation of multiwall carbon nanotubes and graphenes.

Structural evaluation of reduced graphene oxide in graphene oxide during ion irradiation: X-ray absorption spectroscopy and in-situ sheet resistance studies

NASA Astrophysics Data System (ADS)

Saravanan, K.; Jayalakshmi, G.; Suresh, K.; Sundaravel, B.; Panigrahi, B. K.; Phase, D. M.

2018-03-01

We report the structural evolution of reduced graphene oxide (rGO) in graphene oxide (GO) flakes during 1 MeV Si+ ion irradiation. In-situ electrical resistivity measurements facilitate monitoring the sheet resistance with the increase in the fluence. The electrical sheet resistance of the GO flake shows the exponential decay behaviour with the increasing ion fluence. Raman spectra of the GO flake reveal the increase in the ID/IG ratio, indicating restoration of the sp2 network upon irradiation. The C/O ratio estimated from resonant Rutherford backscattering spectrometry analysis directly evidenced the reduction of oxygen moieties upon irradiation. C K-edge X-ray absorption near edge structure spectra reveal the restoration of C=C sp2-hybridized carbon atoms and the removal of oxygen-containing functional groups in the GO flake. STM data reveal the higher conductance in the rGO regime in comparison with the regime, where the oxygen functional groups are present. The experimental investigation demonstrates that the ion irradiation can be employed for efficient reduction of GO with tunable electrical and structural properties.

Structure and function of nematode communities across the Indian western continental margin and its oxygen minimum zone

NASA Astrophysics Data System (ADS)

Singh, R.; Ingole, B. S.

2016-01-01

We studied patterns of nematode distribution along the western Indian continental margin to determine the influence of habitat heterogeneity and low oxygen levels on the community's taxonomic and functional structure. A single transect, perpendicular to the coast at 14° N latitude was sampled from 34 to 2546 m depth for biological and environmental variables during August 2007. The oxygen minimum zone extended from 102 to 1001 m. Nematodes (described and undescribed) were identified to species and classified according to biological and functional traits. A total of 110 nematode species belonging to 24 families were found along the transect. Three depth zones were identified: the shelf (depth range: 34-102 m; highest nematode mean density: 176.6 ± 37 ind 10 cm-2), the slope (525-1524 m; 124.3 ± 16 ind 10 cm-2), and the basin (2001-2546 m; 62.9 ± 2 ind 10 cm-2). Across the entire study area, the dominant species were Terschellingia longicaudata, Desmodora sp. 1, Sphaerolaimus gracilis, and Theristus ensifer; their maximum density was at shelf stations. Nematode communities in different zones differed in species composition. Chromadorita sp. 2 (2.78 %) and Sphaerolaimus gracilis (2.21 %) were dominant on the shelf, whereas Terschellingia longicaudata (4.73 %) and Desmodora sp. 1 (4.42 %) were dominant on the slope, but in the basin, Halalaimus sp. 1(1.11 %) and Acantholaimus elegans (1.11 %) were dominant. The information in a particular functional group was not a simple reflection of the information in species abundance. Ecological information captured by adult length, adult shape, and life-history strategy was less site-specific and thus differed notably from information contained in other taxonomic groups. The functional composition of nematodes was strongly linked to the organic-carbon and dissolved-oxygen concentration. Seven species were found exclusively in the oxygen minimum zone: Pselionema sp. 1, Choanolaimus sp. 2, Halichoanolaimus sp. 1, Cobbia dentata, Daptonema sp. 1, Trissonchulus sp. 1, and Minolaimus sp. 1. Correlation with a number of environmental variables indicated that food quantity (measured as the organic-carbon content and chlorophyll content) and oxygen level were the major factors that influenced nematode community structure and function.

Biochar supported nanoscale zerovalent iron composite used as persulfate activator for removing trichloroethylene.

PubMed

Yan, Jingchun; Han, Lu; Gao, Weiguo; Xue, Song; Chen, Mengfang

2015-01-01

Biochar (BC) supported nanoscale zerovalent iron (nZVI) composite was synthesized and used as an activator for persulfate to enhance the trichloroethylene (TCE) removal in aqueous solutions. The degradation efficiency of TCE (0.15mmolL(-1)) was 99.4% in the presence of nZVI/BC (4.5mmolL(-1), nZVI to BC mass ratio was 1:5) and persulfate (4.5mmolL(-1)) within 5min, which was significantly higher than that (56.6%) in nZVI-persulfate system under the same conditions. Owing to large specific surface area and oxygen-containing functional groups of BC, nZVI/BC enhanced the SO4(-) generation and accelerated TCE degradation. On the basis of the characterization and analysis data, possible activation mechanisms of the Fe(2+)/Fe(3+) (Fe(II)/Fe(III)) redox action and the electron-transfer mediator of the BC oxygen functional groups promoting the generation of SO4(-) in nZVI/BC-persulfate system were clarified. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrical resistance behavior of oxyfluorinated graphene under oxidizing and reducing gas exposure.

PubMed

Im, Ji Sun; Bae, Tae-Sung; Shin, Eunjeong; Lee, Young-Seak

2014-03-01

The electrical resistance behavior of graphene was studied under oxidizing and reducing gas exposure. The graphene surface was modified via oxyfluorination to obtain a specific surface area and oxygen functional groups. Fluorine radicals provided improved pore structure and introduction of an oxygen functional group. A high-performance gas sensor was obtained based on enlarged target gas adsorption sites and an enhanced electron charge transfer between the target gas and carbon surface via improved pore structure and the introduction of oxygen functional groups, respectively.

Low temperature hydrolysis of laboratory tholins in ammonia-water solutions: Implications for prebiotic chemistry on Titan

NASA Astrophysics Data System (ADS)

Neish, Catherine D.; Somogyi, Árpád; Lunine, Jonathan I.; Smith, Mark A.

2009-05-01

Laboratory tholins react rapidly in 13 wt% ammonia-water at low temperature, producing complex organic molecules containing both oxygen and altered nitrogen functional groups. These reactions display first-order kinetics with half-lives between 0.3 and 14 days at 253 K. The reaction timescales are much shorter than the freezing timescales of impact melts and volcanic sites on Titan, providing ample time for the formation of oxygenated, possibly prebiotic, molecules on its surface. Comparing the rates of the hydrolysis reactions in ammonia-water to those measured in pure water [Neish, C.D, Somogyi, A., Imanaka, H., Lunine, J.I., Smith, M.A., 2008a. Astrobiology 8, 273-287], we find that incorporation of oxygen into the tholins is faster in the presence of ammonia. The rate increases could be due to the increased pH of the solution, or to the availability of new reaction pathways made possible by the presence of ammonia. Using labeled 15NH 3 water, we find that ammonia does incorporate into some products, and that the reactions with ammonia are largely independent of those with water. A related study in HO18 confirms water as the source of the oxygen incorporated into the oxygen containing products.

Chemical functionalization of graphene to augment stem cell osteogenesis and inhibit biofilm formation on polymer composites for orthopedic applications.

PubMed

Kumar, Sachin; Raj, Shammy; Kolanthai, Elayaraja; Sood, A K; Sampath, S; Chatterjee, Kaushik

2015-02-11

Toward designing the next generation of resorbable biomaterials for orthopedic applications, we studied poly(ε-caprolactone) (PCL) composites containing graphene. The role, if any, of the functionalization of graphene on mechanical properties, stem cell response, and biofilm formation was systematically evaluated. PCL composites of graphene oxide (GO), reduced GO (RGO), and amine-functionalized GO (AGO) were prepared at different filler contents (1%, 3%, and 5%). Although the addition of the nanoparticles to PCL markedly increased the storage modulus, this increase was largest for GO followed by AGO and RGO. In vitro cell studies revealed that the AGO and GO particles significantly increased human mesenchymal stem cell proliferation. AGO was most effective in augmenting stem cell osteogenesis leading to mineralization. Bacterial studies revealed that interaction with functionalized GO induced bacterial cell death because of membrane damage, which was further accentuated by amine groups in AGO. As a result, AGO composites were best at inhibiting biofilm formation. The synergistic effect of oxygen containing functional groups and amine groups on AGO imparts the optimal combination of improved modulus, favorable stem cell response, and biofilm inhibition in AGO-reinforced composites desired for orthopedic applications. This work elucidates the importance of chemical functionalization of graphene in polymer composites for biomedical applications.

Photophysical and electrical properties of polyphenylquinolines containing carbazole or indolo[3,2-b]carbazole fragments as new optoelectronic materials

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

Svetlichnyi, V. M., E-mail: valsvet@hq.macro.ru; Aleksandrova, E. L.; Myagkova, L. A.

2011-10-15

Photophysical and electrical properties of new synthesized 2,6-polyphenylquinolines (PPQs) containing an oxygen or phenylamine bridging group between quinoline cycles and, as an arylene radical, alkylated derivatives of carbazole or indolo[3,2-b]carbazole are studied. It is shown that the photosensitivity for new PPQs is 10{sup 4}-10{sup 5} cm{sup 2}/J and the photogeneration quantum yield of free carriers is as high as 0.15. Photophysical parameters increase with the phenylamine bridging group in place of the oxygen one and when using indolocarbazole instead of carbazole. It is found that a film of polyphenylquinoline containing an oxygen bridging group and an alkylcarbazole fragment in themore » polymer repeat unit exhibits 'white' luminescence. Both electron and hole transport with a mobility of {approx}10{sup -6} cm{sup 2}/(V s) are detected in films of all studied polymers. The conductivity value and type can be controlled by varying the chemical structure of the (oxygen or phenylamine) bridging group between PPQ cycles and by choosing carbazole or indolo[3,2-b]carbazole derivatives as an arylene radical.« less

Electrochemical Characterization of O2 Plasma Functionalized Multi-Walled Carbon Nanotube Electrode for Legionella pneumophila DNA Sensor

NASA Astrophysics Data System (ADS)

Park, Eun Jin; Lee, Jun-Yong; Hyup Kim, Jun; Kug Kim, Sun; Lee, Cheol Jin; Min, Nam Ki

2010-08-01

An electrochemical DNA sensor for Legionella pneumophila detection was constructed using O2 plasma functionalized multi-walled carbon nanotube (MWCNT) film as a working electrode (WE). The cyclic voltammetry (CV) results revealed that the electrocatalytic activity of plasma functionalized MWCNT (pf-MWCNT) significantly changed depending on O2 plasma treatment time due to some oxygen containing functional groups on the pf-MWCNT surface. Scanning electron microscope (SEM) images and X-ray photoelectron spectroscopy (XPS) spectra were also presented the changes of their surface morphologies and oxygen composition before and after plasma treatment. From a comparison study, it was found that the pf-MWCNT WEs had higher electrocatalytic activity and more capability of probe DNA immobilization: therefore, electrochemical signal changes by probe DNA immobilization and hybridization on pf-MWCNT WEs were larger than on Au WEs. The pf-MWCNT based DNA sensor was able to detect a concentration range of 10 pM-100 nM of target DNA to detect L. pneumophila.

Catalytic, Enantioselective Sulfenofunctionalisation of Alkenes: Mechanistic, Crystallographic, and Computational Studies

PubMed Central

Denmark, Scott E.; Hartmann, Eduard; Kornfilt, David J. P.; Wang, Hao

2015-01-01

The stereocontrolled introduction of vicinal heteroatomic substituents into organic molecules is one of the most powerful ways of adding value and function. Whereas many methods exist for the introduction of oxygen- and nitrogen-containing substituents, the number stereocontrolled methods for the introduction of sulfur-containing substituents pales by comparison. Previous reports from these laboratories have described the sulfenofunctionalization of alkenes that construct vicinal carbon-sulfur and carbon-oxygen, carbon-nitrogen as well as carbon-carbon bonds with high levels of diastereospecificity and enantioselectivity. This process is enabled by the concept of Lewis base activation of Lewis acids that provides activation of Group 16 electrophiles. To provide a foundation for expansion of substrate scope and improved selectivities, we have undertaken a comprehensive study of the catalytically active species. Insights gleaned from kinetic, crystallographic and computational methods have led to the introduction of a new family of sulfenylating agents that provide significantly enhanced selectivities. PMID:25411883

Physical origins of weak H{sub 2} binding on carbon nanostructures: Insight from ab initio studies of chemically functionalized graphene nanoribbons

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

Ulman, Kanchan; Bhaumik, Debarati; Wood, Brandon C.

2014-05-07

We have performed ab initio density functional theory calculations, incorporating London dispersion corrections, to study the absorption of molecular hydrogen on zigzag graphene nanoribbons whose edges have been functionalized by OH, NH{sub 2}, COOH, NO{sub 2}, or H{sub 2}PO{sub 3}. We find that hydrogen molecules always preferentially bind at or near the functionalized edge, and display induced dipole moments. Binding is generally enhanced by the presence of polar functional groups. The largest gains are observed for groups with oxygen lone pairs that can facilitate local charge reorganization, with the biggest single enhancement in adsorption energy found for “strong functionalization” bymore » H{sub 2}PO{sub 3} (115 meV/H{sub 2} versus 52 meV/H{sub 2} on bare graphene). We show that for binding on the “outer edge” near the functional group, the presence of the group can introduce appreciable contributions from Debye interactions and higher-order multipole electrostatic terms, in addition to the dominant London dispersion interactions. For those functional groups that contain the OH moiety, the adsorption energy is linearly proportional to the number of lone pairs on oxygen atoms. Mixed functionalization with two different functional groups on a graphene edge can also have a synergistic effect, particularly when electron-donating and electron-withdrawing groups are combined. For binding on the “inner edge” somewhat farther from the functional group, most of the binding again arises from London interactions; however, there is also significant charge redistribution in the π manifold, which directly reflects the electron donating or withdrawing capacity of the functional group. Our results offer insight into the specific origins of weak binding of gas molecules on graphene, and suggest that edge functionalization could perhaps be used in combination with other strategies to increase the uptake of hydrogen in graphene. They also have relevance for the storage of hydrogen in porous carbon materials, such as activated carbons.« less

Interfacial Strength and Physical Properties of Functionalized Graphene - Epoxy Nanocomposites

NASA Technical Reports Server (NTRS)

Miller, Sandi G.; Heimann, Paula; Scheiman, Daniel; Adamson, Douglas H.; Aksay, Iihan A.; Prud'homme, Robert K.

2006-01-01

The toughness and coefficient of thermal expansion of a series of functionalized graphene sheet - epoxy nanocomposites are investigated. Functionalized graphene sheets are produced by splitting graphite oxide into single graphene sheets through a rapid thermal expansion process. These graphene sheets contain approx. 10% oxygen due to the presence of hydroxide, epoxide, and carboxyl functional groups which assist in chemical bond formation with the epoxy matrix. Intrinsic surface functionality is used to graft alkyl amine chains on the graphene sheets, and the addition of excess hardener insures covalent bonding between the epoxide matrix and graphene sheets. Considerable improvement in the epoxy dimensional stability is obtained. An increase in nanocomposite toughness is observed in some cases.

Molecular Structures and Sorption Mechanisms of Biochars as Heterogeneous Carbon Materials

NASA Astrophysics Data System (ADS)

Chen, Baoliang; Chen, Zaiming; Xiao, Xin; Fang, Qile

2015-04-01

Surface functional groups such as carboxyl play a vital role in the environmental applications of biochar as a soil amendment. However, the quantification of oxygen-containing groups on a biochar surface still lacks systematical investigation. An integrated method combining chemical and spectroscopic techniques was established to quantitatively identify the chemical states, dissociation constants (pKa), and contents of oxygen-containing groups on dairy manure-derived biochars prepared at 100-700 °C. The dissociation pH of carboxyl groups on the biochar surface covered a wide range of pH values (pH 2-11), due to the varied structural micro-environments and chemical states. For low temperature biochars (≤350 °C), carboxyl existed not only as hydrogen-bonded carboxyl and unbonded carboxyl groups but also formed esters at the surface of biochars. The esters consumed OH‒ via saponification in the alkaline pH region and enhanced the dissolution of organic matter from biochars. For high temperature biochars (≥500 °C), esters came from carboxyl were almost eliminated via carbonization (ester pyrolysis), while lactones were developed. The surface density of carboxyl groups on biochars decreased sharply with the increase of the biochar-producing temperature, but the total contents of the surface carboxyls for different biochars were comparable (with a difference < 3-fold) as a result of the expanded surface area at high pyrolytic temperatures. Understanding the wide pKa ranges and the abundant contents of carboxyl groups on biochars is a prerequisite to recognition of the multi-functional applications and biogeochemical cycling of biochars. A schematic diagram for the dissociation of acid/base groups on biochar surfaces and their related functions was depicted. The protonated biochars favor inorganic anion adsorption and ionizable organic chemical sorption, while the deprotonated biochars favor cationic nutrient retention, heavy metal immobilization, and the release of dissolved materials. For low temperature biochars (i.e., DM100, DM250 and DM350), the acid/base group dissociation directly controls the pH buffering properties of biochars. The resulting surface charges regulate biochars in nutrient retention, sorption/immobilization of hazardous pollutants and biochar particle dispersing properties. Meanwhile, dissociation of acid/base groups affects carbon and silica biogeochemical cycling by regulating the release of organic matter from the cleavage of esters and dissolution of the Si-containing minerals. For high temperature biochars (i.e., DM500 and DM700), the effect of acid/base dissociation on organic matter dissolution is eliminated, but other functions are similar. CGs are the major acid/base groups on biochar surfaces. In field applications, such abundant CGs are worthy of concern in terms of multiple functions of biochars, such as soil pH adjustment, soil nutrient retention, and toxic metals immobilization.

Surface energy modification for biomedical material by corona streamer plasma processing to mitigate bacterial adhesion

NASA Astrophysics Data System (ADS)

Alhamarneh, Ibrahim; Pedrow, Patrick

2011-10-01

Bacterial adhesion initiates biofouling of biomedical material but the processes can be reduced by adjusting the material's surface energy. The surface of surgical-grade 316L stainless steel (316L SS) had its hydrophilic property enhanced by processing in a corona streamer plasma reactor using atmospheric pressure Ar mixed with O2. Reactor excitation was 60 Hz ac high-voltage (<= 10 kV RMS) applied to a multi-needle-to-grounded-torus electrode configuration. Applied voltage and streamer current pulses were monitored with a broadband sensor system. When Ar/O2 plasma was used, the surface energy was enhanced more than with Ar plasma alone. Composition of the surface before and after plasma treatment was characterized by XPS. As the hydrophilicity of the treated surface increased so did percent of oxygen on the surface thus we concluded that reduction in contact angle was mainly due to new oxygen-containing functionalities. FTIR was used to identify oxygen containing groups on the surface. The aging effect that accompanies surface free energy adjustments was also observed.

Emission FTIR analyses of thin microscopic patches of jet fuel residue deposited on heated metal surface

NASA Technical Reports Server (NTRS)

Lauer, J. L.; Vogel, P.

1984-01-01

Deposits laid down in patches on metal strips in a high pressure/high temperature fuel system simulator operated with aerated fuel at varying flow rates were analyzed by emission FTIR in terms of functional groups. Significant differences were found in the spectra and amounts of deposits derived from fuels to which small concentrations of oxygen-, nitrogen-, or sulfur-containing heterocyclics or metal naphthenates were added. The spectra of deposits generated on strips by heating fuels and air in a closed container were very different from those of the flowing fluid deposits. One such closed-container dodecane deposit on silver gave a strong surface-enhanced Raman spectrum.

The role of dietary long chain fatty acids in mitochondrial structure and function. Effects on rat cardiac mitochondrial respiration.

PubMed

Clandinin, M T

1978-02-01

To evaluate the effect of dietary rapeseed oils on cardiac mitochondrial function and metabolic conservation of energy, male weanling rats derived from the Sprague-Dawley strain were fed three rations containing either 15% (w/w) soybean oil, low erucic acid rapeseed oil or a high erucic acid rapeseed oil. Cardiac mitochondria were isolated for measurement of mitochondrial respiratory functions. Pyruvate and malate plus malonate or succinate plus amytal, or alpha-ketoglutarate and malate plus malonate were utilized as substrates for oxidative phosphorylation. Net rates of state 3 oxygen uptake and therefore ATP synthesis were found to decline with chronic feeding of the 15% (w/w) oil containing diets. Significantly reduced ADP/O ratios were observed for groups fed high erucic acid rapeseed oil containing diets for 11 days. Decreased ADP/O ratios were also observed for groups fed high or low erucic acid rapeseed oils for 112 days. When pyruvate and malate plus malonate were utilized as substrates, reduced rates of ATP synthesis were observed after chronic feeding of high erucic acid rapeseed oil diets. Only prolonged feeding of low erucic acid rapeseed oils resulted in significant alterations in the efficiency of oxidative phosphorylation.

Function evaluation of asphalt mixture with industrially produced BOF slag aggregate.

PubMed

Zhao, Meiling; Wu, Shaopeng; Chen, Zongwu; Li, Chao

2016-07-04

Laboratory research suggested that basic oxygen furnace (BOF) slag-based asphalt mixture was a functional material. However, the BOF slag aggregate's quality was difficult to control when it was heavily used in entity engineering. The primary objective of this research was to evaluate the functional performances of asphalt mixture containing BOF slag coarse aggregate (BSCA), which was from an industrialized production line. Limestone mixture was a control group. The Marshall method was first adopted to design asphalt mixtures. The performances of limestone asphalt mixture and BOF slag asphalt mixture including fatigue failure resistance and moisture stability were then evaluated and compared. Results showed that the asphalt mixture containing BSCA possessed better durability, which meant the quality of BSCA from industrialized production lines was well controlled and this BSCA can be heavily used in entity engineering.

Oxygen sensitive, refractory oxide composition

DOEpatents

Holcombe, Jr., Cressie E.; Smith, Douglas D.

1976-01-01

Oxide compositions containing niobium pentoxide and an oxide selected from the group consisting of hafnia, titania, and zirconia have electrical conductivity characteristics which vary greatly depending on the oxygen content.

Capacity and mechanisms of ammonium and cadmium sorption on different wetland-plant derived biochars.

PubMed

Cui, Xiaoqiang; Hao, Hulin; Zhang, Changkuan; He, Zhenli; Yang, Xiaoe

2016-01-01

The objective of this study was to investigate the relationship between Cd(2+)/NH4(+) sorption and physicochemical properties of biochars produced from different wetland plants. Biochars from six species of wetland plants (i.e., Canna indica, Pennisetum purpureum Schum, Thalia dealbata, Zizania caduciflora, Phragmites australis and Vetiveria zizanioides) were obtained at 500°C and characterized, and their sorption for ammonium and cadmium was determined. There were significant differences in elemental composition, functional groups and specific surface area among the biochars derived from different wetland plant species. Sorption of ammonium and cadmium on the biochars could be described by a pseudo second order kinetic model, and the simple Langmuir model fits the isotherm data better than the Freundlich or Temkin model. The C. indica derived biochar had the largest sorption capacity for NH4(+) and Cd(2+), with a maximum sorption of 13.35 and 125.8mgg(-1), respectively. P. purpureum Schum derived biochar had a similar maximum sorption (119.3mgg(-1)) for Cd(2+). Ammonium sorption was mainly controlled by cation exchange, surface complexation with oxygen-containing functional groups and the formation of magnesium ammonium phosphate compounds, whereas for Cd(2+) sorption, the formation of cadmium phosphate precipitates, cation exchange and binding to oxygen-containing groups were the major possible mechanisms. In addition, the sorption of ammonium and cadmium was not affected by surface area and microporosity of the biochars. Copyright © 2015 Elsevier B.V. All rights reserved.

[Biochemical characteristics of compensation of posthemorrhagic anemia in patients presenting with nasal bleeding].

PubMed

Boĭko, N V; Kolmakova, T S; Bykova, V V

2010-01-01

This work was designed to study the development of compensatory processes during posthemorrhagic anemia in 82 patients presenting with nasal bleeding (NB). The patients were allocated to three groups. Group 1 included patients with isolated episodes of NB, group 2 was comprised of patients in a moderately severe condition with recurring NB, group 3 was composed of patients in a severe condition with recurring NB. The general medical examination was supplemented by the evaluation of factors maintaining the oxygen-transporting function of the blood (hemoglobin affinity for oxygen, erythrocyte content of 2.3-diphosphoglyceric (2.3-DPG) acid as the principal modulator of hemoglobin affinity for oxygen) and indicators of energy (carbohydrate) metabolism in plasma and erythrocytes (glucose-6-phosphate dehydrogenase (G-6-PDH) activity, pyruvic acid (PA), lactate and lactate dehydrogenase (LDH) levels). Changes of biochemical parameters in patients presenting with incidental episodes of NB (group 1) suggested a compensatory increase in functional potential of the blood oxygen-transporting system. Patients of group 2 showed evidence of development of the modulation-type adaptive and compensatory mechanisms. Those of group 3 experienced a decrease of the 2.3-DPH level in erythrocytes and enhancement of hemoglobin affinity for oxygen which slowed down its uptake by the tissues. Tissue hypoxia and accompanying acidosis aggravated the impairment of gas-transporting function of the blood. In is concluded that patients of group 3 are at risk of uncompensated hypoxic hypoxia associated with the unfavourable changes in the oxygen-transporting function and the impairment of the functional potential of erythrocytes. Taken together, these untoward factors may be responsible for the severe clinical conditions of these patients.

Effects of HMX exposure upon metabolic rate of northern bobwhite quail (Colinus virginianus) in ovo.

PubMed

Liu, Jun; Cox, Stephen B; Beall, Blake; Brunjes, Kristina J; Pan, Xiaoping; Kendall, Ronald J; Anderson, Todd A; McMurry, Scott T; Cobb, George P; Smith, Philip N

2008-05-01

We evaluated the use of the gas exchange rate as an ecologically relevant indicator of chemical stress in avian embryos/eggs. Northern bobwhite quail (Colinus virginianus) were exposed to octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) via feed containing nominal concentrations of 0, 12.5, 50.0, and 125.0 mg kg(-1). Metabolic rates (oxygen consumption) of developing quail eggs were then measured via respirometry to examine potential effects of HMX exposure. Metabolic rates were examined on 5, 9, and 21 d of incubation. Next, concentrations of HMX in embryos/eggs were determined by liquid chromatography-mass spectrometry. Mean (+/-SE) concentrations of HMX in eggs were 21.0+/-5.9, 1113+/-79.0, 3864+/-154.0, and 7426+/-301.1 ng g(-1) in control, low, medium and high dose groups, respectively. There were significant differences in oxygen consumption among the three embryo ages, however differences among the ages were not consistent among dose groups (age x dose group interaction p<0.0001). Oxygen consumption rates did not vary as a function of HMX in embryos (p=0.18). No evidence was observed for alterations of in ovo metabolic rates associated with HMX exposure.

Improving the capacity of lithium-sulfur batteries by tailoring the polysulfide adsorption efficiency of hierarchical oxygen/nitrogen-functionalized carbon host materials.

PubMed

Schneider, Artur; Janek, Jürgen; Brezesinski, Torsten

2017-03-22

The use of monolithic carbons with structural hierarchy and varying amounts of nitrogen and oxygen functionalities as sulfur host materials in high-loading lithium-sulfur cells is reported. The primary focus is on the strength of the polysulfide/carbon interaction with the goal of assessing the effect of (surface) dopant concentration on cathode performance. The adsorption capacity - which is a measure of the interaction strength between the intermediate lithium polysulfide species and the carbon - was found to scale almost linearly with the nitrogen level. Likewise, the discharge capacity of lithium-sulfur cells increased linearly. This positive correlation can be explained by the favorable effect of nitrogen on both the chemical and electronic properties of the carbon host. The incorporation of additional oxygen-containing surface groups into highly nitrogen-functionalized carbon helped to further enhance the polysulfide adsorption efficiency, and therefore the reversible cell capacity. Overall, the areal capacity could be increased by almost 70% to around 3 mA h cm -2 . We believe that the design parameters described here provide a blueprint for future carbon-based nanocomposites for high-performance lithium-sulfur cells.

Nitrogen-doped partially reduced graphene oxide rewritable nonvolatile memory.

PubMed

Seo, Sohyeon; Yoon, Yeoheung; Lee, Junghyun; Park, Younghun; Lee, Hyoyoung

2013-04-23

As memory materials, two-dimensional (2D) carbon materials such as graphene oxide (GO)-based materials have attracted attention due to a variety of advantageous attributes, including their solution-processability and their potential for highly scalable device fabrication for transistor-based memory and cross-bar memory arrays. In spite of this, the use of GO-based materials has been limited, primarily due to uncontrollable oxygen functional groups. To induce the stable memory effect by ionic charges of a negatively charged carboxylic acid group of partially reduced graphene oxide (PrGO), a positively charged pyridinium N that served as a counterion to the negatively charged carboxylic acid was carefully introduced on the PrGO framework. Partially reduced N-doped graphene oxide (PrGODMF) in dimethylformamide (DMF) behaved as a semiconducting nonvolatile memory material. Its optical energy band gap was 1.7-2.1 eV and contained a sp2 C═C framework with 45-50% oxygen-functionalized carbon density and 3% doped nitrogen atoms. In particular, rewritable nonvolatile memory characteristics were dependent on the proportion of pyridinum N, and as the proportion of pyridinium N atom decreased, the PrGODMF film lost memory behavior. Polarization of charged PrGODMF containing pyridinium N and carboxylic acid under an electric field produced N-doped PrGODMF memory effects that followed voltage-driven rewrite-read-erase-read processes.

Synthesis and biological screening by novel hybrid fluorocarbon hydrocarbon compounds for use as artificial blood substitutes

NASA Technical Reports Server (NTRS)

Moacanin, J.; Scherer, K.; Toronto, A.; Lawson, D.; Terranova, T.; Yavrouian, A.; Astle, L.; Harvey, S.; Kaaelble, D. H.

1979-01-01

A series of hybrid fluorochemicals of general structure R(1)R(2)R(3)CR(4) was prepared where the R(i)'s (i=1,2,3) is a saturated fluoroalkyl group of formula C sub N F sub 2n+1, and R(4) is an alkyl group C sub n H sub 2n+1 or a related moiety containing amino, ether, or ester functions but no CF bonds. Compounds of this class containing approximately eight to twenty carbons total have physical properties suitable for use as the oxygen carrying phase of fluorochemical emulsion artificial blood. The chemical synthesis, and physical and biological testing of pure single isomers of the proposed artificial blood candidate compounds are included. Significant results are given.

Correlation between the microstructures of graphite oxides and their catalytic behaviors in air oxidation of benzyl alcohol.

PubMed

Geng, Longlong; Wu, Shujie; Zou, Yongcun; Jia, Mingjun; Zhang, Wenxiang; Yan, Wenfu; Liu, Gang

2014-05-01

A series of graphite oxide (GO) materials were obtained by thermal treatment of oxidized natural graphite powder at different temperatures (from 100 to 200 °C). The microstructure evolution (i.e., layer structure and surface functional groups) of the graphite oxide during the heating process is studied by various characterization means, including XRD, N2 adsorption, TG-DTA, in situ DRIFT, XPS, Raman, TEM and Boehm titration. The characterization results show that the structures of GO materials change gradually from multilayer sheets to a transparent ultrathin 2D structure of the carbon sheets. The concentration of surface COH and HOCO groups decrease significantly upon treating temperature increasing. Benzyl alcohol oxidation with air as oxidant source was carried out to detect the catalytic behaviors of different GO materials. The activities of GO materials decrease with the increase of treating temperatures. It shows that the structure properties, including ultrathin sheets and high specific surface area, are not crucial factors affecting the catalytic activity. The type and amount of surface oxygen-containing functional groups of GO materials tightly correlates with the catalytic performance. Carboxylic groups on the surface of GO should act as oxidative sites for benzyl alcohol and the reduced form could be reoxidized by molecular oxygen. Copyright © 2014 Elsevier Inc. All rights reserved.

High electrochemical capacitor performance of oxygen and nitrogen enriched activated carbon derived from the pyrolysis and activation of squid gladius chitin

NASA Astrophysics Data System (ADS)

Raj, C. Justin; Rajesh, Murugesan; Manikandan, Ramu; Yu, Kook Hyun; Anusha, J. R.; Ahn, Jun Hwan; Kim, Dong-Won; Park, Sang Yeup; Kim, Byung Chul

2018-05-01

Activated carbon containing nitrogen functionalities exhibits excellent electrochemical property which is more interesting for several renewable energy storage and catalytic applications. Here, we report the synthesis of microporous oxygen and nitrogen doped activated carbon utilizing chitin from the gladius of squid fish. The activated carbon has large surface area of 1129 m2 g-1 with microporous network and possess ∼4.04% of nitrogen content in the form of pyridinic/pyrrolic-N, graphitic-N and N-oxide groups along with oxygen and carbon species. The microporous oxygen/nitrogen doped activated carbon is utilize for the fabrication of aqueous and flexible supercapacitor electrodes, which presents excellent electrochemical performance with maximum specific capacitance of 204 Fg-1 in 1 M H2SO4 electrolyte and 197 Fg-1 as a flexible supercapacitor. Moreover, the device displays 100% of specific capacitance retention after 25,000 subsequent charge/discharge cycles in 1 M H2SO4 electrolyte.

New singlet oxygen donors based on naphthalenes: synthesis, physical chemical data, and improved stability.

PubMed

Klaper, Matthias; Linker, Torsten

2015-06-01

Singlet oxygen donors are of current interest for medical applications, but suffer from a short half-life leading to low singlet oxygen yields and problems with storage. We have synthesized more than 25 new singlet oxygen donors based on differently substituted naphthalenes in only a few steps. The influence of functional groups on the reaction rate of the photooxygenations, thermolysis, half-life, and singlet oxygen yield has been thoroughly studied. We determined various thermodynamic data and compared them with density functional calculations. Interestingly, remarkable stabilities of functional groups during the photooxygenations and stabilizing effects for some endoperoxides during the thermolysis have been found. Furthermore, we give evidence for a partly concerted and partly stepwise thermolysis mechanism leading to singlet and triplet oxygen, respectively. Our results might be interesting for "dark oxygenations" and future applications in medicine. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural Dynamics of Carbon Dots in Water and N, N-Dimethylformamide Probed by All-Atom Molecular Dynamics Simulations.

PubMed

Paloncýová, Markéta; Langer, Michal; Otyepka, Michal

2018-04-10

Carbon dots (CDs), one of the youngest members of the carbon nanostructure family, are now widely experimentally studied for their tunable fluorescence properties, bleaching resistance, and biocompatibility. Their interaction with biomolecular systems has also been explored experimentally. However, many atomistic details still remain unresolved. Molecular dynamics (MD) simulations enabling atomistic and femtosecond resolutions simultaneously are a well-established tool of computational chemistry which can provide useful insights into investigated systems. Here we present a full procedure for performing MD simulations of CDs. We developed a builder for generating CDs of a desired size and with various oxygen-containing surface functional groups. Further, we analyzed the behavior of various CDs differing in size, surface functional groups, and degrees of functionalization by MD simulations. These simulations showed that surface functionalized CDs are stable in a water environment through the formation of an extensive hydrogen bonding network. We also analyzed the internal dynamics of individual layers of CDs and evaluated the role of surface functional groups on CD stability. We observed that carboxyl groups interconnected the neighboring layers and decreased the rate of internal rotations. Further, we monitored changes in the CD shape caused by an excess of charged carboxyl groups or carbonyl groups. In addition to simulations in water, we analyzed the behavior of CDs in the organic solvent DMF, which decreased the stability of pure CDs but increased the level of interlayer hydrogen bonding. We believe that the developed protocol, builder, and parameters will facilitate future studies addressing various aspects of structural features of CDs and nanocomposites containing CDs.

Unravelling Some of the Structure-Property Relationships in Graphene Oxide at Low Degree of Oxidation.

PubMed

Savazzi, Filippo; Risplendi, Francesca; Mallia, Giuseppe; Harrison, Nicholas M; Cicero, Giancarlo

2018-04-05

Graphene oxide (GO) is a versatile 2D material whose properties can be tuned by changing the type and concentration of oxygen-containing functional groups attached to its surface. However, a detailed knowledge of the dependence of the chemo/physical features of this material on its chemical composition is largely unknown. We combine classical molecular dynamics and density functional theory simulations to predict the structural and electronic properties of GO at low degree of oxidation and suggest a revision of the Lerf-Klinowski model. We find that layer deformation is larger for samples containing high concentrations of epoxy groups and that correspondingly the band gap increases. Targeted chemical modification of the GO surface appears to be an effective route to tailor the electronic properties of the monolayer for given applications. Our simulations also show that the chemical shift of the C-1s XPS peak allows one to unambiguously characterize GO composition, resolving the peak attribution  uncertainty often encountered in experiments.

Investigation of surface potentials in reduced graphene oxide flake by Kelvin probe force microscopy

NASA Astrophysics Data System (ADS)

Negishi, Ryota; Takashima, Kai; Kobayashi, Yoshihiro

2018-06-01

The surface potential (SP) of reduced graphene oxide (rGO) flakes prepared by thermal treatments of GO under several conditions was analyzed by Kelvin probe force microscopy. The low-crystalline rGO flakes in which a significant amount of oxygen functional groups and structural defects remain have a much lower SP than mechanically exfoliated graphene free from oxygen and defects. On the other hand, the highly crystalline rGO flake after a thermal treatment for the efficient removal of oxygen functional groups and healing of structural defects except for domain boundary shows SP equivalent to that of the mechanically exfoliated graphene. These results indicate that the work function of rGO is sensitively modulated by oxygen functional groups and structural defects remaining after the thermal reduction process, but is not affected significantly by the domain boundary remaining after the healing of structural defects through the thermal treatment at high temperature.

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

Jia, Y.F.; Thomas, K.M.

Various types of oxygen functional groups were introduced onto the surface of coconut shell derived activated carbon by oxidation using nitric acid. Fourier-transform infrared spectroscopy (FTIR), temperature-programmed desorption (TPD), and selective neutralization were used to characterize the surface oxygen functional groups. The oxidized carbons were also heat treated to provide a suite of carbons where the oxygen functional groups of various thermal stabilities were varied progressively. The adsorption of cadmium ions was enhanced dramatically by oxidation of the carbon. The ratio of released protons to adsorbed cadmium ions on oxidized carbon was approximately 2, indicating cation exchange was involved inmore » the process of adsorption. Na{sup +} exchange studies with the oxidized carbon gave a similar ratio. After heat treatment of the oxidized carbons to remove oxygen functional groups, the ratio of H{sup +} released to Cd{sup 2+} adsorbed and the adsorption capacity decreased significantly. Both reversible and irreversible processes were involved in cadmium ion adsorption with reversible adsorption having higher enthalpy. The irreversible adsorption resulted from cation exchange with carboxylic acid groups, whereas the reversible adsorption probably involved physisorption of the partially hydrated cadmium ion.« less

Experimental study of the thermal stability of materials in high temperature oxygen-containing media

NASA Technical Reports Server (NTRS)

Abaltusov, Y. Y.; Bagramyan, A. R.; Grishin, A. M.; Yukhvid, V. I.

1986-01-01

An experimental study is made of the interaction of several materials with a high temperature medium containing oxygen. The temperature of the surface was measured as a function of time. It is found that the higher the velocity of mass removal from the surface, the more effective is the material from the viewpoint of heat resistance.

N-doped structures and surface functional groups of reduced graphene oxide and their effect on the electrochemical performance of supercapacitor with organic electrolyte

NASA Astrophysics Data System (ADS)

Li, Shin-Ming; Yang, Shin-Yi; Wang, Yu-Sheng; Tsai, Hsiu-Ping; Tien, Hsi-Wen; Hsiao, Sheng-Tsung; Liao, Wei-Hao; Chang, Chien-Liang; Ma, Chen-Chi M.; Hu, Chi-Chang

2015-03-01

Nitrogen-doped reduced graphene oxide (N-rGO) has been synthesized using a simple, efficient method combining instant thermal exfoliation and covalent bond transformation from a melamine-graphene oxide mixture. The capacitive performance of N-rGO has been tested in both aqueous (0.5 M H2SO4) and organic (1 M tetraethyl-ammonium tetrafluoroborate (TEABF4) in propylene carbonate (PC)) electrolytes, which are compared with those obtained from thermal-reduced graphene oxide (T-rGO) and chemical-reduced graphene oxide (C-rGO). The contributions of scan-rate-independent (double-layer-like) and scan-rate-dependent (pseudo-capacitance-like) capacitance of all reduced graphene oxides in both aqueous and organic electrolytes were evaluated and compared. The results show that relatively rich oxygen-containing functional groups on C-rGO form significant ion-diffusion barrier, resulting in worse electrochemical responses in organic electrolyte. By contrast, the N-doped structures, large surface area, and lower density of oxygen-containing groups make N-rGO become a promising electrode material for organic electric double-layer capacitors (EDLCs). The capacitance rate-retention of N-rGO reaches 71.1% in 1 M TEABF4/PC electrolyte when the scan rate is elevated to 200 mVs-1, demonstrating that N-rGO improves the relatively low-power drawback of EDLCs in organic electrolytes. The specific energy and power of a symmetric N-rGO cell in the organic electrolyte reach 25 Wh kg-1 and 10 kW kg-1, respectively.

A multifunctional material based on co-electrospinning for developing biosensors with optical oxygen transduction.

PubMed

Ramon-Marquez, Teresa; Medina-Castillo, Antonio L; Nagiah, Naveen; Fernandez-Gutierrez, Alberto; Fernandez-Sanchez, Jorge F

2018-07-26

A multifunctional material based on co-electrospinning has been developed as a basic material for the development of biosensors with optical oxygen transduction. It is based on coaxial nanofibres: inner fibres containing an oxygen sensitive dye and outer fibres containing aldehyde groups to allow the formation of Schiff bases with the amino groups of the enzyme. The resulting material preserves the oxygen sensing properties of the inner optical transducer as well as exhibits a high capacity for immobilizing molecules on its surface. Uricase has been selected as model enzyme and several parameters (temperature, pH, reaction time, buffer, and enzyme concentration) have been optimised to demonstrate the versatility of this novel multifunctional material in the development of biosensors with optical oxygen transduction for determining uric acid in serum samples. It suggests that the proposed multifunctional material can provide a promising multifunctional platform for biosensing applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Promiscuous anaerobes: new and unconventional metabolism in methanogenic archaea.

PubMed

Grochowski, Laura L; White, Robert H

2008-03-01

The development of an oxygenated atmosphere on earth resulted in the polarization of life into two major groups, those that could live in the presence of oxygen and those that could not-the aerobes and the anaerobes. The evolution of aerobes from the earliest anaerobic prokaryotes resulted in a variety of metabolic adaptations. Many of these adaptations center on the need to sustain oxygen-sensitive reactions and cofactors to function in the new oxygen-containing atmosphere. Still other metabolic pathways that were not sensitive to oxygen also diverged. This is likely due to the physical separation of the organisms, based on their ability to live in the presence of oxygen, which allowed for the independent evolution of the pathways. Through the study of metabolic pathways in anaerobes and comparison to the more established pathways from aerobes, insight into metabolic evolution can be gained. This, in turn, can allow for extra- polation to those metabolic pathways occurring in the Last Universal Common Ancestor (LUCA). Some of the unique and uncanonical metabolic pathways that have been identified in the archaea with emphasis on the biochemistry of an obligate anaerobic methanogen, Methanocaldococcus jannaschii are reviewed.

Intraoperative Oxygen Consumption During Liver Transplantation.

PubMed

Shibata, M; Matsusaki, T; Kaku, R; Umeda, Y; Yagi, T; Morimatsu, H

2015-12-01

The aim of this study was to investigate the changes in oxygen consumption during liver transplantation and to examine the relationship between intraoperatively elevated systemic oxygen consumption and postoperative liver function. This study was performed in 33 adult patients undergoing liver transplantation between September 2011 and March 2014. We measured intraoperative oxygen consumption through the use of indirect calorimetry, preoperative and intraoperative data, liver function tests, and postoperative complications and outcomes. The mean age of patients was 52 ± 9.7 years; 14 (42%) of them were women. Average Model for End-Stage Liver Disease scores were 20 ± 8.9. Oxygen consumption significantly increased after reperfusion from 172 ± 30 mL/min during the anhepatic phase to 209 ± 30 mL/min (P < .0001). We divided patients into 2 groups according to the increase in oxygen consumption after reperfusion (oxygen consumption after reperfusion minus anhepatic phase oxygen consumption: 40 mL/min increase as cutoff). The higher consumption group had a longer cold ischemia time and higher postoperative aspartate aminotransferase and alanine aminotransferase levels as compared with the lower oxygen consumption group. There were no statistically significant differences in major postoperative complications, but the higher oxygen consumption group tended to have shorter hospital stays than the lower consumption group (58 versus 95 days). We have demonstrated that oxygen consumption significantly increased after reperfusion. Furthermore, this increased oxygen consumption was associated with a longer cold ischemia time and shorter hospital stays. Copyright © 2015 Elsevier Inc. All rights reserved.

Oxygen Supplementation Improves Protein Milieu Supportive of Protein Synthesis and Antioxidant Function in the Cortex of Alzheimer's Disease Model Mice-a Quantitative Proteomic Study.

PubMed

Wang, Hao; Hong, Xiaoyu; Li, Shuiming; Wang, Yong

2017-10-01

Protein synthesis has been reported to be impaired in early-stage Alzheimer's disease (AD). Previously, we found that oxygen supplementation improved cognitive function and reduced mitochondrial damage in AD model mice. In the present study, we examined the effects of supplemental oxygen treatment on protein synthesis and oxidative damage. The synthesis of numerous proteins involved in mRNA splicing, transcription regulation, and translation was found to be significantly upregulated in cortex tissues of AD model mice given a supplemental oxygen treatment (OT group), relative to those of non-treated control AD model mice (Ctrl group), suggesting that impairment in protein synthesis may be alleviated by increased oxygen inhalation. Methionine oxidation and oxidation levels in general were similar between the OT and Ctrl groups, indicating that the oxygen supplementation treatment did not cause increases in peptide oxidation levels. On the contrary, the OT group exhibited upregulation of several proteins associated with antioxidant defense. These results support further exploration into the development of supplementary oxygen treatment as a potential therapy for AD.

Structural and functional properties of hemoglobins from unicellular organisms as revealed by resonance Raman spectroscopy.

PubMed

Egawa, Tsuyoshi; Yeh, Syun-Ru

2005-01-01

Hemoglobins have been discovered in organisms from virtually all kingdoms. Their presence in unicellular organisms suggests that the gene for hemoglobin is very ancient and that the hemoglobins must have functions other than oxygen transport, in view of the fact that O2 delivery is a diffusion-controlled process in these organisms. Based on sequence alignment, three groups of hemoglobins have been characterized in unicellular organisms. The group-one hemoglobins, termed truncated hemoglobins, consist of proteins with 110-140 amino acid residues and a novel two-over-two alpha-helical sandwich motif. The group-two hemoglobins, termed flavohemoglobins, consist of a hemoglobin domain, with a classical three-over-three alpha-helical sandwich motif, and a flavin-containing reductase domain that is covalently attached to it. The group-three hemoglobins consist of myoglobin-like proteins that have high sequence homology and structural similarity to the hemoglobin domain of flavohemoglobins. In this review, recent resonance Raman studies of each group of these proteins are presented. Their implications are discussed in the context of the structural and functional properties of these novel hemoglobins.

Hydrothermally Driven Transformation of Oxygen Functional Groups at Multiwall Carbon Nanotubes for Improved Electrocatalytic Applications.

PubMed

Suryanto, Bryan H R; Chen, Sheng; Duan, Jingjing; Zhao, Chuan

2016-12-28

The role of carbon nanotubes in the advancement of energy conversion and storage technologies is undeniable. In particular, carbon nanotubes have attracted significant applications for electrocatalysis. However, one central issue related to the use of carbon nanotubes is the required oxidative pretreatment that often leads to significant damage of graphitic structures which deteriorates their electrochemical properties. Traditionally, the oxidized carbon nanomaterials are treated at high temperature under an inert atmosphere to repair the oxidation-induced defect sites, which simultaneously removes a significant number of oxygen functional groups. Nevertheless, recent studies have shown that oxygen functional groups on the surface of MWCNT are the essential active centers for a number of important electrocatalytic reactions such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Herein we first show that hydrothermal treatment as a mild method to improve the electrochemical properties and activities of surface-oxidized MWCNT for OER, HER, and ORR without significantly altering the oxygen content. The results indicate that hydrothermal treatment could potentially repair the defects without significantly reducing the pre-existing oxygen content, which has never been achieved before with conventional high-temperature annealing treatment.

Stable trifluorostyrene containing compounds grafted to base polymers, and their use as polymer electrolyte membranes

DOEpatents

Yang, Zhen-Yu; Roelofs, Mark Gerrit

2010-11-09

A fluorinated ion exchange polymer prepared by grafting at least one grafting monomer on to at least one base polymer, wherein the grafting monomer comprises structure 1a or 1b: wherein Z comprises S, SO.sub.2, or POR wherein R comprises a linear or branched perfluoroalkyl group of 1 to 14 carbon atoms optionally containing oxygen or chlorine, an alkyl group of 1 to 8 carbon atoms, an aryl group of 6 to 12 carbon atoms or a substituted aryl group of 6 to 12 carbon atoms; RF comprises a linear or branched perfluoroalkene group of 1 to 20 carbon atoms, optionally containing oxygen or chlorine; Q is chosen from F, --OM, NH.sub.2, --N(M)SO.sub.2R.sup.2.sub.F, and C(M)(SO.sub.2R.sup.2.sub.F).sub.2, wherein M comprises H, an alkali cation, or ammonium; R.sup.2.sub.F groups comprises alkyl of 1 to 14 carbon atoms which may optionally include ether oxygens or aryl of 6 to 12 carbon atoms where the alkyl or aryl groups may be perfluorinated or partially fluorinated; and n is 1 or 2 for 1a, and n is 1, 2, or 3 for 1b. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

Stable trifluorostyrene containing compounds grafted to base polymers, and their use as polymer electrolyte membranes

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

Yang, Zhen-Yu; Roelofs, Mark Gerrit

2010-11-09

A fluorinated ion exchange polymer prepared by grafting at least one grafting monomer on to at least one base polymer, wherein the grafting monomer comprises structure 1a or 1b: wherein Z comprises S, SO.sub.2, or POR wherein R comprises a linear or branched perfluoroalkyl group of 1 to 14 carbon atoms optionally containing oxygen or chlorine, an alkyl group of 1 to 8 carbon atoms, an aryl group of 6 to 12 carbon atoms or a substituted aryl group of 6 to 12 carbon atoms; RF comprises a linear or branched perfluoroalkene group of 1 to 20 carbon atoms, optionallymore » containing oxygen or chlorine; Q is chosen from F, --OM, NH.sub.2, --N(M)SO.sub.2R.sup.2.sub.F, and C(M)(SO.sub.2R.sup.2.sub.F).sub.2, wherein M comprises H, an alkali cation, or ammonium; R.sup.2.sub.F groups comprises alkyl of 1 to 14 carbon atoms which may optionally include ether oxygens or aryl of 6 to 12 carbon atoms where the alkyl or aryl groups may be perfluorinated or partially fluorinated; and n is 1 or 2 for 1a, and n is 1, 2, or 3 for 1b. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.« less

[Influence of raising oxygen content on function of platelet concentrate during preservation].

PubMed

Zhan, Tong; Xiao, Jian-Yu; Tao, Jing; Miao, Xi-Feng; Liu, Yan-Cun; Tang, Rong-Cai

2006-08-01

To explore the influence of raising oxygen (dissolved oxygen) content on function of platelet concentrate, the platelet concentrate was prepared by a CS-3000 plus blood cell separator. Experiments were divided into 2 groups: test group and control group. After raising oxygen content in platelet plasma under sterile operation, the platelet samples of two groups were preserved in oscillator with horizontal oscillation at 22 +/- 2 degrees C. The platelet count, platelet aggregation rate, lactic acid content and CD62p expression level of platelet were detected on 0, 1, 2, 3, 4, 5 days of platelet preservation. The results showed that the platelet count and platelet aggregation rate decreased with prolongation of preserved time, while the lactic acid content and CD62p expression level of platelet increased gradually. Compared with control group, there were significant differences in aggregation rate of platelet preserved for 2-3 days, and in CD62p expression level of platelet preserved for 1-3 days, while significant difference was found in lactic acid content of platelet preserved for 1-3 days. It is concluded that raising content of oxygen in platelet plasma can provide more oxygen to compensate oxygen supply deficiency for platelet metabolism and improve the efficiency of platelet oxygenic metabolism and the quality of platelet during preservation.

The adsorption of biogenic amines on carbon nanotubes

NASA Astrophysics Data System (ADS)

Sidorenko, I. G.; Markitan, O. V.; Vlasova, N. N.; Zagorovskii, G. M.; Lobanov, V. V.

2009-06-01

The adsorption of phenylethylamine, tryptamine, and tyramine on carbon nanotubes from aqueous solutions (pH 7.4) was studied depending on time and sorbate concentration. The suggestion was made that their interaction with electrodes was determined by electrostatic attraction between protonated amino groups and oxygen-containing functional groups of the surface of carbon. An increase in the adsorption of biological amines was caused by the interaction of the π systems of their aromatic rings with carbon surface hexagons. The adsorption of biogenic amines on carbon nanotubes was necessary for their possible electrooxidation and analytic determination by electrochemical methods with the use of carbon electrodes.

The importance of surface functional groups in the adsorption of copper onto walnut shell derived activated carbon.

PubMed

Xie, Ruzhen; Jin, Yan; Chen, Yao; Jiang, Wenju

2017-12-01

In this study, activated carbon (AC) was prepared from walnut shell using chemical activation. The surface chemistry of the prepared AC was modified by introducing or blocking certain functional groups, and the role of the different functional groups involved in the copper uptake was investigated. The structural and chemical heterogeneity of the produced carbons are characterized by Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, Boehm titration method and N 2 /77 K adsorption isotherm analysis. The equilibrium and the kinetics of copper adsorption onto AC were studied. The results demonstrated that the functional groups on AC played an important role in copper uptake. Among various surface functional groups, the oxygen-containing group was found to play a critical role in the copper uptake, and oxidation is the most effective way to improve Cu (II) adsorption onto AC. Ion-exchange was identified to be the dominant mechanism in the copper uptake by AC. Some other types of interactions, like complexation, were also proven to be involved in the adsorption process, while physical force was found to play a small role in the copper uptake. The regeneration of copper-loaded AC and the recovery of copper were also studied to evaluate the reusability of the oxidized AC.

An investigation of cerebral oxygen utilization, blood flow and cognition in healthy aging.

PubMed

Catchlove, Sarah J; Macpherson, Helen; Hughes, Matthew E; Chen, Yufen; Parrish, Todd B; Pipingas, Andrew

2018-01-01

Understanding how vascular and metabolic factors impact on cognitive function is essential to develop efficient therapies to prevent and treat cognitive losses in older age. Cerebral metabolic rate of oxygen (CMRO2), cerebral blood flow (CBF) and venous oxygenation (Yv) comprise key physiologic processes that maintain optimum functioning of neural activity. Changes to these parameters across the lifespan may precede neurodegeneration and contribute to age-related cognitive decline. This study examined differences in blood flow and metabolism between 31 healthy younger (<50 years) and 29 healthy older (>50 years) adults; and investigated whether these parameters contribute to cognitive performance. Participants underwent a cognitive assessment and MRI scan. Grey matter CMRO2 was calculated from measures of CBF (phase contrast MRI), arterial and venous oxygenation (TRUST MRI) to assess group differences in physiological function and the contribution of these parameters to cognition. Performance on memory (p<0.001) and attention tasks (p<0.001) and total CBF were reduced (p<0.05), and Yv trended toward a decrease (p = .06) in the older group, while grey matter CBF and CMRO2 did not differ between the age groups. Attention was negatively associated with CBF when adjusted (p<0.05) in the older adults, but not in the younger group. There was no such relationship with memory. Neither cognitive measure was associated with oxygen metabolism or venous oxygenation in either age group. Findings indicated an age-related imbalance between oxygen delivery, consumption and demand, evidenced by a decreased supply of oxygen with unchanged metabolism resulting in increased oxygen extraction. CBF predicted attention when the age-effect was controlled, suggesting a task- specific CBF- cognition relationship.

Effects of double and triple bonds on the spatial representations of odorants in the rat olfactory bulb.

PubMed

Johnson, Brett A; Ong, Joan; Lee, Kaman; Ho, Sabrina L; Arguello, Spart; Leon, Michael

2007-02-01

Many naturally occurring volatile chemicals that are detected through the sense of smell contain unsaturated (double or triple) carbon-carbon bonds. These bonds can affect odors perceived by humans, yet in a prior study of unsaturated hydrocarbons we found only very minor effects of unsaturated bonds. In the present study, we tested the possibility that unsaturated bonds affect the recognition of oxygen-containing functional groups, because humans perceive odor differences between such molecules. We therefore compared spatial activity patterns across the entire glomerular layer of the rat olfactory bulb evoked by oxygen-containing odorants differing systematically in the presence, position, number, and stereochemistry of unsaturated bonds. We quantified activity patterns by mapping [(14)C]2-deoxyglucose uptake into anatomically standardized data matrices, which we compared statistically. We found that the presence and number of unsaturated bonds consistently affected activity patterns, with the largest effect related to the presence of a triple bond. Effects of bond saturation included a loss of activity in glomeruli strongly activated by the corresponding saturated odorants and/or the presence of activity in areas not stimulated by the corresponding saturated compounds. The position of double bonds also affected patterns of activity, but cis vs. trans configuration had no measurable impact in all five sets of stereoisomers that we studied. These results simultaneously indicate the importance of interactions between carbon-carbon bond types and functional groups in the neural coding of odorant chemical information and highlight the emerging concept that the rat olfactory system is more sensitive to certain types of chemical differences than others. (c) 2006 Wiley-Liss, Inc.

Extraterrestrial platinum group nuggets in deep-sea sediments

NASA Technical Reports Server (NTRS)

Brownlee, D. E.; Bates, B. A.; Wheelock, M. M.

1984-01-01

A previously unrecognized property of iron cosmic spheres is reported. The most common spheres larger than 300 microns do not, in fact, contain FeNi metal cores, but instead contain a micrometer-sized nugget composed almost entirely of platinum group elements. These elements appear to have been concentrated by the oxidation of molten meteoritic metal during atmospheric entry. This process is critically dependent on the relative abundance of oxygen in the atmosphere, and the first appearance of the nuggets in the geological record may provide a marker indicating when the oxygen abundance attained half of its present level.

Low-Temperature Catalytic Process To Produce Hydrocarbons From Sugars

DOEpatents

Cortright, Randy D.; Dumesic, James A.

2005-11-15

Disclosed is a method of producing hydrogen from oxygenated hydrocarbon reactants, such as methanol, glycerol, sugars (e.g. glucose and xylose), or sugar alcohols (e.g. sorbitol). The method takes place in the condensed liquid phase. The method includes the steps of reacting water and a water-soluble oxygenated hydrocarbon in the presence of a metal-containing catalyst. The catalyst contains a metal selected from the group consisting of Group VIIIB transitional metals, alloys thereof, and mixtures thereof. The disclosed method can be run at lower temperatures than those used in the conventional steam reforming of alkanes.

Renal Blood Flow, Glomerular Filtration Rate, and Renal Oxygenation in Early Clinical Septic Shock.

PubMed

Skytte Larsson, Jenny; Krumbholz, Vitus; Enskog, Anders; Bragadottir, Gudrun; Redfors, Bengt; Ricksten, Sven-Erik

2018-06-01

Data on renal hemodynamics, function, and oxygenation in early clinical septic shock are lacking. We therefore measured renal blood flow, glomerular filtration rate, renal oxygen consumption, and oxygenation in patients with early septic shock. Prospective comparative study. General and cardiothoracic ICUs. Patients with norepinephrine-dependent early septic shock (n = 8) were studied within 24 hours after arrival in the ICU and compared with postcardiac surgery patients without acute kidney injury (comparator group, n = 58). None. Data on systemic hemodynamics and renal variables were obtained during two 30-minute periods. Renal blood flow was measured by the infusion clearance of para-aminohippuric acid, corrected for renal extraction of para-aminohippuric acid. Renal filtration fraction was measured by renal extraction of chromium-51 labeled EDTA. Renal oxygenation was estimated from renal oxygen extraction. Renal oxygen delivery (-24%; p = 0.037) and the renal blood flow-to-cardiac index ratio (-21%; p = 0.018) were lower, renal vascular resistance was higher (26%; p = 0.027), whereas renal blood flow tended to be lower (-19%; p = 0.068) in the septic group. Glomerular filtration rate (-32%; p = 0.006) and renal sodium reabsorption (-29%; p = 0.014) were both lower in the septic group. Neither renal filtration fraction nor renal oxygen consumption differed significantly between groups. Renal oxygen extraction was significantly higher in the septic group (28%; p = 0.022). In the septic group, markers of tubular injury were elevated. In early clinical septic shock, renal function was lower, which was accompanied by renal vasoconstriction, a lower renal oxygen delivery, impaired renal oxygenation, and tubular sodium reabsorption at a high oxygen cost compared with controls.

Surface characterization studies of walnut-shell biochar catalysts for simultaneously removing of organic sulfur from yellow phosphorus tail gas

NASA Astrophysics Data System (ADS)

Song, Xin; Li, Kai; Ning, Ping; Wang, Chi; Sun, Xin; Tang, Lihong; Ruan, Haotian; Han, Shuang

2017-12-01

The influences of different preparation conditions for surface characteristics on removing organic sulfur were studied. From BET, XRD, FTIR, DRIFTS, TG/DTA, CO2-TPD results, it can be seen that these preparation conditions had great influences on the pore structure, specific surface area, crystal structure and surface functional groups. The micropore volume, amorphous structure and alkalinity site strength played major roles in desulfurization process. H2S was oxidized by oxygen containing functional groups, such as sbnd COO, sbnd Cdbnd O. H2O molecule could be converted into some groups, such as sbnd CH and Csbnd OH groups, and promoted the hydrolysis reaction. The strong alkalinity site was the key factor for chemical adsorption and hydrolysis. H2O molecule, sbnd CH, Csbnd OH groups promoted the hydrolysis reaction and sbnd COO, sbnd Cdbnd O groups promoted the oxidation of H2S on the surface of WSB. Meanwhile, the main desulfurization process over WSB after carbonization was adsorption and it changed to hydrolysis reaction after activation on the surface of WSB. Furthermore, the reaction mechanism was investigated by DRIFTS measurement according to the change of surface functional groups.

Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions

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

Dellon, Lauren D.; Sung, Chun-Yi; Robichaud, David J.

Bio-oil produced from biomass fast pyrolysis often requires catalytic upgrading to remove oxygen and acidic species over zeolite catalysts. The elementary reactions in the mechanism for this process involve carbenium and oxonium ions. In order to develop a detailed kinetic model for the catalytic upgrading of biomass, rate constants are required for these elementary reactions. The parameters in the Arrhenius equation can be related to thermodynamic properties through structure-reactivity relationships, such as the Evans-Polanyi relationship. For this relationship, enthalpies of formation of each species are required, which can be reasonably estimated using group additivity. However, the literature previously lacked groupmore » additivity values for oxygenates, oxonium ions, and oxygen-containing carbenium ions. In this work, 71 group additivity values for these types of groups were regressed, 65 of which had not been reported previously and six of which were newly estimated based on regression in the context of the 65 new groups. Heats of formation based on atomization enthalpy calculations for a set of reference molecules and isodesmic reactions for a small set of larger species for which experimental data was available were used to demonstrate the accuracy of the Gaussian-4 quantum mechanical method in estimating enthalpies of formation for species involving the moieties of interest. Isodesmic reactions for a total of 195 species were constructed from the reference molecules to calculate enthalpies of formation that were used to regress the group additivity values. The results showed an average deviation of 1.95 kcal/mol between the values calculated from Gaussian-4 and isodesmic reactions versus those calculated from the group additivity values that were newly regressed. Importantly, the new groups enhance the database for group additivity values, especially those involving oxonium ions.« less

Enhanced Adsorption of Trivalent Arsenic from Water by Functionalized Diatom Silica Shells

PubMed Central

Zhang, Zhijian; Xu, Liping; Zhang, Chunlong

2015-01-01

The potential of porous diatom silica shells as a naturally abundant low-cost sorbent for the removal of arsenic in aqueous solutions was investigated in a batch study. The objective of this work was to chemically modify the silica shells of a diatom Melosira sp. with bifunctional (thiol and amino) groups to effectively remove arsenic in its toxic As(III) form (arsenite) predominant in the aquatic environment. Sorption experiments with this novel sorbent were conducted under varying conditions of pH, time, dosage, and As(III) concentration. A maximum adsorption capacity of 10.99 mg g-1 was achieved within 26 h for a solution containing 12 mg L-1 As(III) at pH 4 and sorbent dosage of 2 g L-1. The functionalized diatom silica shells had a surface morphological change which was accompanied by increased pore size at the expense of reduced specific surface area and total pore volume. As(III) adsorption was best fitted with the Langmuir-Freundlich model, and the adsorption kinetic data using pore surface diffusion model showed that both the external (film) and internal (intraparticle) diffusion can be rate-determining for As(III) adsorption. Fourier transform infrared spectroscopy (FTIR) indicated that the thiol and amino groups potentially responsible for As(III) adsorption were grafted on the surface of diatom silica shells. X-ray photoelectron spectroscopy (XPS) further verified that this unique sorbent proceeded via a chemisorption mechanism through the exchange between oxygen-containing groups of neutral As(III) and thiol groups, and through the surface complexation between As(III) and protonated nitrogen and hydroxyl groups. Results indicate that this functionalized bioadsorbent with a high As(III) adsorption capacity holds promise for the treatment of As(III) containing wastewater. PMID:25837498

Mesoporous poly(ionic liquid) supported palladium(II) catalyst for oxidative coupling of benzene under atmospheric oxygen

NASA Astrophysics Data System (ADS)

Liu, Yangqing; Wang, Kai; Hou, Wei; Shan, Wanjian; Li, Jing; Zhou, Yu; Wang, Jun

2018-01-01

Multi-functional mesoporous poly(ionic liquid) (MPIL) containing pyridine-based ionic liquid (IL) moieties and adjacent double sbnd COOH groups was synthesized through the free radical copolymerization of IL monomer N-propane sulfonate-4-vinylpyridine, maleic anhydride and divinylbenzene. Palladium(II) species were anchored on this MPIL support, affording the first efficient heterogeneous catalyst for the oxidative coupling of benzene to biphenyl under atmospheric oxygen at low temperature. The biphenyl yield of 15.0% (selectivity: 98.5%, turnover number: 62) was even higher than the one over the homogeneous counterpart palladium acetate. The catalyst can be facilely separated and reused. The IL moiety in the polymeric framework endowed the formation of immobilized palladium(II) species with high electrophilicity, which responds to the high performance.

Experimental and Theoretical Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures

NASA Technical Reports Server (NTRS)

Nguyen, Quynhgiao N.; Myers, Dwight L.; Jacobson, Nathan S.; Opila, Elizabeth J.

2014-01-01

The transpiration method was used to determine the volatility of titanium dioxide (TiO2) in water vapor-containing environments at temperatures between 1473 and 1673 K. Water contents ranged from 0 to 76 mole % in oxygen or argon carrier gases for 20 to 250 hr exposure times. Results indicate that oxygen is not a key contributor to volatilization and the primary reaction for volatilization in this temperature range is: TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods to extract an enthalpy and entropy of formation. The geometry and vibrational frequencies of TiO(OH)2(g) were computed using B3LYP density functional theory, and the enthalpy of formation was computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. Thermal functions are calculated using both a structure with bent and linear hydroxyl groups. Calculated second and third heats show closer agreement with the linear hydroxyl group, suggesting more experimental and computational spectroscopic and structural work is needed on this system.

Spectroscopic investigation of the wettability of multilayer graphene using highly ordered pyrolytic graphite as a model material.

PubMed

Ashraf, Ali; Wu, Yanbin; Wang, Michael C; Aluru, Narayana R; Dastgheib, Seyed A; Nam, SungWoo

2014-11-04

We report the intrinsic water contact angle (WCA) of multilayer graphene, explore different methods of cleaning multilayer graphene, and evaluate the efficiency of those methods on the basis of spectroscopic analysis. Highly ordered pyrolytic graphite (HOPG) was used as a model material system to study the wettability of the multilayer graphene surface by WCA measurements. A WCA value of 45° ± 3° was measured for a clean HOPG surface, which can serve as the intrinsic WCA for multilayer graphene. A 1 min plasma treatment (100 W) decreased the WCA to 6°, owing to the creation of surface defects and functionalization by oxygen-containing groups. Molecular dynamics simulations of water droplets on the HOPG surface with or without the oxygen-containing defect sites confirmed the experimental results. Heat treatment at near atmospheric pressure and wet chemical cleaning methods using hydrofluoric acid and chloroform did not change the WCA significantly. Low-pressure, high-temperature annealing under argon and hydrogen reduced the WCA to 54°, close to the intrinsic WCA of HOPG. Raman spectroscopy and atomic force microscopy did not show any significant change for the HOPG surface after this treatment, confirming low-pressure, high-temperature annealing as an effective technique to clean multilayer graphene without damaging the surface. Time-of-flight secondary ion mass spectrometry indicated the existence of hydrocarbon species on the surface of the HOPG sample that was exposed to air for <5 min and the absence of these impurities in the bulk. X-ray photoelectron spectroscopy analyses of the sample surfaces after the different cleaning techniques were performed to correlate the WCA to the surface chemistry. X-ray photoelectron spectroscopy results revealed that the WCA value changed drastically, depending on the amounts of oxygen-containing and hydrocarbon-containing groups on the surface.

In situ one-step hydrothermal synthesis of oxygen-containing groups-modified g-C3N4 for the improved photocatalytic H2-evolution performance

NASA Astrophysics Data System (ADS)

Wu, Xinhe; Chen, Fengyun; Wang, Xuefei; Yu, Huogen

2018-01-01

Surface modification of g-C3N4 is one of the most effective strategies to boost its photocatalytic H2-evolution performance via promoting the interfacial catalytic reactions. In this study, an in situ one-step hydrothermal method was developed to prepare the oxygen-containing groups-modified g-C3N4 (OG/g-C3N4) by a facile and green hydrothermal treatment of bulk g-C3N4 in pure water without any additives. It was found that the hydrothermal treatment (180 °C) not only could greatly increase the specific surface area (from 2.3 to 69.8 m2 g-1), but also caused the formation of oxygen-containing groups (sbnd OH and Cdbnd O) on the OG/g-C3N4 surface, via the interlayer delamination and intralayer depolymerization of bulk g-C3N4. Photocatalytic experimental results indicated that after hydrothermal treatment, the resultant OG/g-C3N4 samples showed an obviously improved H2-evolution performance. Especially, when the hydrothermal time was 6 h, the resultant OG/g-C3N4(6 h) exhibited the highest photocatalytic activity, which was clearly higher than that of the bulk g-C3N4 by a factor of ca. 7. In addition to the higher specific surface area, the enhanced H2-evolution rate of OG/g-C3N4 photocatalysts can be mainly attributed to the formation of oxygen-containing groups, which possibly works as the effective H2-evolution active sites. Considering the facie and green synthesis method, the present work may provide a new insight for the development of highly efficient photocatalytic materials.

Heterogeneous reaction of SO2 with soot: The roles of relative humidity and surface composition of soot in surface sulfate formation

NASA Astrophysics Data System (ADS)

Zhao, Yan; Liu, Yongchun; Ma, Jinzhu; Ma, Qingxin; He, Hong

2017-03-01

The conversion of SO2 to sulfates on the surface of soot is still poorly understood. Soot samples with different fractions of unsaturated hydrocarbons and oxygen-containing groups were prepared by combusting n-hexane under well-controlled conditions. The heterogeneous reaction of SO2 with soot was investigated using in situ attenuated total internal reflection infrared (ATR-IR) spectroscopy, ion chromatography (IC) and a flow tube reactor at the ambient pressure and relative humidity (RH). Water promoted SO2 adsorption and sulfate formation at the RH range from 6% to 70%, while exceeded water condensed on soot was unfavorable for sulfate formation due to inhibition of SO2 adsorption when RH was higher than 80%. The surface composition of soot, which was governed by combustion conditions, also played an important role in the heterogeneous reaction of SO2 with soot. This effect was found to greatly depend on RH. At low RH of 6%, soot with the highest fuel/oxygen ratio of 0.162 exhibited a maximum uptake capacity for SO2 because it contained a large amount of aromatic Csbnd H groups, which acted as active sites for SO2 adsorption. At RH of 54%, soot produced with a fuel/oxygen ratio of 0.134 showed the highest reactivity toward SO2 because it contained appropriate amounts of aromatic Csbnd H groups and oxygen-containing groups, subsequently leading to the optimal surface concentrations of both SO2 and water. These results suggest that variation in the surface composition of soot from different sources and/or resulting from chemical aging in the atmosphere likely affects the conversion of SO2 to sulfates.

X-Ray diffraction and mu-Raman investigation of the monoclinic-orthorhombic phase transition in Th(1-x)U(x)(C(2)O(4))(2).2H(2)O solid solutions.

PubMed

Clavier, Nicolas; Hingant, Nina; Rivenet, Murielle; Obbade, Saïd; Dacheux, Nicolas; Barré, Nicole; Abraham, Francis

2010-02-15

A complete Th(1-x)U(x)(C(2)O(4))(2).2H(2)O solid solution was prepared by mild hydrothermal synthesis from a mixture of hydrochloric solutions containing cations and oxalic acid. The crystal structure has been solved from twinned single crystals for x = 0, 0.5, and 1 with monoclinic symmetry, space group C2/c, leading to unit cell parameters of a approximately 10.5 A, b approximately 8.5 A, and c approximately 9.6 A. The crystal structure consists of a two-dimensional arrangement of actinide centers connected through bis-bidentate oxalate ions forming squares. The actinide metal is coordinated by eight oxygen atoms from four oxalate entities and two water oxygen atoms forming a bicapped square antiprism. The connection between the layers is assumed by hydrogen bonds between the water molecules and the oxygen of oxalate of an adjacent layer. Under these conditions, the unit cell contains two independent oxalate ions. From high-temperature mu-Raman and X-ray diffraction studies, the compounds were found to undergo a transition to an orthorhombic form (space group Ccca). The major differences in the structural arrangement concern the symmetry of uranium, which decreases from C2 to D2, leading to a unique oxalate group. Consequently, the nu(s)(C-O) double band observed in the Raman spectra recorded at room temperature turned into a singlet. This transformation was then used to make the phase transition temperature more precise as a function of the uranium content of the sample.

Selected annotated bibliography of the geology of uraniferous and radioactive native bituminous substances, exclusive of coals, in the United States

USGS Publications Warehouse

Jones, Harriet Nell

1956-01-01

Native bituminous substances are divided into two groups, 1) bitumens and, 2) pyrobitumens. Bitumens are composed principally of hydrocarbons substantially free from oxygenated bodies, are fusible, and are soluble in carbon disulfide. Native bitumens occur in liquid and solid forms. The native liquid bitumens include all petroleums or crude oils. Native solid bitumens include native waxes such as ozocerite, asphalts or petroleum tars, and asphaltites such as gilsonite and grahamite. Pyrobitumens are composed principally of hydrocarbons which may contain oxygenated bodies. They are infusible and are insoluble, or nearly insoluble, in carbon disulfide. Native pyrobitumens are divided into an oxygen-containing group including peats, lignites, and coals, and an essentially oxygen-free, asphaltic group including such substances as wurtzilite, albertite, impsonite, and ingramite. Thucholites, which are carbonaceous substances that may contain uranium, thorium, and rare earths, commonly are considered to be pyrobitumens. Their compositions are variable and may fall into either the oxygen-containing or oxygen-free group. All varieties of native bituminous substances may be associated with mineral matter. The nomenclature of bitumens and pyrobitumens is used very loosely in the literature. This circumstance arises from the difficulty in recognizing many of these substances by visual examination, and because many of them can be identified accurately only by chemical methods. Inasmuch as some of the chemical procedures are time-consuming and satisfactory analytical methods have not been devised for all these substances, geologists generally have not obtained precise identifications but rather have used names that appeared most appropriate to the circumstances. It is expected that future research will show many substances called "asphaltite," "thucholite," etc., to be incorrectly identified. The nomenclature used by the authors of the various references of this bibliography is followed without deviation or further discussion. The stratigraphic nomenclature also is that used by the authors. In this bibliography emphasis is placed on reports dealing with the uranium contents and radioactivity of native bituminous substances rather than on mineralogical and chemical studies of these substances. The distribution of the substances described in the references is shown on the accompanying map. The indicated presence of these substances does not infer that they contain sufficient radioactive elements to constitute ores.

Carotenoids from Marine Organisms: Biological Functions and Industrial Applications

PubMed Central

Galasso, Christian; Corinaldesi, Cinzia; Sansone, Clementina

2017-01-01

As is the case for terrestrial organisms, carotenoids represent the most common group of pigments in marine environments. They are generally biosynthesized by all autotrophic marine organisms, such as bacteria and archaea, algae and fungi. Some heterotrophic organisms also contain carotenoids probably accumulated from food or partly modified through metabolic reactions. These natural pigments are divided into two chemical classes: carotenes (such as lycopene and α- and β-carotene) that are composed of hydrogen and carbon; xanthophylls (such as astaxanthin, fucoxanthin and lutein), which are constituted by hydrogen, carbon and oxygen. Carotenoids, as antioxidant compounds, assume a key role in the protection of cells. In fact, quenching of singlet oxygen, light capture and photosynthesis protection are the most relevant biological functions of carotenoids. The present review aims at describing (i) the biological functions of carotenoids and their benefits for human health, (ii) the most common carotenoids from marine organisms and (iii) carotenoids having large success in pharmaceutical, nutraceutical and cosmeceutical industries, highlighting the scientific progress in marine species cultivation for natural pigments production. PMID:29168774

Plasma functionalization of powdery nanomaterials using porous filter electrode and sample circulation

NASA Astrophysics Data System (ADS)

Lee, Deuk Yeon; Choi, Jae Hong; Shin, Jung Chul; Jung, Man Ki; Song, Seok Kyun; Suh, Jung Ki; Lee, Chang Young

2018-06-01

Compared with wet processes, dry functionalization using plasma is fast, scalable, solvent-free, and thus presents a promising approach for grafting functional groups to powdery nanomaterials. Previous approaches, however, had difficulties in maintaining an intimate sample-plasma contact and achieving uniform functionalization. Here, we demonstrate a plasma reactor equipped with a porous filter electrode that increases both homogeneity and degree of functionalization by capturing and circulating powdery carbon nanotubes (CNTs) via vacuum and gas blowing. Spectroscopic measurements verify that treatment with O2/air plasma generates oxygen-containing groups on the surface of CNTs, with the degree of functionalization readily controlled by varying the circulation number. Gas sensors fabricated using the plasma-treated CNTs confirm alteration of molecular adsorption on the surface of CNTs. A sequential treatment with NH3 plasma following the oxidation pre-treatment results in the functionalization with nitrogen species of up to 3.2 wt%. Our approach requiring no organic solvents not only is cost-effective and environmentally friendly, but also serves as a versatile tool that applies to other powdery micro or nanoscale materials for controlled modification of their surfaces.

Function and maturation of the Fe-S center in dihydroxyacid dehydratase from Arabidopsis.

PubMed

Gao, Huanyao; Azam, Tamanna; Randeniya, Sajini; Couturier, Jérémy; Rouhier, Nicolas; Johnson, Michael K

2018-03-23

Dihydroxyacid dehydratase (DHAD) is the third enzyme required for branched-chain amino acid biosynthesis in bacteria, fungi, and plants. DHAD enzymes contain two distinct types of active-site Fe-S clusters. The best characterized examples are Escherichia coli DHAD, which contains an oxygen-labile [Fe 4 S 4 ] cluster, and spinach DHAD, which contains an oxygen-resistant [Fe 2 S 2 ] cluster. Although the Fe-S cluster is crucial for DHAD function, little is known about the cluster-coordination environment or the mechanism of catalysis and cluster biogenesis. Here, using the combination of UV-visible absorption and circular dichroism and resonance Raman and electron paramagnetic resonance, we spectroscopically characterized the Fe-S center in DHAD from Arabidopsis thaliana ( At ). Our results indicated that At DHAD can accommodate [Fe 2 S 2 ] and [Fe 4 S 4 ] clusters. However, only the [Fe 2 S 2 ] cluster-bound form is catalytically active. We found that the [Fe 2 S 2 ] cluster is coordinated by at least one non-cysteinyl ligand, which can be replaced by the thiol group(s) of dithiothreitol. In vitro cluster transfer and reconstitution reactions revealed that [Fe 2 S 2 ] cluster-containing NFU2 protein is likely the physiological cluster donor for in vivo maturation of At DHAD. In summary, At DHAD binds either one [Fe 4 S 4 ] or one [Fe 2 S 2 ] cluster, with only the latter being catalytically competent and capable of substrate and product binding, and NFU2 appears to be the physiological [Fe 2 S 2 ] cluster donor for DHAD maturation. This work represents the first in vitro characterization of recombinant At DHAD, providing new insights into the properties, biogenesis, and catalytic role of the active-site Fe-S center in a plant DHAD. © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

Click-electron microscopy for imaging metabolically tagged non-protein biomolecules

PubMed Central

Ngo, John T.; Adams, Stephen R.; Deerinck, Thomas J.; Boassa, Daniela; Rodriguez-Rivera, Frances; Palida, Sakina F.; Bertozzi, Carolyn R.; Ellisman, Mark H.; Tsien, Roger Y.

2016-01-01

Electron microscopy (EM) has long been the main technique to image cell structures with nanometer resolution, but has lagged behind light microscopy in the crucial ability to make specific molecules stand out. Here we introduce “Click-EM,” a labeling technique for correlative light microscopy and EM imaging of non-protein biomolecules. In this approach, metabolic labeling substrates containing bioorthogonal functional groups are provided to cells for incorporation into biopolymers by endogenous biosynthetic machinery. The unique chemical functionality of these analogs is exploited for selective attachment of singlet oxygen-generating fluorescent dyes via bioorthogonal “click chemistry” ligations. Illumination of dye-labeled structures generates singlet oxygen to locally catalyze the polymerization of diaminobenzidine into an osmiophilic reaction product that is readily imaged by EM. We describe the application of Click-EM in imaging metabolically tagged DNA, RNA, and lipids in cultured cells and neurons, and highlight its use in tracking peptidoglycan synthesis in the Gram-positive bacterium Listeria monocytogenes. PMID:27110681

Blood transfusion improves renal oxygenation and renal function in sepsis-induced acute kidney injury in rats.

PubMed

Zafrani, Lara; Ergin, Bulent; Kapucu, Aysegul; Ince, Can

2016-12-20

The effects of blood transfusion on renal microcirculation during sepsis are unknown. This study aimed to investigate the effect of blood transfusion on renal microvascular oxygenation and renal function during sepsis-induced acute kidney injury. Twenty-seven Wistar albino rats were randomized into four groups: a sham group (n = 6), a lipopolysaccharide (LPS) group (n = 7), a LPS group that received fluid resuscitation (n = 7), and a LPS group that received blood transfusion (n = 7). The mean arterial blood pressure, renal blood flow, and renal microvascular oxygenation within the kidney cortex were recorded. Acute kidney injury was assessed using the serum creatinine levels, metabolic cost, and histopathological lesions. Nitrosative stress (expression of endothelial (eNOS) and inducible nitric oxide synthase (iNOS)) within the kidney was assessed by immunohistochemistry. Hemoglobin levels, pH, serum lactate levels, and liver enzymes were measured. Fluid resuscitation and blood transfusion both significantly improved the mean arterial pressure and renal blood flow after LPS infusion. Renal microvascular oxygenation, serum creatinine levels, and tubular damage significantly improved in the LPS group that received blood transfusion compared to the group that received fluids. Moreover, the renal expression of eNOS was markedly suppressed under endotoxin challenge. Blood transfusion, but not fluid resuscitation, was able to restore the renal expression of eNOS. However, there were no significant differences in lactic acidosis or liver function between the two groups. Blood transfusion significantly improved renal function in endotoxemic rats. The specific beneficial effect of blood transfusion on the kidney could have been mediated in part by the improvements in renal microvascular oxygenation and sepsis-induced endothelial dysfunction via the restoration of eNOS expression within the kidney.

Role of oxygen functionality on the band structure evolution and conductance of reduced graphene oxide

NASA Astrophysics Data System (ADS)

Roy, Rajarshi; Thapa, Ranjit; Chakrabarty, Soubhik; Jha, Arunava; Midya, Priyanka R.; Kumar, E. Mathan; Chattopadhyay, Kalyan K.

2017-06-01

Here we report, structural and electrical transport properties of reduced graphene oxide as a function of oxygen bonding configuration. We find that mainly epoxy (Csbnd Osbnd C) and carbonyl (Cdbnd O) functional groups remain as major residual components after reduction using three different reducing agents. We calculate the band structure in the presence of epoxy and carbonyl groups and defects. Finally, we calculate the theoretical band mobility and find that it is less for the carbonyl with epoxy system. We correlate the distortion of linear dispersion and opening of bandgap at K-point with conductance for different graphene system in presence of oxygen moieties.

Interactions of human hemoglobin with charged ligand-functionalized iron oxide nanoparticles and effect of counterions

NASA Astrophysics Data System (ADS)

Ghosh, Goutam; Panicker, Lata

2014-12-01

Human hemoglobin is an important metalloprotein. It has tetrameric structure with each subunit containing a `heme' group which carries oxygen and carbon dioxide in blood. In this work, we have investigated the interactions of human hemoglobin (Hb) with charged ligand-functionalized iron oxide nanoparticles and the effect of counterions, in aqueous medium. Several techniques like DLS and ζ-potential measurements, UV-vis, fluorescence, and CD spectroscopy have been used to characterize the interaction. The nanoparticle size was measured to be in the range of 20-30 nm. Our results indicated the binding of Hb with both positively as well as negatively charged ligand-functionalized iron oxide nanoparticles in neutral aqueous medium which was driven by the electrostatic and the hydrophobic interactions. The electrostatic binding interaction was not seen in phosphate buffer at pH 7.4. We have also observed that the `heme' groups of Hb remained unaffected on binding with charged nanoparticles, suggesting the utility of the charged ligand-functionalized nanoparticles in biomedical applications.

Incorporation of Oxygen into Abscisic Acid and Phaseic Acid from Molecular Oxygen 1

PubMed Central

Creelman, Robert A.; Zeevaart, Jan A. D.

1984-01-01

Abscisic acid accumulates in detached, wilted leaves of Xanthium strumarium. When these leaves are subsequently rehydrated, phaseic acid, a catabolite of abscisic acid, accumulates. Analysis by gas chromatography-mass spectrometry of phaseic acid isolated from stressed and subsequently rehydrated leaves placed in an atmosphere containing 20% 18O2 and 80% N2 indicates that one atom of 18O is incorporated in the 6′-hydroxymethyl group of phaseic acid. This suggests that the enzyme that converts abscisic acid to phaseic acid is an oxygenase. Analysis by gas chromatography-mass spectrometry of abscisic acid isolated from stressed leaves kept in an atmosphere containing 18O2 indicates that one atom of 18O is present in the carboxyl group of abscisic acid. Thus, when abscisic acid accumulates in water-stressed leaves, only one of the four oxygens present in the abscisic acid molecule is derived from molecular oxygen. This suggests that either (a) the oxygen present in the 1′-, 4′-, and one of the two oxygens at the 1-position of abscisic acid arise from water, or (b) there exists a stored precursor with oxygen atoms already present in the 1′- and 4′-positions of abscisic acid which is converted to abscisic acid under conditions of water stress. PMID:16663564

Incorporation of oxygen into abscisic Acid and phaseic Acid from molecular oxygen.

PubMed

Creelman, R A; Zeevaart, J A

1984-05-01

Abscisic acid accumulates in detached, wilted leaves of Xanthium strumarium. When these leaves are subsequently rehydrated, phaseic acid, a catabolite of abscisic acid, accumulates. Analysis by gas chromatography-mass spectrometry of phaseic acid isolated from stressed and subsequently rehydrated leaves placed in an atmosphere containing 20% (18)O(2) and 80% N(2) indicates that one atom of (18)O is incorporated in the 6'-hydroxymethyl group of phaseic acid. This suggests that the enzyme that converts abscisic acid to phaseic acid is an oxygenase.Analysis by gas chromatography-mass spectrometry of abscisic acid isolated from stressed leaves kept in an atmosphere containing (18)O(2) indicates that one atom of (18)O is present in the carboxyl group of abscisic acid. Thus, when abscisic acid accumulates in water-stressed leaves, only one of the four oxygens present in the abscisic acid molecule is derived from molecular oxygen. This suggests that either (a) the oxygen present in the 1'-, 4'-, and one of the two oxygens at the 1-position of abscisic acid arise from water, or (b) there exists a stored precursor with oxygen atoms already present in the 1'- and 4'-positions of abscisic acid which is converted to abscisic acid under conditions of water stress.

Neuroimaging, Pain Sensitivity, and Neuropsychological Functioning in School-Age Neonatal Extracorporeal Membrane Oxygenation Survivors Exposed to Opioids and Sedatives.

PubMed

van den Bosch, Gerbrich E; IJsselstijn, Hanneke; van der Lugt, Aad; Tibboel, Dick; van Dijk, Monique; White, Tonya

2015-09-01

Animal studies found negative long-term effects of exposure to sedatives and opioids in early life, especially when administered in the absence of pain. Around the world, children who require extracorporeal membrane oxygenation receive opioids and sedatives for extended periods, generally in the absence of major pain as extracorporeal membrane oxygenation cannulation is considered minor surgery. Therefore, our objective was to determine the long-term effects of extracorporeal membrane oxygenation treatment with respect to pain sensitivity, brain functioning during pain, brain morphology, and neuropsychological functioning in humans. Prospective follow-up study. Level III university hospital. Thirty-six extracorporeal membrane oxygenation survivors (8.1-15.5 yr) and 64 healthy controls (8.2-15.3 yr). We measured detection and pain thresholds, brain activity during pain (functional MRI), brain morphology (high-resolution structural MRI), and neuropsychological functioning and collected information regarding the subject's experience of chronic pain. We found a significant difference in the detection threshold for cold measured in a reaction time-dependent fashion (extracorporeal membrane oxygenation group, 29.9°C [SD, 1.4]; control group, 30.6°C [SD, 0.8]; p < 0.01), but no differences in other modalities or in pain sensitivity between groups. Furthermore, no differences in brain activation during pain, brain morphology, or in the occurrence of chronic pain were observed. However, extracorporeal membrane oxygenation survivors performed significantly worse on a verbal memory test compared with controls (p = 0.001). While the most critically ill newborns receive extracorporeal membrane oxygenation and, relatedly, large doses of opioids and sedatives for extended periods, global measures of pain sensitivity and neurobiological and neuropsychological development appear to have minor long-term consequences. Possible memory deficits in extracorporeal membrane oxygenation survivors require additional study, but neonatal extracorporeal membrane oxygenation treatment and associated exposure to opioids and sedatives seem less harmful to humans than expected from animal studies.

Stretchable and flexible thermoelectric polymer composites

NASA Astrophysics Data System (ADS)

Slobodian, P.; Riha, P.; Matyas, J.; Olejnik, R.

2018-03-01

Polymer composites were manufactured from pristine and oxidized multi-walled carbon nanotubes and ethylene-octene copolymer. The composites had thermoelectric properties and exhibit thermoelectric effect, that is, the conversion of temperature differences into electricity. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy of the multi-walled carbon nanotubes in ethylene-octene copolymer matrix showed that the oxidation with HNO3 or KMnO4 enhanced its p-type electrical conductivity and that the thermoelectric power increase was proportional to the formation of new oxygen-containing functional groups on the surface of carbon nanotubes.

[Oxygen-transport function of the blood and endothelial dysfunction in patients with angina pectoris and arterial hypertension].

PubMed

Iankovskaia, A V; Zinchuk, M A

2007-01-01

Parameters of oxygen-transport function of the blood and function of the endothelium were studied in 49 patients with stable angina pectoris of I and II functional class with or without concomitant 2nd degree arterial hypertension. All patients received pathogenetic therapy. Signs of endothelial dysfunction were found in group III in which endothelium dependent vasodilation (8.22 +/- 1.71%) was 73.4% (p1 < 0.001) lower than in control group and 47.2% (p3 < 0.05) lower than in patients with class I angina. In all groups baseline content of nitrates/nitrites was lower. Main parameters of acid-base balance were lowered in patients of group III evidencing for emergence of signs of metabolic acidosis and hypoxia. Lowering of hemoglobin affinity to oxygen and its rise after therapy was also revealed. Maximal lowering of this parameter (-10.2%, p2 < 0.05) reflecting shift of oxyhemoglobin dissociation curve to the right was noted in group II. Endothelium can participate in formation of these disturbances because its dysfunction is associated with deranged release of NO in various parts of vascular tree. This affects formation of various NO-derivatives of hemoglobin and oxygen transport system of the blood.

[Influence of surface chemical properties and pore structure characteristics of activated carbon on the adsorption of nitrobenzene from aqueous solution].

PubMed

Liu, Shou-Xin; Chen, Xi; Zhang, Xian-Quan

2008-05-01

Commercial activated carbon was treated by HNO3 oxidation and then subsequently heat treated under N2 atmosphere. Effect of surface chemical properties and pore structure on the adsorption performance of nitrobenzene was investigated. N2/77K adsorption isotherm and scanning electron microscopy (SEM) were used to characterize the pore structure and surface morphology of carbon. Boehm titration, Fourier transform infrared spectroscopy (FTIR), the point of zero charge (pH(PZC)) measurement and elemental analysis were used to characterize the surface properties. The results reveal that HNO3 oxidation can modify the surface chemical properties, increase the number of acidic surface oxygen-containing groups and has trivial effect on the pore structure of carbon. Further heat treatment can cause the decomposition of surface oxygen-containing groups, and increase the external surface area and the number of mesopores. Adsorption capacity of nitrobenzene on AC(NO-T), AC(raw) and AC(NO) was 1011.31, 483.09 and 321.54 mg x g(-1), respectively. Larger external surface area and the number of meso-pores, together with the less acid surface oxygen-containing groups were the main reason for the larger adsorption capacity AC(NO-T).

Signal transduction and phosphoryl transfer by a FixL hybrid kinase with low oxygen affinity: importance of the vicinal PAS domain and receiver aspartate.

PubMed

Sousa, Eduardo H S; Tuckerman, Jason R; Gondim, Ana C S; Gonzalez, Gonzalo; Gilles-Gonzalez, Marie-Alda

2013-01-22

FixL is a prototype for heme-based sensors, multidomain proteins that typically couple a histidine protein kinase activity to a heme-binding domain for sensing of diatomic gases such as oxygen, carbon monoxide, and nitric oxide. Despite the relatively well-developed understanding of FixL, the importance of some of its domains has been unclear. To explore the impact of domain-domain interactions on oxygen sensing and signal transduction, we characterized and investigated Rhizobium etli hybrid sensor ReFixL. In ReFixL, the core heme-containing PAS domain and kinase region is preceded by an N-terminal PAS domain of unknown function and followed by a C-terminal receiver domain. The latter resembles a target substrate domain that usually occurs independently of the kinase and contains a phosphorylatable aspartate residue. We isolated the full-length ReFixL as a soluble holoprotein with a single heme b cofactor. Despite a low affinity for oxygen (K(d) for O₂ of 738 μM), the kinase activity was completely switched off by O₂ at concentrations well below the K(d). A deletion of the first PAS domain strongly increased the oxygen affinity but essentially prohibited autophosphorylation, although the truncated protein was competent to accept phosphoryl groups in trans. These studies provide new insights into histidyl-aspartyl phosphoryl transfers in two-component systems and suggest that the control of ligand affinity and signal transduction by PAS domains can be direct or indirect.

Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

DOEpatents

Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

2003-09-23

Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

Role of oxygen functional groups for structure and dynamics of interfacial water on low rank coal surface: a molecular dynamics simulation

NASA Astrophysics Data System (ADS)

You, Xiaofang; Wei, Hengbin; Zhu, Xianchang; Lyu, Xianjun; Li, Lin

2018-07-01

Molecular dynamics simulations were employed to study the effects of oxygen functional groups for structure and dynamics properties of interfacial water molecules on the subbituminous coal surface. Because of complex composition and structure, the graphite surface modified by hydroxyl, carboxyl and carbonyl groups was used to represent the surface model of subbituminous coal according to XPS results, and the composing proportion for hydroxyl, carbonyl and carboxyl is 25:3:5. The hydration energy with -386.28 kJ/mol means that the adsorption process between water and coal surface is spontaneous. Density profiles for oxygen atoms and hydrogen atoms indicate that the coal surface properties affect the structural and dynamic characteristics of the interfacial water molecules. The interfacial water exhibits much more ordering than bulk water. The results of radial distribution functions, mean square displacement and local self-diffusion coefficient for water molecule related to three oxygen moieties confirmed that the water molecules prefer to absorb with carboxylic groups, and adsorption of water molecules at the hydroxyl and carbonyl is similar.

Monolayer group-III monochalcogenides by oxygen functionalization: a promising class of two-dimensional topological insulators

NASA Astrophysics Data System (ADS)

Zhou, Si; Liu, Cheng-Cheng; Zhao, Jijun; Yao, Yugui

2018-03-01

Monolayer group-III monochalcogenides (MX, M = Ga, In; X = S, Se, Te), an emerging category of two-dimensional (2D) semiconductors, hold great promise for electronics, optoelectronics and catalysts. By first-principles calculations, we show that the phonon dispersion and Raman spectra, as well as the electronic and topological properties of monolayer MX can be tuned by oxygen functionalization. Chemisorption of oxygen atoms on one side or both sides of the MX sheet narrows or even closes the band gap, enlarges work function, and significantly reduces the carrier effective mass. More excitingly, InS, InSe, and InTe monolayers with double-side oxygen functionalization are 2D topological insulators with sizeable bulk gap up to 0.21 eV. Their low-energy bands near the Fermi level are dominated by the px and py orbitals of atoms, allowing band engineering via in-plane strains. Our studies provide viable strategy for realizing quantum spin Hall effect in monolayer group-III monochalcogenides at room temperature, and utilizing these novel 2D materials for high-speed and dissipationless transport devices.

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

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

Coan, Patrick D.; Ellis, Lucas D.; Griffin, Michael B.

Here, cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al 2O 3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivitymore » for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al 2O 3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.« less

Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

DOE PAGES

Coan, Patrick D.; Ellis, Lucas D.; Griffin, Michael B.; ...

2018-03-05

Here, cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al 2O 3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivitymore » for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al 2O 3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.« less

Adsorption of SO2 onto oxidized and heat-treated activated carbon fibers (ACFs)

USGS Publications Warehouse

Daley, M.A.; Mangun, C.L.; DeBarr, J.A.; Riha, S.; Lizzio, A.A.; Donnals, G.L.; Economy, J.

1997-01-01

Oxidation of the ACFs, using an aqueous oxidant, decreased their adsorption capacity for SO2 from flue gas due to a decrease in pore volume and repulsion of the SO2 from acidic surface groups. If these samples were heat-treated to desorb the oxygen containing function groups, the amount of SO2 adsorption increased. This increase in adsorption capacity was directly correlated to the amount of CO2 evolved during heat-treatment of the oxidized ACFs. The amount of SO2 adsorbed for these samples was related to the pore size, pore surface chemistry and pore volume. This analysis is explained in more detail in this paper.

Thermolysis of phenethyl phenyl ether: A model of ether linkages in low rank coal

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

Britt, P.F.; Buchanan, A.C. III; Malcolm, E.A.

Currently, an area of interest and frustration for coal chemists has been the direct liquefaction of low rank coal. Although low rank coals are more reactive than bituminous coals, they are more difficult to liquefy and offer lower liquefaction yields under conditions optimized for bituminous coals. Solomon, Serio, and co-workers have shown that: in the pyrolysis and liquefaction of low rank coals, a low temperature cross-linking reaction associated with oxygen functional groups occurs before tar evolution. A variety of pretreatments (demineralization, alkylation, and ion-exchange) have been shown to reduce these retrogressive reactions and increase tar yields, but the actual chemicalmore » reactions responsible for these processes have not been defined. In order to gain insight into the thermochemical reactions leading to cross-linking in low rank coal, we have undertaken a study of the pyrolysis of oxygen containing coal model compounds. Solid state NMR studies suggest that the alkyl aryl ether linkage may be present in modest amounts in low rank coal. Therefore, in this paper, we will investigate the thermolysis of phenethyl phenyl ether (PPE) as a model of 0-aryl ether linkages found in low rank coal, lignites, and lignin, an evolutionary precursor of coal. Our results have uncovered a new reaction channel that can account for 25% of the products formed. The impact of reaction conditions, including restricted mass transport, on this new reaction pathway and the role of oxygen functional groups in cross-linking reactions will be investigated.« less

Intracellular singlet oxygen photosensitizers: on the road to solving the problems of sensitizer degradation, bleaching and relocalization.

PubMed

da Silva, Elsa F F; Pimenta, Frederico M; Pedersen, Brian W; Blaikie, Frances H; Bosio, Gabriela N; Breitenbach, Thomas; Westberg, Michael; Bregnhøj, Mikkel; Etzerodt, Michael; Arnaut, Luis G; Ogilby, Peter R

2016-02-01

Selected singlet oxygen photosensitizers have been examined from the perspective of obtaining a molecule that is sufficiently stable under conditions currently employed to study singlet oxygen behavior in single mammalian cells. Reasonable predictions about intracellular sensitizer stability can be made based on solution phase experiments that approximate the intracellular environment (e.g., solutions containing proteins). Nevertheless, attempts to construct a stable sensitizer based solely on the expected reactivity of a given functional group with singlet oxygen are generally not sufficient for experiments in cells; it is difficult to construct a suitable chromophore that is impervious to all of the secondary and/or competing degradative processes that are present in the intracellular environment. On the other hand, prospects are reasonably positive when one considers the use of a sensitizer encapsulated in a specific protein; the local environment of the chromophore is controlled, degradation as a consequence of bimolecular reactions can be mitigated, and genetic engineering can be used to localize the encapsulated sensitizer in a given cellular domain. Also, the option of directly exciting oxygen in sensitizer-free experiments provides a useful complementary tool. These latter systems bode well with respect to obtaining more accurate control of the "dose" of singlet oxygen used to perturb a cell; a parameter that currently limits mechanistic studies of singlet-oxygen-mediated cell signaling.

Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

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

Abdullah, Mohd Zamri, E-mail: zamriab@petronas.com.my; Ismail, Siti Salwa

2015-07-22

The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent.more » From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.« less

Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

NASA Astrophysics Data System (ADS)

Abdullah, Mohd. Zamri; Ismail, Siti Salwa

2015-07-01

The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.

Effect of hyperbaric oxygen therapy combined with autologous platelet concentrate applied in rabbit fibula fraction healing

PubMed Central

Neves, Paulo César Fagundes; de Campos Vieira Abib, Simone; Neves, Rogério Fagundes; Pircchio, Oronzo; Saad, Karen Ruggeri; Saad, Paulo Fernandes; Simões, Ricardo Santos; Moreira, Marcia Bento; de Souza Laurino, Cristiano Frota

2013-01-01

OBJECTIVES: The purpose is to study the effects of hyperbaric oxygen therapy and autologous platelet concentrates in healing the fibula bone of rabbits after induced fractures. METHODS: A total of 128 male New Zealand albino rabbits, between 6–8 months old, were subjected to a total osteotomy of the proximal portion of the right fibula. After surgery, the animals were divided into four groups (n = 32 each): control group, in which animals were subjected to osteotomy; autologous platelet concentrate group, in which animals were subjected to osteotomy and autologous platelet concentrate applied at the fracture site; hyperbaric oxygen group, in which animals were subjected to osteotomy and 9 consecutive daily hyperbaric oxygen therapy sessions; and autologous platelet concentrate and hyperbaric oxygen group, in which animals were subjected to osteotomy, autologous platelet concentrate applied at the fracture site, and 9 consecutive daily hyperbaric oxygen therapy sessions. Each group was divided into 4 subgroups according to a pre-determined euthanasia time points: 2, 4, 6, and 8 weeks postoperative. After euthanasia at a specific time point, the fibula containing the osseous callus was prepared histologically and stained with hematoxylin and eosin or picrosirius red. RESULTS: Autologous platelet concentrates and hyperbaric oxygen therapy, applied together or separately, increased the rate of bone healing compared with the control group. CONCLUSION: Hyperbaric oxygen therapy and autologous platelet concentrate combined increased the rate of bone healing in this experimental model. PMID:24141841

Photophysicochemical behaviour and antimicrobial properties of monocarboxy Mg (II) and Al (III) phthalocyanine-magnetite conjugates

NASA Astrophysics Data System (ADS)

Idowu, Mopelola Abidemi; Xego, Solami; Arslanoglu, Yasin; Mark, John; Antunes, Edith; Nyokong, Tebello

2018-03-01

Asymmetric Mg (II) or Al (III) phthalocyanine (containing a COOH group and 3-pyridylsulfanyl units) was conjugated via an amide bond to amino functionalized magnetic nanoparticle (AIMN) to form MgPc-AIMN or AlPc-AIMN conjugate, and characterized. The photophysicochemical behaviour of the phthalocyanine-AIMN conjugates was investigated and compared to the asymmetric Pcs and to the simple mixture of Pc with AIMNs without a chemical bond, (MPc-AIMN (mixed)). The directed covalent linkage of AIMNs to the asymmetrical metallopthalocyanines afforded improvements in the singlet oxygen (VΔ) and triplet state quantum yield (VT) as well as singlet oxygen lifetimes for the MPcs-AIMN-linked conjugates compared to MPc-AIMN (mixed) and MPcs alone. The asymmetric phthalocyanines and their conjugates showed effective antimicrobial activity against Escherichia coli bacteria under illumination.

Catalytic oxidation of 1,2-DCBz over V2O5/TiO2-CNTs: effect of CNT diameter and surface functional groups.

PubMed

Du, Cuicui; Wang, Qiulin; Peng, Yaqi; Lu, Shengyong; Ji, Longjie; Ni, Mingjiang

2017-02-01

A series of V 2 O 5 /TiO 2 -carbon nanotube (CNT) catalysts were prepared and tested to decompose gaseous 1,2-dichlorobenzene (1,2-DCBz). Several physicochemical methods, including nitrogen adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and H 2 temperature-programmed reduction (TPR) were employed to characterise their physicochemical properties. To better understand the effect of CNT properties on the reactivity of V 2 O 5 /TiO 2 -CNT catalysts, the 1,2-DCBz residue remaining in the off-gas and on the catalyst surface were both collected and analysed. The results indicate that the outer diameter and the surface functional groups (hydroxide radical and carboxyl) of CNTs significantly influence upon the catalytic activity of CNT-containing V 2 O 5 /TiO 2 catalysts: the CNT outer diameter mainly affects the aggregation of CNTs and the π-π interaction between the benzene ring and CNTs, while the introduction of -OH and -COOH groups by acid treatment can further enlarge specific surface area (SSA) and contribute to a higher average oxidation state of vanadium (V aos ) and supplemental surface chemisorbed oxygen (O ads ). In addition, the enhanced mobility of lattice oxygen (O latt) also improves the oxidation ability of the catalysts.

Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO2 Additions Impact Gas-Phase OH Oxidation Products of α- and β-Pinene.

PubMed

Friedman, Beth; Brophy, Patrick; Brune, William H; Farmer, Delphine K

2016-02-02

In order to probe how anthropogenic pollutants can impact the atmospheric oxidation of biogenic emissions, we investigated how sulfur dioxide (SO2) perturbations impact the oxidation of two monoterpenes, α-and β-pinene. We used chemical ionization mass spectrometry to examine changes in both individual molecules and gas-phase bulk properties of oxidation products as a function of SO2 addition. SO2 perturbations impacted the oxidation systems of α-and β-pinene, leading to an ensemble of products with a lesser degree of oxygenation than unperturbed systems. These changes may be due to shifts in the OH:HO2 ratio from SO2 oxidation and/or to SO3 reacting directly with organic molecules. Van Krevelen diagrams suggest a shift from gas-phase functionalization by alcohol/peroxide groups to functionalization by carboxylic acid or carbonyl groups, consistent with a decreased OH:HO2 ratio. Increasing relative humidity dampens the impact of the perturbation. This decrease in oxygenation may impact secondary organic aerosol formation in regions dominated by biogenic emissions with nearby SO2 sources. We observed sulfur-containing organic compounds following SO2 perturbations of monoterpene oxidation; whether these are the result of photochemistry or an instrumental artifact from ion-molecule clustering remains uncertain. However, our results demonstrate that the two monoterpene isomers produce unique suites of oxidation products.

Japan Flavour and Fragrance Materials Association's (JFFMA) safety assessment of food-flavouring substances uniquely used in Japan that belong to the class of aliphatic primary alcohols, aldehydes, carboxylic acids, acetals and esters containing additional oxygenated functional groups.

PubMed

Saito, Kenji; Hasegawa-Baba, Yasuko; Sekiya, Fumiko; Hayashi, Shim-Mo; Mirokuji, Yoshiharu; Okamura, Hiroyuki; Maruyama, Shinpei; Ono, Atsushi; Nakajima, Madoka; Degawa, Masakuni; Ozawa, Shogo; Shibutani, Makoto; Maitani, Tamio

2017-09-01

We performed a safety evaluation using the procedure devised by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) of the following four flavouring substances that belong to the class of 'aliphatic primary alcohols, aldehydes, carboxylic acids, acetals, and esters containing additional oxygenated functional groups' and are uniquely used in Japan: butyl butyrylacetate, ethyl 2-hydroxy-4-methylpentanoate, 3-hydroxyhexanoic acid and methyl hydroxyacetate. Although no genotoxicity study data were found in the published literature, none of the four substances had chemical structural alerts predicting genotoxicity. All four substances were categorised as class I by using Cramer's classification. The estimated daily intake of each of the four substances was determined to be 0.007-2.9 μg/person/day by using the maximised survey-derived intake method and based on the annual production data in Japan in 2001, 2005 and 2010, and was determined to be 0.250-600.0 μg/person/day by using the single-portion exposure technique and based on average-use levels in standard portion sizes of flavoured foods. Both of these estimated daily intake ranges were below the threshold of toxicological concern for class I substances, which is 1800 μg/person/day. Although no information from in vitro and in vivo toxicity studies for the four substances was available, these substances were judged to raise no safety concerns at the current levels of intake.

Extracorporeal membrane oxygenation as a bridge to lung transplantation: A single-center experience in the present era.

PubMed

Todd, Emily M; Biswas Roy, Sreeja; Hashimi, A Samad; Serrone, Rosemarie; Panchanathan, Roshan; Kang, Paul; Varsch, Katherine E; Steinbock, Barry E; Huang, Jasmine; Omar, Ashraf; Patel, Vipul; Walia, Rajat; Smith, Michael A; Bremner, Ross M

2017-11-01

Extracorporeal membrane oxygenation has been used as a bridge to lung transplantation in patients with rapid pulmonary function deterioration. The reported success of this modality and perioperative and functional outcomes are varied. We retrospectively reviewed all patients who underwent lung transplantation at our institution over 1 year (January 1, 2015, to December 31, 2015). Patients were divided into 2 groups depending on whether they required extracorporeal membrane oxygenation support as a bridge to transplant; preoperative characteristics, lung transplantation outcomes, and survival were compared between groups. Of the 93 patients, 12 (13%) received bridge to transplant, and 81 (87%) did not. Patients receiving bridge to transplant were younger, had higher lung allocation scores, had lower functional status, and were more often on mechanical ventilation at listing. Most patients who received bridge to transplant (n = 10, 83.3%) had pulmonary fibrosis. Mean pretransplant extracorporeal membrane oxygenation support was 103.6 hours in duration (range, 16-395 hours). All patients who received bridge to transplant were decannulated immediately after lung transplantation but were more likely to return to the operating room for secondary chest closure or rethoracotomy. Grade 3 primary graft dysfunction within 72 hours was similar between groups. Lung transplantation success and hospital discharge were 100% in the bridge to transplant group; however, these patients experienced longer hospital stays and higher rates of discharge to acute rehabilitation. The 1-year survival was 100% in the bridge to transplant group and 91% in the non-bridge to transplant group (log-rank, P = .24). The 1-year functional status was excellent in both groups. Extracorporeal membrane oxygenation can be used to safely bridge high-acuity patients with end-stage lung disease to lung transplantation with good 30-day, 90-day, and 1-year survival and excellent 1-year functional status. Long-term outcomes are being studied. Copyright © 2017. Published by Elsevier Inc.

Influence of perioperative oxygen fraction on pulmonary function after abdominal surgery: a randomized controlled trial

PubMed Central

2012-01-01

Background A high perioperative inspiratory oxygen fraction (FiO2) may reduce the frequency of surgical site infection. Perioperative atelectasis is caused by absorption, compression and reduced function of surfactant. It is well accepted, that ventilation with 100% oxygen for only a few minutes is associated with significant formation of atelectasis. However, it is still not clear if a longer period of 80% oxygen results in more atelectasis compared to a low FiO2. Our aim was to assess if a high FiO2 is associated with impaired oxygenation and decreased pulmonary functional residual capacity (FRC). Methods Thirty-five patients scheduled for laparotomy for ovarian cancer were randomized to receive either 30% oxygen (n = 15) or 80% oxygen (n = 20) during and for 2 h after surgery. The oxygenation index (PaO2/FiO2) was measured every 30 min during anesthesia and 90 min after extubation. FRC was measured the day before surgery and 2 h after extubation by a rebreathing method using the inert gas SF6. Results Five min after intubation, the median PaO2/FiO2 was 69 kPa [53-71] in the 30%-group vs. 60 kPa [47-69] in the 80%-group (P = 0.25). At the end of anesthesia, the PaO2/FiO2 was 58 kPa [40-70] vs. 57 kPa [46-67] in the 30%- and 80%-group, respectively (P = 0.10). The median FRC was 1993 mL [1610-2240] vs. 1875 mL [1545-2048] at baseline and 1615 mL [1375-2318] vs. 1633 mL [1343-1948] postoperatively in the 30%- and 80%-group, respectively (P = 0.70). Conclusion We found no significant difference in oxygenation index or functional residual capacity between patients given 80% and 30% oxygen for a period of approximately 5 hours. Trial registration ClinicalTrials.gov Identifier: NCT00637936. PMID:22840231

Heart Rate and Oxygen Uptake Kinetics in Type 2 Diabetes Patients - A Pilot Study on the Influence of Cardiovascular Medication on Regulatory Processes.

PubMed

Koschate, Jessica; Drescher, Uwe; Baum, Klaus; Brinkmann, Christian; Schiffer, Thorsten; Latsch, Joachim; Brixius, Klara; Hoffmann, Uwe

2017-05-01

The aim of this pilot study was to investigate whether there are differences in heart rate and oxygen uptake kinetics in type 2 diabetes patients, considering their cardiovascular medication. It was hypothesized that cardiovascular medication would affect heart rate and oxygen uptake kinetics and that this could be detected using a standardized exercise test. 18 subjects were tested for maximal oxygen uptake. Kinetics were measured in a single test session with standardized, randomized moderate-intensity work rate changes. Time series analysis was used to estimate kinetics. Greater maxima in cross-correlation functions indicate faster kinetics. 6 patients did not take any cardiovascular medication, 6 subjects took peripherally acting medication and 6 patients were treated with centrally acting medication. Maximum oxygen uptake was not significantly different between groups. Significant main effects were identified regarding differences in muscular oxygen uptake kinetics and heart rate kinetics. Muscular oxygen uptake kinetics were significantly faster than heart rate kinetics in the group with no cardiovascular medication (maximum in cross-correlation function of muscular oxygen uptake vs. heart rate; 0.32±0.08 vs. 0.25±0.06; p=0.001) and in the group taking peripherally acting medication (0.34±0.05 vs. 0.28±0.05; p=0.009) but not in the patients taking centrally acting medication (0.28±0.05 vs. 0.30±0.07; n.s.). It can be concluded that regulatory processes for the achievement of a similar maximal oxygen uptake are different between the groups. The used standardized test provided plausible results for heart rate and oxygen uptake kinetics in a single measurement session in this patient group. © Georg Thieme Verlag KG Stuttgart · New York.

Low work function, stable compound clusters and generation process

DOEpatents

Dinh, Long N.; Balooch, Mehdi; Schildbach, Marcus A.; Hamza, Alex V.; McLean, II, William

2000-01-01

Low work function, stable compound clusters are generated by co-evaporation of a solid semiconductor (i.e., Si) and alkali metal (i.e., Cs) elements in an oxygen environment. The compound clusters are easily patterned during deposition on substrate surfaces using a conventional photo-resist technique. The cluster size distribution is narrow, with a peak range of angstroms to nanometers depending on the oxygen pressure and the Si source temperature. Tests have shown that compound clusters when deposited on a carbon substrate contain the desired low work function property and are stable up to 600.degree. C. Using the patterned cluster containing plate as a cathode baseplate and a faceplate covered with phosphor as an anode, one can apply a positive bias to the faceplate to easily extract electrons and obtain illumination.

Sunlight-Triggered Nanoparticle Synergy: Teamwork of Reactive Oxygen Species and Nitric Oxide Released from Mesoporous Organosilica with Advanced Antibacterial Activity.

PubMed

Gehring, Julia; Trepka, Bastian; Klinkenberg, Nele; Bronner, Hannah; Schleheck, David; Polarz, Sebastian

2016-03-09

Colonization of surfaces by microorganisms is an urging problem. In combination with the increasing antibiotic resistance of pathogenic bacteria, severe infections are reported more frequently in medical settings. Therefore, there is a large demand to explore innovative surface coatings that provide intrinsic and highly effective antibacterial activity. Materials containing silver nanoparticles have been developed in the past for this purpose, but this solution has come into criticism due to various disadvantages like notable toxicity against higher organisms, the high price, and low abundance of silver. Here, we introduce a new, sunlight-mediated organosilica nanoparticle (NP) system based on silver-free antibacterial activity. The simultaneous release of nitric oxide (NO) in combination with singlet oxygen and superoxide radicals (O2(•-)) as reactive oxygen species (ROS) leads to the emergence of highly reactive peroxynitrite molecules with significantly enhanced biocidal activity. This special cooperative effect can only be realized, if the ROS-producing moieties and the functional entities releasing NO are spatially separated from each other. In one type of particle, Rose Bengal as an efficient singlet oxygen ((1)O2) producer was covalently bound to SH functionalities applying thiol-ene click chemistry. "Charging" the second type of particles with NO was realized by quantitatively transferring the thiol groups into S-nitrosothiol functionalities. We probed the oxidation power of ROS-NP alone and in combination with NO-NP using sunlight as a trigger. The high antibacterial efficiency of dual-action nanoparticles was demonstrated using disinfection assays with the pathogenic bacterium Pseudomonas aeruginosa.

Functionalization and characterization of pyrolyzed polymer based carbon microstructures for bionanoelectronics platforms

NASA Astrophysics Data System (ADS)

Hirabayashi, Mieko; Mehta, Beejal; Vahidi, Nasim W.; Khosla, Ajit; Kassegne, Sam

2013-11-01

In this study, the investigation of surface-treatment of chemically inert graphitic carbon microelectrodes (derived from pyrolyzed photoresist polymer) for improving their attachment chemistry with DNA molecular wires and ropes as part of a bionanoelectronics platform is reported. Polymer microelectrodes were fabricated on a silicon wafer using standard negative lithography procedures with negative-tone photoresist. These microelectrode structures were then pyrolyzed and converted to a form of conductive carbon that is referred to as PP (pyrolyzed polymer) carbon throughout this paper. Functionalization of the resulting pyrolyzed structures was done using nitric, sulfuric, 4-amino benzoic acids (4-ABA), and oxygen plasma etching and the surface modifications confirmed with Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and electron dispersion x-ray spectroscopy (EDS). Post surface-treatment analysis of microelectrodes with FTIR and Raman spectroscopy showed signature peaks characteristics of carboxyl functional groups while EDS showed an increase in oxygen content in the surface-treatment procedures (except 4-ABA) indicating an increase in carboxyl functional group. These functional groups form the basis for peptide bond with aminated oligonucleotides that in turn could be used as molecular wires and interconnects in a bionanoelectronics platform. Post-pyrolysis analysis using EDS showed relatively higher oxygen concentrations at the edges and location of defects compared to other locations on these microelectrodes. In addition, electrochemical impedance measurements showed metal-like behavior of PP carbon with high conductivity (|Z| <1 KΩ) and no detectable detrimental effect of oxygen plasma surface-treatment on electrical characteristic. In general, characterization results—taken together—indicated that oxygen plasma surface-treatment produced more reliable, less damaging, and consistently repeatable generation of carboxyl functional groups than diazonium salt and strong acid treatments.

Formation and emission of large furans and oxygenated hydrocarbons from flames

PubMed Central

Johansson, K. Olof; Dillstrom, Tyler; Monti, Matteo; El Gabaly, Farid; Campbell, Matthew F.; Schrader, Paul E.; Popolan-Vaida, Denisia M.; Richards-Henderson, Nicole K.; Wilson, Kevin R.; Violi, Angela; Michelsen, Hope A.

2016-01-01

Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that furans are produced in the high-temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ∼100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbon- and oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming. PMID:27410045

Formation and emission of large furans and oxygenated hydrocarbons from flames.

PubMed

Johansson, K Olof; Dillstrom, Tyler; Monti, Matteo; El Gabaly, Farid; Campbell, Matthew F; Schrader, Paul E; Popolan-Vaida, Denisia M; Richards-Henderson, Nicole K; Wilson, Kevin R; Violi, Angela; Michelsen, Hope A

2016-07-26

Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that furans are produced in the high-temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ∼100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbon- and oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming.

Formation and emission of large furans and oxygenated hydrocarbons from flames

DOE PAGES

Johansson, K. Olof; Dillstrom, Tyler; Monti, Matteo; ...

2016-07-07

Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. Wemore » used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that fura ns are produced in the high- Temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ~100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbonand oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming.« less

The Effects of Non-Redox Active Metal Ions on the Activation of Dioxygen: Isolation and Characterization of a Heterobimetallic Complex Containing a MnIII–(μ-OH)–CaII core

PubMed Central

Park, Young Jun; Ziller, Joseph W.; Borovik, A. S.

2011-01-01

Rate enhancements for the reduction of dioxygen by a MnII complex were observed in the presence of redox inactive Group 2 metal ions. The rate changes correlated with an increase in the Lewis acidity of the Group 2 metal ions. These studies led to the isolation of heterobimetallic complexes that contain MnIII-(μ-OH)-MII cores (MII = CaII, BaII), in which the hydroxo oxygen atom is derived from O2. This type of core structure has relevance to the oxygen evolving complexes within photosystem II. PMID:21595481

Stereochemistry of silicon in oxygen-containing compounds

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

Serezhkin, V. N., E-mail: Serezhkin@samsu.ru; Urusov, V. S.

2017-01-15

Specific stereochemical features of silicon in oxygen-containing compounds, including hybrid silicates with all oxygen atoms of SiO{sub n} groups ({sub n} = 4, 5, or 6) entering into the composition of organic anions or molecules, are described by characteristics of Voronoi—Dirichlet polyhedra. It is found that in rutile-like stishovite and post-stishovite phases with the structures similar to those of СаСl{sub 2}, α-PbO{sub 2}, or pyrite FeS{sub 2}, the volume of Voronoi—Dirichlet polyhedra of silicon and oxygen atoms decreases linearly with pressure increasing to 268 GPa. Based on these results, the possibility of formation of new post-stishovite phases is shown, namely,more » the fluorite-like structure (transition predicted at ~400 GPa) and a body-centered cubic lattice with statistical arrangement of silicon and oxygen atoms (~900 GPa).« less

Radiosensitizing Pancreatic Cancer Xenografts by an Implantable Micro-Oxygen Generator.

PubMed

Cao, Ning; Song, Seung Hyun; Maleki, Teimour; Shaffer, Michael; Stantz, Keith M; Cao, Minsong; Kao, Chinghai; Mendonca, Marc S; Ziaie, Babak; Ko, Song-Chu

2016-04-01

Over the past decades, little progress has been made to improve the extremely low survival rates in pancreatic cancer patients. Extreme hypoxia observed in pancreatic tumors contributes to the aggressive and metastatic characteristics of this tumor and can reduce the effectiveness of conventional radiation therapy and chemotherapy. In an attempt to reduce hypoxia-induced obstacles to effective radiation treatment, we used a novel device, the implantable micro-oxygen generator (IMOG), for in situ tumor oxygenation. After subcutaneous implantation of human pancreatic xenograft tumors in athymic rats, the IMOG was wirelessly powered by ultrasonic waves, producing 30 μA of direct current (at 2.5 V), which was then utilized to electrolyze water and produce oxygen within the tumor. Significant oxygen production by the IMOG was observed and corroborated using the NeoFox oxygen sensor dynamically. To test the radiosensitization effect of the newly generated oxygen, the human pancreatic xenograft tumors were subcutaneously implanted in nude mice with either a functional or inactivated IMOG device. The tumors in the mice were then exposed to ultrasonic power for 10 min, followed by a single fraction of 5 Gy radiation, and tumor growth was monitored thereafter. The 5 Gy irradiated tumors containing the functional IMOG exhibited tumor growth inhibition equivalent to that of 7 Gy irradiated tumors that did not contain an IMOG. Our study confirmed that an activated IMOG is able to produce sufficient oxygen to radiosensitize pancreatic tumors, enhancing response to single-dose radiation therapy.

Thermodynamic and redox properties of graphene oxides for lithium-ion battery applications: a first principles density functional theory modeling approach.

PubMed

Kim, Sunghee; Kim, Ki Chul; Lee, Seung Woo; Jang, Seung Soon

2016-07-27

Understanding the thermodynamic stability and redox properties of oxygen functional groups on graphene is critical to systematically design stable graphene-based positive electrode materials with high potential for lithium-ion battery applications. In this work, we study the thermodynamic and redox properties of graphene functionalized with carbonyl and hydroxyl groups, and the evolution of these properties with the number, types and distribution of functional groups by employing the density functional theory method. It is found that the redox potential of the functionalized graphene is sensitive to the types, number, and distribution of oxygen functional groups. First, the carbonyl group induces higher redox potential than the hydroxyl group. Second, more carbonyl groups would result in higher redox potential. Lastly, the locally concentrated distribution of the carbonyl group is more beneficial to have higher redox potential compared to the uniformly dispersed distribution. In contrast, the distribution of the hydroxyl group does not affect the redox potential significantly. Thermodynamic investigation demonstrates that the incorporation of carbonyl groups at the edge of graphene is a promising strategy for designing thermodynamically stable positive electrode materials with high redox potentials.

Synthesis of sulfonated porous carbon nanospheres solid acid by a facile chemical activation route

NASA Astrophysics Data System (ADS)

Chang, Binbin; Guo, Yanzhen; Yin, Hang; Zhang, Shouren; Yang, Baocheng

2015-01-01

Generally, porous carbon nanospheres materials are usually prepared via a template method, which is a multi-steps and high-cost strategy. Here, we reported a porous carbon nanosphere solid acid with high surface area and superior porosity, as well as uniform nanospheical morphology, which prepared by a facile chemical activation with ZnCl2 using resorcinol-formaldehyde (RF) resins spheres as precursor. The activation of RF resins spheres by ZnCl2 at 400 °C brought high surface area and large volume, and simultaneously retained numerous oxygen-containing and hydrogen-containing groups due to the relatively low processing temperature. The presence of these functional groups is favorable for the modification of -SO3H groups by a followed sulfonation treating with sulphuric acid and organic sulfonic acid. The results of N2 adsorption-desorption and electron microscopy clearly showed the preservation of porous structure and nanospherical morphology. Infrared spectra certified the variation of surface functional groups after activation and the successful modification of -SO3H groups after sulfonation. The acidities of catalysts were estimated by an indirect titration method and the modified amount of -SO3H groups were examined by energy dispersive spectra. The results suggested sulfonated porous carbon nanospheres catalysts possessed high acidities and -SO3H densities, which endowed their significantly catalytic activities for biodiesel production. Furthermore, their excellent stability and recycling property were also demonstrated by five consecutive cycles.

The effect of thermal reduction on the photoluminescence and electronic structures of graphene oxides.

PubMed

Chuang, C-H; Wang, Y-F; Shao, Y-C; Yeh, Y-C; Wang, D-Y; Chen, C-W; Chiou, J W; Ray, Sekhar C; Pong, W F; Zhang, L; Zhu, J F; Guo, J H

2014-04-10

Electronic structures of graphene oxide (GO) and hydro-thermally reduced graphene oxides (rGOs) processed at low temperatures (120-180°C) were studied using X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). C K-edge XANES spectra of rGOs reveal that thermal reduction restores C = C sp(2) bonds and removes some of the oxygen and hydroxyl groups of GO, which initiates the evolution of carbonaceous species. The combination of C K-edge XANES and Kα XES spectra shows that the overlapping π and π* orbitals in rGOs and GO are similar to that of highly ordered pyrolytic graphite (HOPG), which has no band-gap. C Kα RIXS spectra provide evidence that thermal reduction changes the density of states (DOSs) that is generated in the π-region and/or in the gap between the π and π* levels of the GO and rGOs. Two-dimensional C Kα RIXS mapping of the heavy reduction of rGOs further confirms that the residual oxygen and/or oxygen-containing functional groups modify the π and σ features, which are dispersed by the photon excitation energy. The dispersion behavior near the K point is approximately linear and differs from the parabolic-like dispersion observed in HOPG.

Diels-Alder reactions onto fluorinated and hydrogenated graphene

NASA Astrophysics Data System (ADS)

Denis, Pablo A.

2017-09-01

We studied Diels-Alder (DA) reactions onto functionalized graphene. When fluorine, hydrogen or oxygen functional groups are present on one side of the sheet, the DA cycloadditions become significantly more exergonic when performed on the opposite side. Hydrogen is more effective than fluorine and oxygen to promote these cycloadditions. In contrast with the results obtained for perfect graphene, the functionalization with H, F or O turns the DA reactions exergonic, with ΔG°298 = -127.2 kcal/mol. The reaction barriers are expected to be considerably lowered with respect to perfect graphene because the functional groups significantly reduce the distortion energy.

Ocular oxygen consumption during vitreoperfusion in the cat.

PubMed

Blair, N P

2000-01-01

Little is known about the total ocular oxygen consumption rate (QO2) in human diseases. Reductions in QO2 may indicate the amount of tissue loss produced by conditions such as retinal ischemia. We sought a method to estimate QO2 that eventually could be used in patients during vitrectomy surgery. We performed vitreoperfusion (perfusion of the vitreous cavity after vitrectomy) in 22 cat eyes with no ocular blood flow. The solution contained nutrients and a high partial pressure of oxygen (PO2). In 8 eyes we placed an oxygen electrode on the sclera, choroid, or outer retina to evaluate oxygen delivery from the vitreoperfusion solution (group 1). In 8 eyes the retinas were undisturbed (group 2), and in 6 eyes we excised the retinas (group 3). In groups 2 and 3 we estimated QO2 from the temporal decline of PO2 in the vitreoperfusion solution according to a pharmacokinetic model. Group 1 demonstrated oxygenation of the entire retina. The means and standard deviations of QO2 were 3.2 +/- 0.8 and 0.4 +/- 0.7 microL/min in groups 2 and 3, respectively, the difference being the retinal contribution, 88%. In group 2, metabolism accounted for an average of 82% of the oxygen loss from the vitreoperfusion solution, whereas flow and diffusion accounted for 13% and 5%, respectively. Ocular oxygen consumption can be estimated by means of vitreoperfusion. Further developments may allow measurements in patients during vitreous surgery to clarify the pathophysiology of their diseases and assess the amount of retinal tissue that has been lost.

Graphene quantum dots as the electrolyte for solid state supercapacitors

PubMed Central

Zhang, Su; Li, Yutong; Song, Huaihe; Chen, Xiaohong; Zhou, Jisheng; Hong, Song; Huang, Minglu

2016-01-01

We propose that graphene quantum dots (GQDs) with a sufficient number of acidic oxygen-bearing functional groups such as -COOH and -OH can serve as solution- and solid- type electrolytes for supercapacitors. Moreover, we found that the ionic conductivity and ion-donating ability of the GQDs could be markedly improved by simply neutralizing their acidic functional groups by using KOH. These neutralized GQDs as the solution- or solid-type electrolytes greatly enhanced the capacitive performance and rate capability of the supercapacitors. The reason for the enhancement can be ascribed to the fully ionization of the weak acidic oxygen-bearing functional groups after neutralization. PMID:26763275

Olfactory sensitivity for sperm-attractant aromatic aldehydes: a comparative study in human subjects and spider monkeys.

PubMed

Kjeldmand, Luna; Salazar, Laura Teresa Hernandez; Laska, Matthias

2011-01-01

Using a three-alternative forced-choice ascending staircase procedure, we determined olfactory detection thresholds in 20 human subjects for seven aromatic aldehydes and compared them to those of four spider monkeys tested in parallel using an operant conditioning paradigm. With all seven odorants, both species detected concentrations <1 ppm, and with several odorants single individuals of both species even discriminated concentrations <1 ppb from the solvent. No generalizable species differences in olfactory sensitivity were found despite marked differences in neuroanatomical and genetic features. The across-odorant patterns of sensitivity correlated significantly between humans and spider monkeys, and both species were more sensitive to bourgeonal than to lilial, cyclamal, canthoxal, helional, lyral, and 3-phenylpropanal. No significant correlation between presence/absence of an oxygen-containing moiety attached to the benzene ring or presence/absence of an additional alkyl group next to the functional aldehyde group, and olfactory sensitivity was found in any of the species. However, the presence of a tertiary butyl group in para position (relative to the functional aldehyde group) combined with a lack of an additional alkyl group next to the functional aldehyde group may be responsible for the finding that both species were most sensitive to bourgeonal.

Tunable Oxygen Functional Groups as Electrocatalysts on Graphite Felt Surfaces for All-Vanadium Flow Batteries.

PubMed

Estevez, Luis; Reed, David; Nie, Zimin; Schwarz, Ashleigh M; Nandasiri, Manjula I; Kizewski, James P; Wang, Wei; Thomsen, Edwin; Liu, Jun; Zhang, Ji-Guang; Sprenkle, Vincent; Li, Bin

2016-06-22

A dual oxidative approach using O2 plasma followed by treatment with H2 O2 to impart oxygen functional groups onto the surface of a graphite felt electrode. When used as electrodes for an all-vanadium redox flow battery (VRB) system, the energy efficiency of the cell is enhanced by 8.2 % at a current density of 150 mA cm(-2) compared with one oxidized by thermal treatment in air. More importantly, by varying the oxidative techniques, the amount and type of oxygen groups was tailored and their effects were elucidated. It was found that O-C=O groups improve the cells performance whereas the C-O and C=O groups degrade it. The reason for the increased performance was found to be a reduction in the cell overpotential after functionalization of the graphite felt electrode. This work reveals a route for functionalizing carbon electrodes to improve the performance of VRB cells. This approach can lower the cost of VRB cells and pave the way for more commercially viable stationary energy storage systems that can be used for intermittent renewable energy storage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Increased transcutaneous oxygen tension in the skin dorsum over the foot in patients with diabetic foot disease in response to the topical use of an emulsion of hyperoxygenated Fatty acids.

PubMed

Lázaro-Martínez, J L; Sánchez-Ríos, J P; García-Morales, E; Cecilia-Matilla, A; Segovia-Gómez, T

2009-12-01

The aim of this study was to examine changes in the skin over the feet of patients with diabetic foot syndrome after local application of a product containing hyperoxygenated fatty acids (HOFAs) by measuring transcutaneous oxygen. In 64 patients, transcutaneous oxygen pressure (TcPo(2)) was measured on days 0, 7, 30, 60, and 90 of the study. Foot skin dryness, shedding, and skin color were also assessed using a clinical score. The patients were grouped on the basis of initial levels of transcutaneous oxygen; group 1 comprised patients with TcPo( 2) >30 mm Hg and group 2 comprised patients with TcPo(2) <30 mm Hg on the skin over the dorsum of the feet. Increases in local oxygenation values were observed at a local level in group 2 patients after 30 days of treatment. Skin trophism showed clinical improvement in all patients and these observations may be attributed to improved local microcirculation.

The myoglobin of Emperor penguin (Aptenodytes forsteri): amino acid sequence and functional adaptation to extreme conditions.

PubMed

Tamburrini, M; Romano, M; Giardina, B; di Prisco, G

1999-02-01

In the framework of a study on molecular adaptations of the oxygen-transport and storage systems to extreme conditions in Antarctic marine organisms, we have investigated the structure/function relationship in Emperor penguin (Aptenodytes forsteri) myoglobin, in search of correlation with the bird life style. In contrast with previous reports, the revised amino acid sequence contains one additional residue and 15 differences. The oxygen-binding parameters seem well adapted to the diving behaviour of the penguin and to the environmental conditions of the Antarctic habitat. Addition of lactate has no major effect on myoglobin oxygenation over a large temperature range. Therefore, metabolic acidosis does not impair myoglobin function under conditions of prolonged physical effort, such as diving.

The effects of Pilates exercise on cardiopulmonary function in the chronic stroke patients: a randomized controlled trials.

PubMed

Lim, Hee Sung; Yoon, Sukhoon

2017-05-01

[Purpose] The purpose of this study was to examine the effect of modified Pilates exercise on cardiopulmonary function in chronic stroke patients. [Subjects and Methods] Twenty participants (age, 62.7 ± 7.3 years; height, 163.3 ± 8.5 cm; weight, 68.8 ± 10.3 kg) were recruited for this study, and randomly allocated to the modified Pilates exercise group (n=10) or the control group (n=10). Graded submaximal treadmill exercise test was used to examine the status of patients' cardiopulmonary function, based on maximal oxygen intake, at the end of a patient's exercise tolerance limit. [Results] The resting heart rates, maximal oxygen intake, and maximal oxygen intake per kilogram were significantly different after 8 weeks of modified Pilates exercise. In addition, these variables were also significantly different between the Pilates and control groups after 8 weeks. [Conclusion] This study has demonstrated that 8 weeks of modified Pilates exercise program can have a positive influence on patients with chronic stroke, potentially by enhancing the cardiopulmonary function, which may have positive implications for increasing their functional ability.

Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials.

PubMed

Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

2017-09-08

It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials

NASA Astrophysics Data System (ADS)

Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

2017-09-01

It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

Utilization of oxygen difluoride for syntheses of fluoropolymers

NASA Technical Reports Server (NTRS)

Toy, M. S. (Inventor)

1976-01-01

The reaction oxygen difluoride, OF2, with ethylenically unsaturated fluorocarbon compounds is examined. Depending upon the fluorocarbon material and reaction conditions, OF2 can chain extend fluoropolyenes, convert functional perfluorovinyl groups to acyl fluoride and/or epoxide groups, and act as a monomer for an addition type copolymerization with diolefins.

The effects of pleural fluid drainage on respiratory function in mechanically ventilated patients after cardiac surgery

PubMed Central

Brims, Fraser J H; Davies, Michael G; Elia, Andy; Griffiths, Mark J D

2015-01-01

Background Pleural effusions occur commonly after cardiac surgery and the effects of drainage on gas exchange in this population are not well established. We examined pulmonary function indices following drainage of pleural effusions in cardiac surgery patients. Methods We performed a retrospective study examining the effects of pleural fluid drainage on the lung function indices of patients recovering from cardiac surgery requiring mechanical ventilation for more than 7 days. We specifically analysed patients who had pleural fluid removed via an intercostal tube (ICT: drain group) compared with those of a control group (no effusion, no ICT). Results In the drain group, 52 ICTs were sited in 45 patients. The mean (SD) volume of fluid drained was 1180 (634) mL. Indices of oxygenation were significantly worse in the drain group compared with controls prior to drainage. The arterial oxygen tension (PaO2)/fractional inspired oxygen (FiO2) (P/F) ratio improved on day 1 after ICT placement (mean (SD), day 0: 31.01 (8.92) vs 37.18 (10.7); p<0.05) and both the P/F ratio and oxygenation index (OI: kPa/cm H2O=PaO2/mean airway pressure×FiO2) demonstrated sustained improvement to day 5 (P/F day 5: 39.85 (12.8); OI day 0: 2.88 (1.10) vs day 5: 4.06 (1.73); both p<0.01). The drain group patients were more likely to have an improved mode of ventilation on day 1 compared with controls (p=0.028). Conclusions Pleural effusion after cardiac surgery may impair oxygenation. Drainage of pleural fluid is associated with a rapid and sustained improvement in oxygenation. PMID:26339492

NOS1 ex1f-VNTR polymorphism influences prefrontal brain oxygenation during a working memory task.

PubMed

Kopf, Juliane; Schecklmann, Martin; Hahn, Tim; Dresler, Thomas; Dieler, Alica C; Herrmann, Martin J; Fallgatter, Andreas J; Reif, Andreas

2011-08-15

Nitric oxide (NO) synthase produces NO, which serves as first and second messenger in neurons, where the protein is encoded by the NOS1 gene. A functional variable number of tandem repeats (VNTR) polymorphism in the promoter region of the alternative first exon 1f of NOS1 is associated with various functions of human behavior, for example increased impulsivity, while another, non-functional variant was linked to decreased verbal working memory and a heightened risk for schizophrenia. We therefore investigated the influence of NOS1 ex 1f-VNTR on working memory function as reflected by both behavioral measures and prefrontal oxygenation. We hypothesized that homozygous short allele carriers exhibit altered brain oxygenation in task-related areas, namely the dorsolateral and ventrolateral prefrontal cortex and the parietal cortex. To this end, 56 healthy subjects were stratified into a homozygous long allele group and a homozygous short allele group comparable for age, sex and intelligence. All subjects completed a letter n-back task (one-, two-, and three-back), while concentration changes of oxygenated (O(2)Hb) hemoglobin in the prefrontal cortex were measured with functional near-infrared spectroscopy (fNIRS). We found load-associated O(2)Hb increases in the prefrontal and parts of the parietal cortex. Significant load-associated oxygenation differences between the two genotype groups could be shown for the dorsolateral prefrontal cortex and the parietal cortex. Specifically, short allele carriers showed a significantly larger increase in oxygenation in all three n-back tasks. This suggests a potential compensatory mechanism, with task-related brain regions being more active in short allele carriers to compensate for reduced NOS1 expression. Copyright © 2011 Elsevier Inc. All rights reserved.

Separating nano graphene oxide from the residual strong-acid filtrate of the modified Hummers method with alkaline solution

NASA Astrophysics Data System (ADS)

Hu, Xuebing; Yu, Yun; Wang, Yongqing; Zhou, Jianer; Song, Lixin

2015-02-01

In the modified Hummers method for preparing graphene oxide, the yellow slurry can be obtained. After filtering through a quantitative filter paper, the strong-acid filtrate containing the unprecipitated nano graphene oxide was gained. The corresponding filtrate was added gradually with an alkaline (NaOH or KOH) solution at room temperature. The unprecipitated nano graphene oxide could undergo fast aggregation when the pH value of the filtrate was about 1.7 and formed the stable floccules. X-ray diffraction analysis shows the dominant peak of the floccules is about 11°, which accords to the peak of graphene oxide. Spectra of X-ray photoelectron spectroscopy confirm the presence in the floccules of an abundance of oxygen functional groups and the purified graphene oxide floccules can be obtained. Atomic force microscopy measurement shows the graphene oxide floccules consists of sheet-like objects, mostly containing only a few layers (about 5 layers). Zeta potential analysis demonstrates the surface charge of the graphene oxide is pH-sensitive and its isoelectric point is ∼1.7. The flocculation mechanism of graphene oxide ascribes to the acid-base interaction with the surface functional groups of the carbon layers.

Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

DOEpatents

Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.

2018-04-24

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

Graphene Oxide Nanoribbon as Hole Extraction Layer to Enhance Efficiency and Stability of Polymer Solar Cells

DTIC Science & Technology

2013-01-01

Oxide Nanoribbon as Hole Extraction Layer to Enhance Effi ciency and Stability of Polymer Solar Cells Jun Liu , Gi-Hwan Kim , Yuhua Xue , Jin...circumvented by oxidizing graphene with acids (e.g., H 2 SO 4 /KMnO 4 ) to produce graphene oxide (GO) with oxygen-containing groups (e.g., –COOH, –OH...introducing the oxygen-rich groups around a graphene nanoribbon, the resultant graphene oxide nanoribbon (GOR) should show a synergistic effect to have

Inhibition of bacterial adhesion on PVC endotracheal tubes by RF-oxygen glow discharge, sodium hydroxide and silver nitrate treatments.

PubMed

Balazs, D J; Triandafillu, K; Wood, P; Chevolot, Y; van Delden, C; Harms, H; Hollenstein, C; Mathieu, H J

2004-05-01

Medical-grade poly(vinyl chloride) (PVC) was chemically modified to study how the incorporation of monovalent silver influences Pseudomonas aeruginosa adhesion and colonization. The modification investigated consisted of a radio frequency-oxygen (RF-O(2)) glow discharge pre-functionalization, followed by a two-step wet-treatment in sodium hydroxide and silver nitrate solutions. X-ray photoelectron spectroscopy (XPS) analysis and contact angle measurements were used to investigate the chemical nature and surface wettability of the films following each step of the modification. XPS analysis proved that the RF-O(2) plasma pre-functionalization of native PVC reproducibly increased the amount of functional groups representative of PVC additives, including ether/alcohol, esters and carboxyl groups. More specifically, we demonstrated that the O-C=O groups representative of the phthalic ester and zinc carboxylate additives identified for native PVC increased by two-fold following the RF-O(2) plasma pre-functionalization step. Although RF-O(2) pre-functionalization did not have an effect on the silver content of the NaOH/AgNO(3) treated substrates, such a modification was necessary for biomaterial products that did not have reproducible surfaces amongst production lots. XPS analysis also demonstrated that saponification with sodium hydroxide (NaOH) of esters, like those of the phthalic ester additives of PVC is a simple, irreversible method of hydrolysis, which produced sodium carboxylate and sodium phthalate salts. Exposure of native PVC to NaOH resulted in an increased surface hydrophilicity (from ca 90 degrees to ca 60 degrees ) due to dechlorination. XPS analysis following further incubation in silver nitrate demonstrated that silver ions can be trapped when the sodium of sodium carboxylate is replaced by silver after performing a second treatment with a monovalent silver-containing solution. The creation of silver salt on native PVC resulted in an ultra-hydrophobic (>120 degrees ) surface. The chemical modifications using NaOH and AgNO(3) wet treatments completely inhibited bacterial adhesion of four strains of P. aeruginosa to both native and oxygen-pre-functionalized PVC, and efficiently prevented colonization over longer periods (72 h). Our results suggest that surface modifications that incorporate silver ions would be extremely effective at reducing bacterial colonization to medical devices.

Neuroprotection of hyperbaric oxygen therapy in sub-acute traumatic brain injury: not by immediately improving cerebral oxygen saturation and oxygen partial pressure.

PubMed

Zhou, Bao-Chun; Liu, Li-Jun; Liu, Bing

2016-09-01

Although hyperbaric oxygen (HBO) therapy can promote the recovery of neural function in patients who have suffered traumatic brain injury (TBI), the underlying mechanism is unclear. We hypothesized that hyperbaric oxygen treatment plays a neuroprotective role in TBI by increasing regional transcranial oxygen saturation (rSO 2 ) and oxygen partial pressure (PaO 2 ). To test this idea, we compared two groups: a control group with 20 healthy people and a treatment group with 40 TBI patients. The 40 patients were given 100% oxygen of HBO for 90 minutes. Changes in rSO 2 were measured. The controls were also examined for rSO 2 and PaO 2 , but received no treatment. rSO 2 levels in the patients did not differ significantly after treatment, but levels before and after treatment were significantly lower than those in the control group. PaO 2 levels were significantly decreased after the 30-minute HBO treatment. Our findings suggest that there is a disorder of oxygen metabolism in patients with sub-acute TBI. HBO does not immediately affect cerebral oxygen metabolism, and the underlying mechanism still needs to be studied in depth.

Predicting adsorption isotherms for aqueous organic micropollutants from activated carbon and pollutant properties.

PubMed

Li, Lei; Quinlivan, Patricia A; Knappe, Detlef R U

2005-05-01

A method based on the Polanyi-Dubinin-Manes (PDM) model is presented to predict adsorption isotherms of aqueous organic contaminants on activated carbons. It was assumed that trace organic compound adsorption from aqueous solution is primarily controlled by nonspecific dispersive interactions while water adsorption is controlled by specific interactions with oxygen-containing functional groups on the activated carbon surface. Coefficients describing the affinity of water for the activated carbon surface were derived from aqueous-phase methyl tertiary-butyl ether (MTBE) and trichloroethene (TCE) adsorption isotherm data that were collected with 12 well-characterized activated carbons. Over the range of oxygen contents covered by the adsorbents (approximately 0.8-10 mmol O/g dry, ash-free activated carbon), a linear relationship between water affinity coefficients and adsorbent oxygen content was obtained. Incorporating water affinity coefficients calculated from the developed relationship into the PDM model, isotherm predictions resulted that agreed well with experimental data for three adsorbents and two adsorbates [tetrachloroethene (PCE), cis-1,2-dichloroethene (DCE)] that were not used to calibrate the model.

Design, development, and validation of a high-throughput drug-screening assay for targeting of human leukemia

PubMed Central

Karjalainen, Katja; Pasqualini, Renata; Cortes, Jorge E.; Kornblau, Steven M.; Lichtiger, Benjamin; O'Brien, Susan; Kantarjian, Hagop M.; Sidman, Richard L.; Arap, Wadih; Koivunen, Erkki

2015-01-01

Background We introduce an ex vivo methodology to perform drug library screening against human leukemia. Method Our strategy relies on human blood or bone marrow cultures under hypoxia; under these conditions, leukemia cells deplete oxygen faster than normal cells, causing a hemoglobin oxygenation shift. We demonstrate several advantages: (I) partial recapitulation of the leukemia microenvironment, (ii) use of native hemoglobin oxygenation as real-time sensor/reporter, (iii) cost-effectiveness, (iv) species-specificity, and (v) format that enables high-throughput screening. Results As a proof-of-concept, we screened a chemical library (size ∼20,000) against human leukemia cells. We identified 70 compounds (“hit” rate=0.35%; Z-factor=0.71) with activity; we examined 20 to find 18 true-positives (90%). Finally, we show that carbonohydraxonic diamide group-containing compounds are potent anti-leukemia agents that induce cell death in leukemia cells and patient-derived samples. Conclusions This unique functional assay can identify novel drug candidates as well as find future applications in personalized drug selection for leukemia patients. PMID:24496871

Iron and oxygen sensing: a tale of 2 interacting elements?

PubMed

Simpson, Robert J; McKie, Andrew T

2015-02-01

Iron and oxygen metabolism are intimately linked with one another. A change in the level of either metabolite results in activation of common pathways. At the heart of these responses lies a group of iron and oxygen dependent enzymes called prolyl hydroxylases. Prolyl hydroxylases (PHDs) require both iron and oxygen for optimal activity and their biological activity is to carry out the critical post-translational modification of the addition of a hydroxyl group to specific proline residues within Hypoxia Inducible Factor (HIFs)-well known transcription factors originally thought to regulate responses to hypoxia but which are now known to regulate key iron metabolism proteins too. The addition of the hydroxyl group ultimately leads to the unbiquitylation and destruction of HIFs, thus PHDs control appropriate HIF transcriptional responses depending on cellular oxygen or iron levels. There are two major HIFs; HIF1α and HIF2α. In terms of responses to iron HIF2α is of major importance in key tissues such as the intestine where several iron transporters (Ferroportin, Dcytb) contain HREs within their promoters which bind HIF2α. Furthermore the recent discovery that HIF2α contains a 5' iron responsive element (IRE) has underlined the importance of HIF2α as a major player in iron metabolism. This review brings together recent findings with regard to the HIF2α/IRP network as well as other aspects of iron sensing in cells and tissues.

Harmful Effects of Hyperoxia in Postcardiac Arrest, Sepsis, Traumatic Brain Injury, or Stroke: The Importance of Individualized Oxygen Therapy in Critically Ill Patients.

PubMed

Vincent, Jean-Louis; Taccone, Fabio Silvio; He, Xinrong

2017-01-01

The beneficial effects of oxygen are widely known, but the potentially harmful effects of high oxygenation concentrations in blood and tissues have been less widely discussed. Providing supplementary oxygen can increase oxygen delivery in hypoxaemic patients, thus supporting cell function and metabolism and limiting organ dysfunction, but, in patients who are not hypoxaemic, supplemental oxygen will increase oxygen concentrations into nonphysiological hyperoxaemic ranges and may be associated with harmful effects. Here, we discuss the potentially harmful effects of hyperoxaemia in various groups of critically ill patients, including postcardiac arrest, traumatic brain injury or stroke, and sepsis. In all these groups, there is evidence that hyperoxia can be harmful and that oxygen prescription should be individualized according to repeated assessment of ongoing oxygen requirements.

Ocular oxygen consumption: estimates using vitreoperfusion in the cat.

PubMed

Blair, Norman P; Liu, Ting; Warren, Keith A; Glaser, David A; Kennedy, Marc; Tran, Huan; Larson, Christopher A; Atluri, Prasant; Saidel, Michael A; Blair, Michael P

2004-02-01

Little is known about the ocular oxygen consumption rate (QO2) in human diseases. Alterations in QO2 must occur in many conditions, such as retinal ischemia. We present a method of estimating QO2 that eventually could be used in patients during vitrectomy surgery. We performed vitreoperfusion (i.e., perfusion of the vitreous cavity after vitrectomy) in 14 cat eyes with no ocular blood flow. The solution contained nutrients at a high partial pressure of oxygen (PO2). In eight eyes, the retinas were undisturbed (Group 1), and in six eyes, we excised the retinas (Group 2). We estimated QO2 in both groups on the basis of the temporal decline of PO2 in the vitreoperfusion solution according to a pharmacokinetic model. The mean and standard deviation of QO2 was 3.2 +/- 0.8 microL/min in Group 1 and 0.4+/- 0.7 microL/min in Group 2, with the difference being the retinal contribution, 88%. In Group 1, metabolism, bulk flow, and diffusion accounted for 82, 13, and 5%, respectively, of the oxygen loss from the vitreoperfusion solution. We estimated ocular oxygen consumption by means of vitreoperfusion. Eventually, the pathophysiology of human diseases may be clarified by similar measurements during vitrectomy.

High temperature volatility and oxidation measurements of titanium and silicon containing ceramic materials

NASA Astrophysics Data System (ADS)

Nguyen, Quynhgiao N.

Titanium (Ti) containing materials are of high interest to the aerospace industry due to its high temperature capability, strength, and light weight. As with most metals an exterior oxide layer naturally exists in environments that contain oxygen (i.e. air). At high temperatures, water vapor plays a key role in the volatility of materials including oxide surfaces. This study first evaluates several hot-pressed Ti-containing compositions at high temperatures as a function of oxidation resistance. This study will also evaluate cold pressed titanium dioxide (TiO2) powder pellets at a temperature range of 1400°C--1200°C in water containing environments to determine the volatile hydoxyl species using the transpiration method. The water content ranged from 0-76 mole % and the oxygen content range was 0-100 mole % during the 20-250 hour exposure times. Preliminary results indicate that oxygen is not a key contributor at these temperatures and the following reaction is the primary volatile equation at all three temperatures: TiO 2 (s) + H2O (g) = TiO(OH)2 (g).

Role of root exudates in dissolution of Cd containing iron oxides

NASA Astrophysics Data System (ADS)

Rosenfeld, C.; Martinez, C. E.

2011-12-01

Dissolved organic matter (DOM) in the rhizosphere contains organic acids, amino acids and more complex organic molecules that can substantially impact the solubility of soil solid phases. Plant roots and soil microorganisms contribute a large fraction of these organic compounds to DOM, potentially accelerating the transfer of solid phase elements into solution. In highly contaminated soils, heavy metals such as Cd are commonly found coprecipitated with common minerals (e.g. iron oxides). Introducing or changing vegetation on these contaminated soils may increase DOM levels in the soil pore fluids and thus enhance the biological and chemical weathering of soil minerals. Here, we investigate the role of root exudates on mineral dissolution and Cd mobility in contaminated soils. We hypothesize that plant exudates containing nitrogen and sulfur functional groups will dissolve Cd-containing mineral phases to a greater extent than exudates containing only oxygen functional groups, resulting in higher Cd concentrations in solution. Two different iron oxide mineral phases were utilized in a laboratory-scale model study system investigating the effects of low molecular weight, oxygen-, nitrogen-, and sulfur-containing organic compounds on mineral dissolution. Goethite (α-FeOOH) was synthesized in the laboratory with 0, 2.4, 5, and 100 theoretical mol% Cd, and franklinite (ZnFe2O4) was prepared with 0, 10, and 25 theoretical mol% Cd. Phase identity of all minerals was verified with X-ray diffraction (XRD). All minerals were reacted with 0.01 mM solutions containing one of four different organic ligands (oxalic acid, citric acid, histidine or cysteine) and aliquots of these solutions were sampled periodically over 40 days. Results from solution samples suggest that oxalic acid, citric acid, and histidine consistently increase mineral dissolution relative to the control (no organic compound present) while cysteine consistently inhibits dissolution relative to the control in all minerals. Increasing Cd substitution in the franklinite resulted in increased release of Fe and Zn to solution in the presence of these organic compounds, while increasing Cd substitution in the goethite generally limited Fe release to solution. In the case of cysteine, sulfur concentrations in solution decrease over time in the presence of Cd-containing minerals, indicating strong binding of the cysteine compound to the mineral surface, inhibiting Cd dissolution from the minerals. Our work indicates that amino acids present in biological soil exudates, in addition to organic acids, may have substantial impacts on iron oxide dissolution in soils, altering the availability of both bioessential (e.g., Fe and Zn) and non-essential, or potentially toxic, (e.g., Cd) elements.

Polystyrene Foam Products Equation of State as a Function of Porosity and Fill Gas

NASA Astrophysics Data System (ADS)

Mulford, R. N.; Swift, D. C.

2009-12-01

An accurate EOS for polystyrene foam is necessary for analysis of numerous experiments in shock compression, inertial confinement fusion, and astrophysics. Plastic to gas ratios vary between various samples of foam, according to the density and cell-size of the foam. A matrix of compositions has been investigated, allowing prediction of foam response as a function of the plastic-to-air ratio. The EOS code CHEETAH allows participation of the air in the decomposition reaction of the foam. Differences between air-filled, Ar-blown, and CO2-blown foams are investigated, to estimate the importance of allowing air to react with products of polystyrene decomposition. O2-blown foams are included in some comparisons, to amplify any consequences of reaction with oxygen in air. He-blown foams are included in some comparisons, to provide an extremum of density. Product pressures are slightly higher for oxygen-containing fill gases than for non-oxygen-containing fill gases. Examination of product species indicates that CO2 decomposes at high temperatures.

CH-19 sweet, a non-pungent cultivar of red pepper, increased body temperature and oxygen consumption in humans.

PubMed

Ohnuki, K; Niwa, S; Maeda, S; Inoue, N; Yazawa, S; Fushiki, T

2001-09-01

We investigated the effect of CH-19 Sweet, a non-pungent cultivar of red pepper, on body temperature and oxygen consumption in humans. CH-19 Sweet was given to 11 healthy volunteers, and core body temperature, body surface temperature and oxygen consumption were measured. The control group ingested California-Wandar, which contained neither capsaicin nor capsiate. The core body temperature in the CH-19 Sweet group was significantly higher than that in the control group (P<0.01). The forehead temperature measured by infrared thermography in the CH-19 Sweet group was significantly higher than that in the control group. The body surface temperature was increased for about 20 min after consumption of CH-19 Sweet intake, and the neck temperature was significantly higher (P<0.001) than when the subjects consumed California-Wandar. We also measured respiratory gas by indirect calorimetry while subjects wore a face mask. A significant difference was detected in oxygen consumption between the two groups, and the value was significantly higher in the CH-19 Sweet group (P<0.03). These results suggest that CH-19 Sweet increased thermogenesis and energy consumption.

Nitrogen-doped carbon monolith for alkaline supercapacitors and understanding nitrogen-induced redox transitions.

PubMed

Wang, Da-Wei; Li, Feng; Yin, Li-Chang; Lu, Xu; Chen, Zhi-Gang; Gentle, Ian R; Lu, Gao Qing; Cheng, Hui-Ming

2012-04-23

A nitrogen-doped porous carbon monolith was synthesized as a pseudo-capacitive electrode for use in alkaline supercapacitors. Ammonia-assisted carbonization was used to dope the surface with nitrogen heteroatoms in a way that replaced carbon atoms but kept the oxygen content constant. Ammonia treatment expanded the micropore size-distributions and increased the specific surface area from 383 m(2) g(-1) to 679 m(2) g(-1). The nitrogen-containing porous carbon material showed a higher capacitance (246 F g(-1)) in comparison with the nitrogen-free one (186 F g(-1)). Ex situ electrochemical spectroscopy was used to investigate the evolution of the nitrogen-containing functional groups on the surface of the N-doped carbon electrodes in a three-electrode cell. In addition, first-principles calculations were explored regarding the electronic structures of different nitrogen groups to determine their relative redox potentials. We proposed possible redox reaction pathways based on the calculated redox affinity of different groups and surface analysis, which involved the reversible attachment/detachment of hydroxy groups between pyridone and pyridine. The oxidation of nitrogen atoms in pyridine was also suggested as a possible reaction pathway. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fragmentation analysis of water-soluble atmospheric organic matter using ultrahigh-resolution FT-ICR mass spectrometry.

PubMed

Leclair, Jeffrey P; Collett, Jeffrey L; Mazzoleni, Lynn R

2012-04-17

Isolated water-soluble atmospheric organic matter (AOM) analytes extracted from radiation fogwater samples were analyzed using collision induced dissociation with ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Tandem mass analysis was performed on several mass ranges between 100 and 400 Da to characterize the functional groups of AOM species. Compounds containing nitrogen and/or sulfur were targeted because of the high number of oxygen atoms contained in their molecular formulas. Due to the large number of isobaric ions in the precursor isolation ranges, large numbers of product ions resulted from collision induced dissociation. Common neutral losses were assigned by matching the molecular formulas of the expected product ions with the detected product ions within the appropriate mass spectra. Since polar functional groups are expected to affect the hygroscopic properties of aerosols, the losses of H(2)O, CO(2), CH(3)OH, HNO(3), CH(3)NO(3), SO(3), SO(4) and combinations of these were specifically targeted. Among the 421 compounds studied, the most frequently observed neutral losses were CO(2) (54%), H(2)O (43%) and CH(3)OH (40%). HNO(3) losses were observed for 63% of the studied nitrogen containing compounds and 33% of the studied compounds containing both nitrogen and sulfur. SO(3) losses were observed for 85% of the studied sulfur containing compounds and 42% of studied compounds containing both nitrogen and sulfur. A number of molecular formulas matching those of monoterpene ozonolysis SOA were observed; they include organonitrates, organosulfates, and nitroxy-organosulfates. Overall, the results of fragmentation analysis of 400+ individual molecular precursors elucidate the complexity and multifunctional nature of the isolated water-soluble AOM.

Molybdoenzyme That Catalyzes the Anaerobic Hydroxylation of a Tertiary Carbon Atom in the Side Chain of Cholesterol*

PubMed Central

Dermer, Juri; Fuchs, Georg

2012-01-01

Cholesterol is a ubiquitous hydrocarbon compound that can serve as substrate for microbial growth. This steroid and related cyclic compounds are recalcitrant due to their low solubility in water, complex ring structure, the presence of quaternary carbon atoms, and the low number of functional groups. Aerobic metabolism therefore makes use of reactive molecular oxygen as co-substrate of oxygenases to hydroxylate and cleave the sterane ring system. Consequently, anaerobic metabolism must substitute oxygenase-catalyzed steps by O2-independent hydroxylases. Here we show that one of the initial reactions of anaerobic cholesterol metabolism in the β-proteobacterium Sterolibacterium denitrificans is catalyzed by an unprecedented enzyme that hydroxylates the tertiary C25 atom of the side chain without molecular oxygen forming a tertiary alcohol. This steroid C25 dehydrogenase belongs to the dimethyl sulfoxide dehydrogenase molybdoenzyme family, the closest relative being ethylbenzene dehydrogenase. It is a heterotrimer, which is probably located at the periplasmic side of the membrane and contains one molybdenum cofactor, five [Fe-S] clusters, and one heme b. The draft genome of the organism contains several genes coding for related enzymes that probably replace oxygenases in steroid metabolism. PMID:22942275

Long-Term Cognitive Outcome and Brain Imaging in Adults After Extracorporeal Membrane Oxygenation.

PubMed

von Bahr, Viktor; Kalzén, Håkan; Hultman, Jan; Frenckner, Björn; Andersson, Christin; Mosskin, Mikael; Eksborg, Staffan; Holzgraefe, Bernhard

2018-05-01

To investigate the presence of cognitive dysfunction and brain lesions in long-term survivors after treatment with extracorporeal membrane oxygenation for severe respiratory failure, and to see whether patients with prolonged hypoxemia were at increased risk. A single-center retrospective cohort study. Tertiary referral center for extracorporeal membrane oxygenation in Sweden. Long-term survivors treated between 1995 and July 2009. Seven patients from a previously published study investigated with a similar protocol were included. Brain imaging, neurocognitive testing, interview. Thirty-eight patients (i.e., n = 31 + 7) were enrolled and investigated in median 9.0 years after discharge. Only memory tests were performed in 10 patients, mainly due to a lack of formal education necessary for the test results to be reliable. Median full-scale intelligence quotient, memory index, and executive index were 97, 101, and 104, respectively (normal, 100 ± 15). Cognitive function was not reduced in the group with prolonged hypoxemia. Brain imaging showed cerebrovascular lesions in 14 of 38 patients (37%), most commonly in the group treated with venoarterial extracorporeal membrane oxygenation (7/11, 64%). In this group, memory function and executive function were significantly reduced. Patients treated with extracorporeal membrane oxygenation for respiratory failure may have normal cognitive function years after treatment, if not affected by cerebrovascular lesions. Permissive hypoxemia was not correlated with long-term cognitive dysfunction in the present study. Further prospective studies with minimal loss to follow-up are direly needed to confirm our findings.

The hemoglobin system of the primitive fish, Amia calva: isolation and functional characterization of the individual hemoglobin components.

PubMed

Weber, R E; Sullivan, B; Bonaventura, J; Bonaventura, C

1976-05-20

Blood from the primitive holostean fish, the bowfin, Amia calva, contains 2 mo of ATP per mol of hemoglobin. The hemolysates contain at least five tetrameric hemoglobin components which differ in their oxygen affinities and their response to cofactors such as ATP. The binding of oxygen by each chromatographically isolated component, including a cathodal component, is influenced by pH and organic phosphates; there is no significant differentiation of function or structure as seen in trout and certain other fish hemolysates. Kinetic analyses of ligand binding indicate that the Bohr and Root effects of Amia calva hemoglobins are best explained by changes in both the "on" and "off" constants. At low pH, the increase in the "off" constant is smaller than for most other Root hemoglobins. The hemoglobin system of Amina calva is functionally undifferentiated and may be representative of the ancestral condition in teleosts.

High temperature sorbents for oxygen

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor)

1994-01-01

A sorbent capable of removing trace amounts of oxygen (ppt) from a gas stream at a high temperature above 200 C comprising a porous alumina silicate support, such as zeolite, containing from 1 to 10 percent by weight of ion exchanged transition metal, such as copper or cobalt ions, and 0.05 to 1.0 percent by weight of an activator selected from a platinum group metal such as platinum is described. The activation temperature, oxygen sorption, and reducibility are all improved by the presence of the platinum activator.

Probing the interactions of phenol with oxygenated functional groups on curved fullerene-like sheets in activated carbon.

PubMed

Yin, Chun-Yang; Ng, Man-Fai; Goh, Bee-Min; Saunders, Martin; Hill, Nick; Jiang, Zhong-Tao; Balach, Juan; El-Harbawi, Mohanad

2016-02-07

The mechanism(s) of interactions of phenol with oxygenated functional groups (OH, COO and COOH) in nanopores of activated carbon (AC) is a contentious issue among researchers. This mechanism is of particular interest because a better understanding of the role of such groups in nanopores would essentially translate to advances in AC production and use, especially in regard to the treatment of organic-based wastewaters. We therefore attempt to shed more light on the subject by employing density functional theory (DFT) calculations in which fullerene-like models integrating convex or concave structure, which simulate the eclectic porous structures on AC surface, are adopted. TEM analysis, EDS mapping and Boehm titration are also conducted on actual phenol-adsorbed AC. Our results suggest the widely-reported phenomenon of decreased phenol uptake on AC due to increased concentration of oxygenated functional groups is possibly attributed to the increased presence of the latter on the convex side of the curved carbon sheets. Such a system effectively inhibits phenol from getting direct contact with the carbon sheet, thus constraining any available π-π interaction, while the effect of groups acting on the concave part of the curved sheet does not impart the same detriment.

Functional significance of cardiac reinnervation in heart transplant recipients.

PubMed

Schwaiblmair, M; von Scheidt, W; Uberfuhr, P; Ziegler, S; Schwaiger, M; Reichart, B; Vogelmeier, C

1999-09-01

There is accumulating evidence of structural sympathetic reinnervation after human cardiac transplantation. However, the functional significance of reinnervation in terms of exercise capacity has not been established as yet; we therefore investigated the influence of reinnervation on cardiopulmonary exercise testing. After orthotopic heart transplantation 35 patients (mean age, 49.1 +/- 8.4 years) underwent positron emission tomography with scintigraphically measured uptake of C11-hydroxyephedrine (HED), lung function testing, and cardiopulmonary exercise testing. Two groups were defined based on scintigraphic findings, indicating a denervated group (n = 15) with a HED uptake of 5.45%/min and a reinnervated group (n = 20) with a HED uptake of 10.59%/min. The two study groups did not show significant differences with regard to anthropometric data, number of rejection episodes, preoperative hemodynamics, and postoperative lung function data. The reinnervated group had a significant longer time interval from transplantation (1625 +/- 1069 versus 800 +/- 1316 days, p < .05). In transplant recipients with reinnervation, heart rate at maximum exercise (137 +/- 15 versus 120 +/- 20 beats/min, p = .012), peak oxygen uptake (21.0 +/- 4 versus 16.1 +/- 5 mL/min/kg, p = .006), peak oxygen pulse (12.4 +/- 2.9 versus 10.2 +/- 2.7 mL/min/beat, p = .031), and anaerobic threshold (11.2 +/- 1.8 versus 9.5 +/- 2.1 mL/min, p = .046) were significantly increased in comparison to denervated transplant recipients. Additionally, a decreased functional dead space ventilation (0.24 +/- 0.05 versus 0.30 +/- 0.05, p = .004) was observed in the reinnervated group. Our study results support the hypothesis that partial sympathetic reinnervation after cardiac transplantation is of functional significance. Sympathetic reinnervation enables an increased peak oxygen uptake. This is most probably due to partial restoration of the chronotropic and inotropic competence of the heart as well as an improved oxygen delivery to the exercising muscles and a reduced ventilation-perfusion mismatching.

Dual Functioning Thieno-Pyrrole Fused BODIPY Dyes for NIR Optical Imaging and Photodynamic Therapy: Singlet Oxygen Generation without Heavy Halogen Atom Assistance.

PubMed

Watley, Ryan L; Awuah, Samuel G; Bio, Moses; Cantu, Robert; Gobeze, Habtom B; Nesterov, Vladimir N; Das, Sushanta K; D'Souza, Francis; You, Youngjae

2015-06-01

We discovered a rare phenomenon wherein a thieno-pyrrole fused BODIPY dye (SBDPiR690) generates singlet oxygen without heavy halogen atom substituents. SBDPiR690 generates both singlet oxygen and fluorescence. To our knowledge, this is the first example of such a finding. To establish a structure-photophysical property relationship, we prepared SBDPiR analogs with electron-withdrawing groups at the para-position of the phenyl groups. The electron-withdrawing groups increased the HOMO-LUMO energy gap and singlet oxygen generation. Among the analogs, SBDPiR688, a CF3 analog, had an excellent dual functionality of brightness (82290 m(-1)  cm(-1) ) and phototoxic power (99170 m(-1)  cm(-1) ) comparable to those of Pc 4, due to a high extinction coefficient (211 000 m(-1)  cm(-1) ) and balanced decay (Φflu =0.39 and ΦΔ =0.47). The dual functionality of the lead compound SBDPiR690 was successfully applied to preclinical optical imaging and for PDT to effectively control a subcutaneous tumor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measuring and predicting sooting tendencies of oxygenates, alkanes, alkenes, cycloalkanes, and aromatics on a unified scale

DOE PAGES

Das, Dhrubajyoti D.; St. John, Peter C.; McEnally, Charles S.; ...

2017-12-27

Databases of sooting indices, based on measuring some aspect of sooting behavior in a standardized combustion environment, are useful in providing information on the comparative sooting tendencies of different fuels or pure compounds. However, newer biofuels have varied chemical structures including both aromatic and oxygenated functional groups, which expands the chemical space of relevant compounds. In this work, we propose a unified sooting tendency database for pure compounds, including both regular and oxygenated hydrocarbons, which is based on combining two disparate databases of yield-based sooting tendency measurements in the literature. Unification of the different databases was made possible by leveragingmore » the greater dynamic range of the color ratio pyrometry soot diagnostic. This unified database contains a substantial number of pure compounds (≥ 400 total) from multiple categories of hydrocarbons important in modern fuels and establishes the sooting tendencies of aromatic and oxygenated hydrocarbons on the same numeric scale for the first time. Then, using this unified sooting tendency database, we have developed a predictive model for sooting behavior applicable to a broad range of hydrocarbons and oxygenated hydrocarbons. The model decomposes each compound into single-carbon fragments and assigns a sooting tendency contribution to each fragment based on regression against the unified database. The model’s predictive accuracy (as demonstrated by leave-one-out cross-validation) is comparable to a previously developed, more detailed predictive model. The fitted model provides insight into the effects of chemical structure on soot formation, and cases where its predictions fail reveal the presence of more complicated kinetic sooting mechanisms. Our work will therefore enable the rational design of low-sooting fuel blends from a wide range of feedstocks and chemical functionalities.« less

Measuring and predicting sooting tendencies of oxygenates, alkanes, alkenes, cycloalkanes, and aromatics on a unified scale

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

Das, Dhrubajyoti D.; St. John, Peter C.; McEnally, Charles S.

Databases of sooting indices, based on measuring some aspect of sooting behavior in a standardized combustion environment, are useful in providing information on the comparative sooting tendencies of different fuels or pure compounds. However, newer biofuels have varied chemical structures including both aromatic and oxygenated functional groups, which expands the chemical space of relevant compounds. In this work, we propose a unified sooting tendency database for pure compounds, including both regular and oxygenated hydrocarbons, which is based on combining two disparate databases of yield-based sooting tendency measurements in the literature. Unification of the different databases was made possible by leveragingmore » the greater dynamic range of the color ratio pyrometry soot diagnostic. This unified database contains a substantial number of pure compounds (≥ 400 total) from multiple categories of hydrocarbons important in modern fuels and establishes the sooting tendencies of aromatic and oxygenated hydrocarbons on the same numeric scale for the first time. Then, using this unified sooting tendency database, we have developed a predictive model for sooting behavior applicable to a broad range of hydrocarbons and oxygenated hydrocarbons. The model decomposes each compound into single-carbon fragments and assigns a sooting tendency contribution to each fragment based on regression against the unified database. The model’s predictive accuracy (as demonstrated by leave-one-out cross-validation) is comparable to a previously developed, more detailed predictive model. The fitted model provides insight into the effects of chemical structure on soot formation, and cases where its predictions fail reveal the presence of more complicated kinetic sooting mechanisms. Our work will therefore enable the rational design of low-sooting fuel blends from a wide range of feedstocks and chemical functionalities.« less

Removing oxygen from a solvent extractant in an uranium recovery process

DOEpatents

Hurst, Fred J.; Brown, Gilbert M.; Posey, Franz A.

1984-01-01

An improvement in effecting uranium recovery from phosphoric acid solutions is provided by sparging dissolved oxygen contained in solutions and solvents used in a reductive stripping stage with an effective volume of a nonoxidizing gas before the introduction of the solutions and solvents into the stage. Effective volumes of nonoxidizing gases, selected from the group consisting of argon, carbon dioxide, carbon monoxide, helium, hydrogen, nitrogen, sulfur dioxide, and mixtures thereof, displace oxygen from the solutions and solvents thereby reduce deleterious effects of oxygen such as excessive consumption of elemental or ferrous and accumulation of complex iron phosphates or cruds.

Synthesis and photooxidation of styrene copolymer bearing camphorquinone pendant groups

PubMed Central

Moszner, Norbert; Lukáč, Ivan

2012-01-01

Summary (±)-10-Methacryloyloxycamphorquinone (MCQ) was synthesized from (±)-10-camphorsulfonic acid either by a known seven-step synthetic route or by a novel, shorter five-step synthetic route. MCQ was copolymerized with styrene (S) and the photochemical behavior of the copolymer MCQ/S was compared with that of a formerly studied copolymer of styrene with monomers containing the benzil (BZ) moiety (another 1,2-dicarbonyl). Irradiation (λ > 380 nm) of aerated films of styrene copolymers with monomers containing the BZ moiety leads to the insertion of two oxygen atoms between the carbonyl groups of BZ and to the formation of benzoyl peroxide (BP) as pendant groups on the polymer backbone. An equivalent irradiation of MCQ/S led mainly to the insertion of only one oxygen atom between the carbonyl groups of camphorquinone (CQ) and to the formation of camphoric anhydride (11) covalently bound to the polymer backbone. While the decomposition of pendant BP groups formed in irradiated films of styrene copolymers with pendant BZ groups leads to crosslinking, only small molecular-weight changes in irradiated MCQ/S were observed. PMID:22509202

A new strategy for integrating abundant oxygen functional groups into carbon felt electrode for vanadium redox flow batteries

PubMed Central

Kim, Ki Jae; Lee, Seung-Wook; Yim, Taeeun; Kim, Jae-Geun; Choi, Jang Wook; Kim, Jung Ho; Park, Min-Sik; Kim, Young-Jun

2014-01-01

The effects of surface treatment combining corona discharge and hydrogen peroxide (H2O2) on the electrochemical performance of carbon felt electrodes for vanadium redox flow batteries (VRFBs) have been thoroughly investigated. A high concentration of oxygen functional groups has been successfully introduced onto the surface of the carbon felt electrodes by a specially designed surface treatment, which is mainly responsible for improving the energy efficiency of VRFBs. In addition, the wettability of the carbon felt electrodes also can be significantly improved. The energy efficiency of the VRFB cell employing the surface modified carbon felt electrodes is improved by 7% at high current density (148 mA cm−2). Such improvement is attributed to the faster charge transfer and better wettability allowed by surface-active oxygen functional groups. Moreover, this method is much more competitive than other surface treatments in terms of processing time, production costs, and electrochemical performance. PMID:25366060

Catalytic Arylation and Vinylation Reactions Directed by Anionic Oxygen Functions via Cleavage of C - H and C - C Bonds

NASA Astrophysics Data System (ADS)

Satoh, Tetsuya; Miura, Masahiro

Aromatic compounds having oxygen-containing substituents such as phenols, phenyl ketones, benzyl alcohols, and benzoic acids undergo regioselective arylation and vinylation via C-H bond cleavage in the presence of transition-metal catalysts. The latter two substrates are also arylated and vinylated via C-C bond cleavage accompanied by liberation of ketones and CO2, respectively. Coordination of their anionic oxygen to the metal center is the key to activate the inert bonds effectively and regioselectively. The recent progress of these oxygen-directed reactions is summarized herein.

Characterization and Neutralization of Recovered Lewisite Munitions

DTIC Science & Technology

2006-12-01

chlorine being rated as 1.0.51 Oxidative Species Relative Oxidizing Strength* Fluorine 2.23 Hydroxyl Radical 2.06 Atomic Oxygen 1.78 Hydrogen...containing carbon-carbon double bonds, aldehyde groups or hydroxyl groups. As an electrophile , the permnanganate ion is strongly attracted to the electrons

Recent advances on edible films based on fruit and vegetables- a review

USDA-ARS?s Scientific Manuscript database

A food packaging system has different functions, including those related to containment, information, and marketing. However, its primary function is to separate food from the surrounding environment, reducing food exposure to deteriorating factors such as microorganisms, oxygen, water vapor, off-fl...

Persistent Postconcussive Symptoms Are Accompanied by Decreased Functional Brain Oxygenation.

PubMed

Helmich, Ingo; Saluja, Rajeet S; Lausberg, Hedda; Kempe, Mathias; Furley, Philip; Berger, Alisa; Chen, Jen-Kai; Ptito, Alain

2015-01-01

Diagnostic methods are considered a major concern in the determination of mild traumatic brain injury. The authors examined brain oxygenation patterns in subjects with severe and minor persistent postconcussive difficulties and a healthy control group during working memory tasks in prefrontal brain regions using functional near-infrared spectroscopy. The results demonstrated decreased working memory performances among concussed subjects with severe postconcussive symptoms that were accompanied by decreased brain oxygenation patterns. An association appears to exist between decreased brain oxygenation, poor performance of working memory tasks, and increased symptom severity scores in subjects suffering from persistent postconcussive symptoms.

Physical deoxygenation of graphene oxide paper surface and facile in situ synthesis of graphene based ZnO films

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

Ding, Jijun; Wang, Minqiang, E-mail: mqwang@mail.xjtu.edu.cn; Zhang, Xiangyu

2014-12-08

In-situ sputtering ZnO films on graphene oxide (GO) paper are used to fabricate graphene based ZnO films. Crystal structure and surface chemical states are investigated. Results indicated that GO paper can be effectively deoxygenated by in-situ sputtering ZnO on them without adding any reducing agent. Based on the principle of radio frequency magnetron sputtering, we propose that during magnetron sputtering process, plasma streams contain large numbers of electrons. These electrons not only collide with argon atoms to produce secondary electrons but also they are accelerated to bombard the substrates (GO paper) resulting in effective deoxygenation of oxygen-containing functional groups. In-situmore » sputtering ZnO films on GO paper provide an approach to design graphene-semiconductor nanocomposites.« less

The effects of Pilates exercise on cardiopulmonary function in the chronic stroke patients: a randomized controlled trials

PubMed Central

Lim, Hee Sung; Yoon, Sukhoon

2017-01-01

[Purpose] The purpose of this study was to examine the effect of modified Pilates exercise on cardiopulmonary function in chronic stroke patients. [Subjects and Methods] Twenty participants (age, 62.7 ± 7.3 years; height, 163.3 ± 8.5 cm; weight, 68.8 ± 10.3 kg) were recruited for this study, and randomly allocated to the modified Pilates exercise group (n=10) or the control group (n=10). Graded submaximal treadmill exercise test was used to examine the status of patients’ cardiopulmonary function, based on maximal oxygen intake, at the end of a patient’s exercise tolerance limit. [Results] The resting heart rates, maximal oxygen intake, and maximal oxygen intake per kilogram were significantly different after 8 weeks of modified Pilates exercise. In addition, these variables were also significantly different between the Pilates and control groups after 8 weeks. [Conclusion] This study has demonstrated that 8 weeks of modified Pilates exercise program can have a positive influence on patients with chronic stroke, potentially by enhancing the cardiopulmonary function, which may have positive implications for increasing their functional ability. PMID:28603381

Interactions between graphene oxide and wide band gap semiconductors

NASA Astrophysics Data System (ADS)

Kawa, M.; Podborska, A.; Szaciłowski, K.

2016-09-01

The graphene oxide (GO) and GO@TiO2 nanocomposite have been synthesised by using modified Hummers method and ultrasonics respectively. The materials were characterized by using X-ray diffraction, Fourier transform infrared spectroscopy and UV-Vis absorption spectroscopy. It was found that the interaction between GO and TiO2 affects the average interlayer spacing in carbonaceous material. The formation of bonds between various oxygen-containing functional groups and surface of titanium dioxide was investigated. One of them formed between the quinone structures (occur in graphene oxide) and titanium atoms exhibited 1.5 bond order. Furthermore the charge-transfer processes in GO@TiO2 composite were observed.

A newly developed solution enhances thirty-hour preservation in a canine lung transplantation model.

PubMed

Liu, C J; Ueda, M; Kosaka, S; Hirata, T; Yokomise, H; Inui, K; Hitomi, S; Wada, H

1996-09-01

Ischemia and reperfusion cause the production of oxygen free radicals. These damage grafts or disrupt normal vascular homeostatic mechanisms, with a parallel reduction in endothelial nitric oxide and adenosine 3',5'-cyclic monophosphate levels. We hypothesized that lung preservation failure may be related to these events. To improve lung preservation, we prepared a new ET-Kyoto solution, which contains N-acetylcysteine (a radical scavenger), nitroglycerin (to elevate the nitric oxide level), and dibutyryl adenosine 3',5'-cyclic monophosphate (to elevate the adenosine 3',5'-cyclic monophosphate level) and examined its efficacy in a canine single-lung transplantation model. Lungs were flushed with new ET-Kyoto solution (group I, n = 9), basal ET-Kyoto solution (group II, n = 6), basal ET-Kyoto solution plus ethanol and propylene glycol (solvents of nitroglycerin; group III, n = 6), or low-potassium dextran glucose solution (group IV, n = 6), and stored at 4 degrees C for 30 hours. After left single-lung transplantation, the right main bronchus and right pulmonary artery were ligated and the functions of the transplanted lung were assessed for 6 hours. Arterial oxygen tension was significantly higher in group I than in groups II, III, and IV (p < 0.05). Peak inspiratory pressure and wet-to-dry lung weight ratio were significantly lower in group I than in groups II and IV (p < 0.01). Histologic and ultrastructural studies showed better preservation in group I than in groups II, III, and IV. We conclude that the new ET-Kyoto solution provides enhanced 30-hour lung preservation.

Deep breathing exercises with positive expiratory pressure at a higher rate improve oxygenation in the early period after cardiac surgery--a randomised controlled trial.

PubMed

Urell, Charlotte; Emtner, Margareta; Hedenström, Hans; Tenling, Arne; Breidenskog, Marie; Westerdahl, Elisabeth

2011-07-01

In addition to early mobilisation, a variety of breathing exercises are used to prevent postoperative pulmonary complications after cardiac surgery. The optimal duration of the treatment is not well evaluated. The aim of this study was to determine the effect of 30 versus 10 deep breaths hourly, while awake, with positive expiratory pressure on oxygenation and pulmonary function the first days after cardiac surgery. A total of 181 patients, undergoing cardiac surgery, were randomised into a treatment group, performing 30 deep breaths hourly the first postoperative days, or into a control group performing 10 deep breaths hourly. The main outcome measurement arterial blood gases and the secondary outcome pulmonary function, evaluated with spirometry, were determined on the second postoperative day. Preoperatively, both study groups were similar in terms of age, SpO(2), forced expiratory volume in 1s and New York Heart Association classification. On the second postoperative day, arterial oxygen tension (PaO(2)) was 8.9 ± 1.7 kPa in the treatment group and 8.1 ± 1.4 kPa in the control group (p = 0.004). Arterial oxygen saturation (SaO(2)) was 92.7 ± 3.7% in the treatment group and 91.1 ± 3.8% in the control group (p = 0.016). There were no differences in measured lung function between the groups or in compliance to the breathing exercises. Compliance was 65% of possible breathing sessions. A significantly increased oxygenation was found in patients performing 30 deep breaths the first two postoperative days compared with control patients performing 10 deep breaths hourly. These results support the implementation of a higher rate of deep breathing exercises in the initial phase after cardiac surgery. Copyright © 2010 European Association for Cardio-Thoracic Surgery. Published by Elsevier B.V. All rights reserved.

Boron and oxygen-codoped porous carbon as efficient oxygen reduction catalysts

NASA Astrophysics Data System (ADS)

Lei, Zhidan; Chen, Hongbiao; Yang, Mei; Yang, Duanguang; Li, Huaming

2017-12-01

A low-cost boron- and oxygen-codoped porous carbon electrocatalyst towards oxygen reduction reaction (ORR) has been fabricated by a facile one-step pyrolysis approach, while a boron- and oxygen-rich polymer network was used as precursor. The boron- and oxygen-codoped carbon catalyst with high ORR electrocatalytic activity is comparable to that of Pt/C and is superior to that of catalysts doped solely with boron atoms or with oxygen atoms. Furthermore, the optimized boron- and oxygen-codoped carbon catalyst possesses excellent methanol tolerance and long-term durability in alkaline media. The high electrocatalytic activity of the dual-doped carbon catalysts can be attributed to the synergistic effects of high surface area, predominant mesostructure, abundant active oxygen-containing groups, and effective boron doping. The present results show that this boron- and oxygen-codoping strategy could be as a promising way for the preparation of highly efficient ORR catalysts.

Oxygen desaturation during night sleep affects decision-making in patients with obstructive sleep apnea.

PubMed

Delazer, Margarete; Zamarian, Laura; Frauscher, Birgit; Mitterling, Thomas; Stefani, Ambra; Heidbreder, Anna; Högl, Birgit

2016-08-01

This study assessed decision-making and its associations with executive functions and sleep-related factors in patients with obstructive sleep apnea. Thirty patients with untreated obstructive sleep apnea and 20 healthy age- and education-matched controls performed the Iowa Gambling Task, a decision-making task under initial ambiguity, as well as an extensive neuropsychological test battery. Patients, but not controls, also underwent a detailed polysomnographic assessment. Results of group analyses showed that patients performed at the same level of controls on the Iowa Gambling Task. However, the proportion of risky performers was significantly higher in the patient group than in the control group. Decision-making did not correlate with executive functions and subjective ratings of sleepiness, whereas there was a significant positive correlation between advantageous performance on the Iowa Gambling Task and percentage of N2 sleep, minimal oxygen saturation, average oxygen saturation and time spent below 90% oxygen saturation level. Also, the minimal oxygen saturation accounted for 27% of variance in decision-making. In conclusion, this study shows that a subgroup of patients with obstructive sleep apnea may be at risk of disadvantageous decision-making under ambiguity. Among the sleep-related factors, oxygen saturation is a significant predictor of advantageous decision-making. © 2016 European Sleep Research Society.

BOLD delay times using group delay in sickle cell disease

NASA Astrophysics Data System (ADS)

Coloigner, Julie; Vu, Chau; Bush, Adam; Borzage, Matt; Rajagopalan, Vidya; Lepore, Natasha; Wood, John

2016-03-01

Sickle cell disease (SCD) is an inherited blood disorder that effects red blood cells, which can lead to vasoocclusion, ischemia and infarct. This disease often results in neurological damage and strokes, leading to morbidity and mortality. Functional Magnetic Resonance Imaging (fMRI) is a non-invasive technique for measuring and mapping the brain activity. Blood Oxygenation Level-Dependent (BOLD) signals contain also information about the neurovascular coupling, vascular reactivity, oxygenation and blood propagation. Temporal relationship between BOLD fluctuations in different parts of the brain provides also a mean to investigate the blood delay information. We used the induced desaturation as a label to profile transit times through different brain areas, reflecting oxygen utilization of tissue. In this study, we aimed to compare blood flow propagation delay times between these patients and healthy subjects in areas vascularized by anterior, middle and posterior cerebral arteries. In a group comparison analysis with control subjects, BOLD changes in these areas were found to be almost simultaneous and shorter in the SCD patients, because of their increased brain blood flow. Secondly, the analysis of a patient with a stenosis on the anterior cerebral artery indicated that signal of the area vascularized by this artery lagged the MCA signal. These findings suggest that sickle cell disease causes blood propagation modifications, and that these changes could be used as a biomarker of vascular damage.

The Effect of Thermal Reduction on the Photoluminescence and Electronic Structures of Graphene Oxides

PubMed Central

Chuang, C.-H.; Wang, Y.-F.; Shao, Y.-C.; Yeh, Y.-C.; Wang, D.-Y.; Chen, C.-W.; Chiou, J. W.; Ray, Sekhar C.; Pong, W. F.; Zhang, L.; Zhu, J. F.; Guo, J. H.

2014-01-01

Electronic structures of graphene oxide (GO) and hydro-thermally reduced graphene oxides (rGOs) processed at low temperatures (120–180°C) were studied using X-ray absorption near-edge structure (XANES), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS). C K-edge XANES spectra of rGOs reveal that thermal reduction restores C = C sp2 bonds and removes some of the oxygen and hydroxyl groups of GO, which initiates the evolution of carbonaceous species. The combination of C K-edge XANES and Kα XES spectra shows that the overlapping π and π* orbitals in rGOs and GO are similar to that of highly ordered pyrolytic graphite (HOPG), which has no band-gap. C Kα RIXS spectra provide evidence that thermal reduction changes the density of states (DOSs) that is generated in the π-region and/or in the gap between the π and π* levels of the GO and rGOs. Two-dimensional C Kα RIXS mapping of the heavy reduction of rGOs further confirms that the residual oxygen and/or oxygen-containing functional groups modify the π and σ features, which are dispersed by the photon excitation energy. The dispersion behavior near the K point is approximately linear and differs from the parabolic-like dispersion observed in HOPG. PMID:24717290

Exopolysaccharides from yeast: insight into optimal conditions for biosynthesis, chemical composition and functional properties - review.

PubMed

Gientka, Iwona; Błażejak, Stanisław; Stasiak-Różańska, Lidia; Chlebowska-Śmigiel, Anna

2015-01-01

xopolysaccharides (EPS) are not a well-established group of metabolites. An industrial scale    of this EPS production is limited mainly by low yield biosynthesis. Until now, enzymes and biosynthesis pathways, as well as the role of regulatory genes, have not been described. Some of yeast EPS show antitumor, immunostimulatory and antioxidant activity. Others, absorb heavy metals and can function as bioactive components of food. Also, the potential of yeast EPS as thickeners or stabilizers can be found. Optimal conditions for the biosynthesis of yeast exopolysaccharides require strong oxygenation and low temperature of the culture, due to the physiology of the producer strains. The medium should contain sucrose as a carbon source and ammonium sulfate as inorganic nitrogen source, wherein the C:N ratio in the substrate should be 15:1. The cultures are long and the largest accumulation of polymers is observed after 4 or 5 days of culturing. The structure of yeast EPS is complex which affects the strain and culture condition. The EPS from yeast are linear mannans, pullulan, glucooligosaccharides, galactooligosaccharides and other heteropolysaccharides containing α-1,2; α-1,3; α-1,6; β-1,3; β-1,4 bonds. Mannose and glucose have the largest participation of carbohydrates for. t exopolysaccharides (EPS) are not a well-established group of metabolites. An industrial scale    of this EPS production is limited mainly by low yield biosynthesis. Until now, enzymes and biosynthesis pathways, as well as the role of regulatory genes, have not been described. Some of yeast EPS show antitumor, immunostimulatory and antioxidant activity. Others, absorb heavy metals and can function as bioactive components of food. Also, the potential of yeast EPS as thickeners or stabilizers can be found. Optimal conditions for the biosynthesis of yeast exopolysaccharides require strong oxygenation and low temperature of the culture, due to the physiology of the producer strains. The medium should contain sucrose as a carbon source and ammonium sulfate as inorganic nitrogen source, wherein the C:N ratio in the substrate should be 15:1. The cultures are long and the largest accumulation of polymers is observed after 4 or 5 days of culturing. The structure of yeast EPS is complex which affects the strain and culture condition. The EPS from yeast are linear mannans, pullulan, glucooligosaccharides, galactooligosaccharides and other heteropolysaccharides containing α-1,2; α-1,3; α-1,6; β-1,3; β-1,4 bonds. Mannose and glucose have the largest participation of carbohydrates formin. t exopolysaccharides (EPS) are not a well-established group of metabolites. An industrial scale    of this EPS production is limited mainly by low yield biosynthesis. Until now, enzymes and biosynthesis pathways, as well as the role of regulatory genes, have not been described. Some of yeast EPS show antitumor, immunostimulatory and antioxidant activity. Others, absorb heavy metals and can function as bioactive components of food. Also, the potential of yeast EPS as thickeners or stabilizers can be found. Optimal conditions for the biosynthesis of yeast exopolysaccharides require strong oxygenation and low temperature of the culture, due to the physiology of the producer strains. The medium should contain sucrose as a carbon source and ammonium sulfate as inorganic nitrogen source, wherein the C:N ratio in the substrate should be 15:1. The cultures are long and the largest accumulation of polymers is observed after 4 or 5 days of culturing. The structure of yeast EPS is complex which affects the strain and culture condition. The EPS from yeast are linear mannans, pullulan, glucooligosaccharides, galactooligosaccharides and other heteropolysaccharides containing α-1,2; α-1,3; α-1,6; β-1,3; β-1,4 bonds. Mannose and glucose have the largest participation of carbohydrates forming EPS.

Calcium-manganese oxides as structural and functional models for active site in oxygen evolving complex in photosystem II: lessons from simple models.

PubMed

Najafpour, Mohammad Mahdi

2011-01-01

The oxygen evolving complex in photosystem II which induces the oxidation of water to dioxygen in plants, algae and certain bacteria contains a cluster of one calcium and four manganese ions. It serves as a model to split water by sunlight. Reports on the mechanism and structure of photosystem II provide a more detailed architecture of the oxygen evolving complex and the surrounding amino acids. One challenge in this field is the development of artificial model compounds to study oxygen evolution reaction outside the complicated environment of the enzyme. Calcium-manganese oxides as structural and functional models for the active site of photosystem II are explained and reviewed in this paper. Because of related structures of these calcium-manganese oxides and the catalytic centers of active site of the oxygen evolving complex of photosystem II, the study may help to understand more about mechanism of oxygen evolution by the oxygen evolving complex of photosystem II. Copyright © 2010 Elsevier B.V. All rights reserved.

Development and characterisation of chitosan or alginate-coated low density polyethylene films containing Satureja hortensis extract.

PubMed

Rahmani, Bahareh; Hosseini, Hedayat; Khani, Mohammadreza; Farhoodi, Mehdi; Honarvar, Zohreh; Feizollahi, Ehsan; Shokri, Babak; Shojaee-Aliabadi, Saeedeh

2017-12-01

This study aimed to develop novel bilayer films based on alginate, chitosan and low-density polyethylene (LDPE) containing different concentrations of summer savory extract (SSE). The cold atmospheric plasma system was used to increase the surface energy of LDPE. Initially, water contact angle, surface roughness and the functional group of LDPE before and after plasma treatment were investigated. Then physical, mechanical, optical, antioxidant and microstructure properties of plasma-treated and untreated bilayer films and antioxidant films incorporated with SSE were characterized. Results showed that plasma treatment increased oxygen-containing the polar group, surface roughness and decreased water contact angle of LDPE surface (from 90.47° to 48.73°) and in result enhanced adhesion between polysaccharide coating and LDPE. Tensile strength of both alginate and chitosan coated-LDPE increased from 10.096 to 14.372 and 11.513 to 13.459MPa, respectively after plasma pretreatment. However chitosan-based films had lower water solubility. Although, incorporation of SSE into chitosan and alginate coated-LDPE despite slight adverse effects on the physical and mechanical properties of films, it provided antioxidant activity. Chitosan coated-LDPE containing SSE had potential to use as antioxidant food packaging. Copyright © 2017 Elsevier B.V. All rights reserved.

Structure Evolution of Graphene Oxide during Thermally Driven Phase Transformation: Is the Oxygen Content Really Preserved?

PubMed Central

Sun, Pengzhan; Wang, Yanlei; Liu, He; Wang, Kunlin; Wu, Dehai; Xu, Zhiping; Zhu, Hongwei

2014-01-01

A mild annealing procedure was recently proposed for the scalable enhancement of graphene oxide (GO) properties with the oxygen content preserved, which was demonstrated to be attributed to the thermally driven phase separation. In this work, the structure evolution of GO with mild annealing is closely investigated. It reveals that in addition to phase separation, the transformation of oxygen functionalities also occurs, which leads to the slight reduction of GO membranes and furthers the enhancement of GO properties. These results are further supported by the density functional theory based calculations. The results also show that the amount of chemically bonded oxygen atoms on graphene decreases gradually and we propose that the strongly physisorbed oxygen species constrained in the holes and vacancies on GO lattice might be responsible for the preserved oxygen content during the mild annealing procedure. The present experimental results and calculations indicate that both the diffusion and transformation of oxygen functional groups might play important roles in the scalable enhancement of GO properties. PMID:25372142

Impact of Prosthesis-Patient Mismatch on Long-term Functional Capacity After Mechanical Aortic Valve Replacement.

PubMed

Petit-Eisenmann, Hélène; Epailly, Eric; Velten, Michel; Radojevic, Jelena; Eisenmann, Bernard; Kremer, Hélène; Kindo, Michel

2016-12-01

The impact of prosthesis-patient mismatch (PPM) after aortic valve replacement (AVR) for aortic stenosis on exercise capacity remains controversial. The aim of this study was to analyze the long-term impact of PPM after mechanical AVR on maximal oxygen uptake (VO 2max ). The study included 75 patients who had undergone isolated mechanical AVR for aortic stenosis with normal left ventricular (LV) function between 1994 and 2012. Their functional capacity was evaluated on average 4.6 years after AVR by exercise testing, including measurement of their VO 2max , and by determining their New York Heart Association functional class and Short Form-36 score. Two groups were defined by measuring the patients' indexed effective orifice area (iEOA) by transthoracic echocardiography: a PPM group (iEOA < 0.85 cm 2 /m 2 ) and a no-PPM group (iEOA ≥ 0.85 cm 2 /m 2 ). PPM was present in 37.0% of the patients. The percentage of the predicted VO 2max achieved was significantly lower in the PPM group (86.7 ± 19.5% vs 97.5 ± 23.0% in the no-PPM group; P = 0.04). Compared with the no-PPM group, the PPM group contained fewer patients in New York Heart Association functional class I and their mean Short Form-36 physical component summary score was significantly lower. The mean transvalvular gradient was significantly higher in the PPM group than in the no-PPM group (P < 0.001). Systolic and diastolic function and LV mass had normalized in both groups. PPM is associated in the long term with moderate but significant impairment of functional capacity, despite optimal LV reverse remodelling and normalization of LV systolic and diastolic function. Copyright © 2016 Canadian Cardiovascular Society. Published by Elsevier Inc. All rights reserved.

Biointerfacial Property of Plasma-Treated Single-Walled Carbon Nanotube Film Electrodes for Electrochemical Biosensors

NASA Astrophysics Data System (ADS)

Kim, Joon Hyub; Lee, Jun-Yong; Jin, Joon-Hyung; Park, Eun Jin; Min, Nam Ki

2013-01-01

The single-walled carbon nanotube (SWCNT)-based thin film was spray-coated on the Pt support and functionalized using O2 plasma. The effects of plasma treatment on the biointerfacial properties of the SWCNT films were analyzed by cyclic voltammogram (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). The plasma-functionalized (pf) SWCNT electrodes modified with Legionella pneumophila-specific probe DNA strands showed a much higher peak current and a smaller peak separation in differential pulse voltammetry and a lower charge transfer resistance, compared to the untreated samples. These results suggest that the pf-SWCNT films have a better electrocatalytic character and an electron transfer capability faster than the untreated SWCNTs, due to the fact that the oxygen-containing functional groups promote direct electron transfer in the biointerfacial region of the electrocatalytic activity of redox-active biomolecules.

Study of mechanism involved in synthesis of graphene oxide and reduced graphene oxide from graphene nanoplatelets

NASA Astrophysics Data System (ADS)

Sharma, Bhasha; Shekhar, Shashank; Malik, Parul; Jain, Purnima

2018-06-01

Graphene, a wonder material has inspired quest among researchers due to its numerous applications and exceptional properties. This paper highlights the mechanism and chemistry behind the fabrication of graphene oxide by using phosphoric acid. Chemical functionalization is of prime importance which avoids agglomeration of nanoparticles to attain inherent properties. As non-homogeneous dispersion limits its utilization due to interfacial interactions which restrict reactive sites to produce intercalated network. Thus, chemically functionalized graphene leads to stable dispersion and enhances thermal, mechanical and electrical properties of the resultant polymer composite materials. Solubility of graphene in aqueous solution is the major issue because graphene is hydrophobic, to rectify this oxygen containing hydrophilic groups must be introduced to make it compatible and this can be attained by covalent functionalization. Among all nanofiller GO has shown average particle size i.e. 95 nm and highest surface charge density. The characteristic changes were estimated using Raman spectra.

Interplay between oxygen and Fe-S cluster biogenesis: insights from the Suf pathway.

PubMed

Boyd, Eric S; Thomas, Khaleh M; Dai, Yuyuan; Boyd, Jeff M; Outten, F Wayne

2014-09-23

Iron-sulfur (Fe-S) cluster metalloproteins conduct essential functions in nearly all contemporary forms of life. The nearly ubiquitous presence of Fe-S clusters and the fundamental requirement for Fe-S clusters in both aerobic and anaerobic Archaea, Bacteria, and Eukarya suggest that these clusters were likely integrated into central metabolic pathways early in the evolution of life prior to the widespread oxidation of Earth's atmosphere. Intriguingly, Fe-S cluster-dependent metabolism is sensitive to disruption by oxygen because of the decreased bioavailability of ferric iron as well as direct oxidation of sulfur trafficking intermediates and Fe-S clusters by reactive oxygen species. This fact, coupled with the ubiquity of Fe-S clusters in aerobic organisms, suggests that organisms evolved with mechanisms that facilitate the biogenesis and use of these essential cofactors in the presence of oxygen, which gradually began to accumulate around 2.5 billion years ago as oxygenic photosynthesis proliferated and reduced minerals that buffered against oxidation were depleted. This review highlights the most ancient of the Fe-S cluster biogenesis pathways, the Suf system, which likely was present in early anaerobic forms of life. Herein, we use the evolution of the Suf pathway to assess the relationships between the biochemical functions and physiological roles of Suf proteins, with an emphasis on the selective pressure of oxygen toxicity. Our analysis suggests that diversification into oxygen-containing environments disrupted iron and sulfur metabolism and was a main driving force in the acquisition of accessory Suf proteins (such as SufD, SufE, and SufS) by the core SufB-SufC scaffold complex. This analysis provides a new framework for the study of Fe-S cluster biogenesis pathways and Fe-S cluster-containing metalloenzymes and their complicated patterns of divergence in response to oxygen.

Chemical aspects of silicon-containing bilayer resists

NASA Astrophysics Data System (ADS)

Boardman, Larry D.; Kessel, Carl R.; Rhyner, Steven J.

1999-06-01

We have prepare several novel silicon-containing polymers containing both low Ea and high Ea protecting groups, and we have evaluated these materials at both 193 nm. Low Ea acetal-containing polymers were prepared by reacting poly(4-vinylphenol) with novel silyl enol ethers. The ease of protecting group cleavage in these materials is manifested in the immediate formation of a strong latent image after exposure. High Ea polymers were prepared by introducing tertiary esters which contain the tris(trimethylsilyl)silyl group, and both methacrylate copolymers and norbornene-maleic anhydride copolymers containing this group have been synthesized. Both of these materials show good oxygen plasma etch resistance, with the latter demonstrating superior adhesion to poly(4- vinylphenol) planarizing layers. The tris(trimethylsilyl)silyl group imparts a high degree of hydrophobicity to coatings of many of these materials. Acid- catalyzed deprotection of these tertiary esters affords the corresponding carboxylic acids and 1-silyl-3-methylbutenes, and the liberation of these olefins is significantly faster than the loss of isobutylene from the tert-butyl analogs.

The forms of alkalis in the biochar produced from crop residues at different temperatures.

PubMed

Yuan, Jin-Hua; Xu, Ren-Kou; Zhang, Hong

2011-02-01

The forms of alkalis of the biochars produced from the straws of canola, corn, soybean and peanut at different temperatures (300, 500 and 700°C) were studied by means of oxygen-limited pyrolysis. The alkalinity and pH of the biochars increased with increased pyrolysis temperature. The X-ray diffraction spectra and the content of carbonates of the biochars suggested that carbonates were the major alkaline components in the biochars generated at the high temperature; they were also responsible for the strong buffer plateau-regions on the acid-base titration curves at 500 and 700°C. The data of FTIR-PAS and zeta potentials indicated that the functional groups such as -COO(-) (-COOH) and -O(-) (-OH) contained by the biochars contributed greatly to the alkalinity of the biochar samples tested, especially for those generated at the lower temperature. These functional groups were also responsible for the negative charges of the biochars. Copyright © 2010 Elsevier Ltd. All rights reserved.

Geoarchaeota: a new candidate phylum in the Archaea from high-temperature acidic iron mats in Yellowstone National Park

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

Kozubal, Mark; Romine, Margaret F.; Jennings, Ryan

Geothermal systems in Yellowstone National Park (YNP) provide an outstanding opportunity to understand the origin and evolution of metabolic processes necessary for life in extreme environments including low pH, high temperature, low oxygen and elevated concentrations of reduced iron. Previous phylogenetic studies of acidic ferric iron mats from YNP have revealed considerable diversity of uncultivated and undescribed archaea. The goal of this study was to obtain replicate de novo genome assemblies for a dominant archaeal population inhabiting acidic iron oxide mats in YNP. Detailed analysis of conserved ribosomal and informational processing genes indicate that the replicate assemblies represent a newmore » phylum-level lineage referred to here as 'novel archaeal group 1 (NAG1)'. The NAG1 organisms contain pathways necessary for the catabolism of peptides and complex carbohydrates as well as a bacterial-like Form I CO dehydrogenase complex likely used for energy conservation. Moreover, this novel population contains genes involved in metabolism of oxygen including a Type A heme copper oxidase, a bd-type terminal oxidase and a putative oxygen sensing protoglobin. NAG1 has a variety of unique bacterial-like cofactor biosynthesis and transport genes and a Type3-like CRISPR system. Discovery of NAG1 is critical to our understanding of microbial community structure and function in extant thermophilic iron mats of YNP, and will provide insight regarding the evolution of Archaea in early Earth environments that may have important analogues active in YNP today.« less

The smallest quaternary ammonium salts with ether groups for high-performance electrochemical double layer capacitors† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc02755a Click here for additional data file.

PubMed Central

Han, Taihee; Park, Min-Sik; Kim, Jeonghun; Kim, Jung Ho

2016-01-01

Electrochemical double layer capacitors (EDLCs) are energy storage devices that have been used for a wide range of electronic applications. In particular, the electrolyte is one of the important components, directly related to the capacitance and stability. Herein, we first report a series of the smallest quaternary ammonium salts (QASs), with ether groups on tails and tetrafluoroborate (BF4) as an anion, for use in EDLCs. To find the optimal structure, various QASs with different sized head groups and ether-containing tail groups were systematically compared. Comparing two nearly identical structures with and without ether groups, QASs with oxygen atoms showed improved capacitance, proving that ions with oxygen atoms move more easily than their counterparts at lower electric fields. Moreover, the ether containing QASs showed low activation energy values of conductivities, leading to smaller IR drops during the charge and discharge processes, resulting in an overall higher capacitance. PMID:28959391

An Assessment of the Influence of the Industry Distribution Chain on the Oxygen Levels in Commercial Modified Atmosphere Packaged Cheddar Cheese Using Non-Destructive Oxygen Sensor Technology.

PubMed

O' Callaghan, Karen A M; Papkovsky, Dmitri B; Kerry, Joseph P

2016-06-20

The establishment and control of oxygen levels in packs of oxygen-sensitive food products such as cheese is imperative in order to maintain product quality over a determined shelf life. Oxygen sensors quantify oxygen concentrations within packaging using a reversible optical measurement process, and this non-destructive nature ensures the entire supply chain can be monitored and can assist in pinpointing negative issues pertaining to product packaging. This study was carried out in a commercial cheese packaging plant and involved the insertion of 768 sensors into 384 flow-wrapped cheese packs (two sensors per pack) that were flushed with 100% carbon dioxide prior to sealing. The cheese blocks were randomly assigned to two different storage groups to assess the effects of package quality, packaging process efficiency, and handling and distribution on package containment. Results demonstrated that oxygen levels increased in both experimental groups examined over the 30-day assessment period. The group subjected to a simulated industrial distribution route and handling procedures of commercial retailed cheese exhibited the highest level of oxygen detected on every day examined and experienced the highest rate of package failure. The study concluded that fluctuating storage conditions, product movement associated with distribution activities, and the possible presence of cheese-derived contaminants such as calcium lactate crystals were chief contributors to package failure.

An Assessment of the Influence of the Industry Distribution Chain on the Oxygen Levels in Commercial Modified Atmosphere Packaged Cheddar Cheese Using Non-Destructive Oxygen Sensor Technology

PubMed Central

O’ Callaghan, Karen A.M.; Papkovsky, Dmitri B.; Kerry, Joseph P.

2016-01-01

The establishment and control of oxygen levels in packs of oxygen-sensitive food products such as cheese is imperative in order to maintain product quality over a determined shelf life. Oxygen sensors quantify oxygen concentrations within packaging using a reversible optical measurement process, and this non-destructive nature ensures the entire supply chain can be monitored and can assist in pinpointing negative issues pertaining to product packaging. This study was carried out in a commercial cheese packaging plant and involved the insertion of 768 sensors into 384 flow-wrapped cheese packs (two sensors per pack) that were flushed with 100% carbon dioxide prior to sealing. The cheese blocks were randomly assigned to two different storage groups to assess the effects of package quality, packaging process efficiency, and handling and distribution on package containment. Results demonstrated that oxygen levels increased in both experimental groups examined over the 30-day assessment period. The group subjected to a simulated industrial distribution route and handling procedures of commercial retailed cheese exhibited the highest level of oxygen detected on every day examined and experienced the highest rate of package failure. The study concluded that fluctuating storage conditions, product movement associated with distribution activities, and the possible presence of cheese-derived contaminants such as calcium lactate crystals were chief contributors to package failure. PMID:27331815

Effects of hyperbaric oxygen and nerve growth factor on the long-term neural behavior of neonatal rats with hypoxic ischemic brain damage.

PubMed

Wei, Lixia; Ren, Qing; Zhang, Yongjun; Wang, Jiwen

2017-04-01

To evaluate the effects of HBO (Hyperbaric oxygen) and NGF (Nerve growth factor) on the long-term neural behavior of neonatal rats with HIBD (Neonatal hypoxic ischemic brain damage). The HIBD model was produced by ligating the right common carotid artery of 7 days old SD (Sprague-Dawley) rats followed by 8% O2 + 92% N2 for 2h. Totally 40 rats were randomly divided into 5 groups including sham-operated group, HIBD control group, HBO treated group, NGF treated group and NGF + HBO treated group. The learning and memory ability of these rats was evaluated by Morris water maze at 30 days after birth, and sensory motor function was assessed by experiments of foot error and limb placement at 42 days after birth. The escape latency of HBO treated group, NGF treated group and NGF + HBO treated group was shorter than that of HIBD control group (p<0.01) and longer than that of sham-operated group. The piercing indexes of 3 treated groups were higher than that of HIBD control group (p<0.01). Hyperbaric oxygen and nerve growth factor treatments may improve learning and memory ability and sensory motor function in neonatal rats after hypoxic ischemic brain damage.

Functional Group Analysis for Diesel-like Mixing-Controlled Compression Ignition Combustion Blendstocks

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

Gaspar, Daniel J.; McCormick, Robert L.; Polikarpov, Evgueni

This report addresses the suitability of hydrocarbon and oxygenate functional groups for use as a diesel-like fuel blending component in an advanced, mixing-controlled, compression ignition combustion engine. The functional groups are chosen from those that could be derived from a biomass feedstock, and represent a full range of chemistries. This first systematic analysis of functional groups will be of value to all who are pursuing new bio-blendstocks for diesel-like fuels.

Oxygen analyzer

DOEpatents

Benner, William H.

1986-01-01

An oxygen analyzer which identifies and classifies microgram quantities of oxygen in ambient particulate matter and for quantitating organic oxygen in solvent extracts of ambient particulate matter. A sample is pyrolyzed in oxygen-free nitrogen gas (N.sub.2), and the resulting oxygen quantitatively converted to carbon monoxide (CO) by contact with hot granular carbon (C). Two analysis modes are made possible: (1) rapid determination of total pyrolyzable oxygen obtained by decomposing the sample at 1135.degree. C., or (2) temperature-programmed oxygen thermal analysis obtained by heating the sample from room temperature to 1135.degree. C. as a function of time. The analyzer basically comprises a pyrolysis tube containing a bed of granular carbon under N.sub.2, ovens used to heat the carbon and/or decompose the sample, and a non-dispersive infrared CO detector coupled to a mini-computer to quantitate oxygen in the decomposition products and control oven heating.

Normal muscle oxygen consumption and fatigability in sickle cell patients despite reduced microvascular oxygenation and hemorheological abnormalities.

PubMed

Waltz, Xavier; Pichon, Aurélien; Lemonne, Nathalie; Mougenel, Danièle; Lalanne-Mistrih, Marie-Laure; Lamarre, Yann; Tarer, Vanessa; Tressières, Benoit; Etienne-Julan, Maryse; Hardy-Dessources, Marie-Dominique; Hue, Olivier; Connes, Philippe

2012-01-01

Although it has been hypothesized that muscle metabolism and fatigability could be impaired in sickle cell patients, no study has addressed this issue. We compared muscle metabolism and function (muscle microvascular oxygenation, microvascular blood flow, muscle oxygen consumption and muscle microvascular oxygenation variability, which reflects vasomotion activity, maximal muscle force and local muscle fatigability) and the hemorheological profile at rest between 16 healthy subjects (AA), 20 sickle cell-hemoglobin C disease (SC) patients and 16 sickle cell anemia (SS) patients. Muscle microvascular oxygenation was reduced in SS patients compared to the SC and AA groups and this reduction was not related to hemorhelogical abnormalities. No difference was observed between the three groups for oxygen consumption and vasomotion activity. Muscle microvascular blood flow was higher in SS patients compared to the AA group, and tended to be higher compared to the SC group. Multivariate analysis revealed that muscle oxygen consumption was independently associated with muscle microvascular blood flow in the two sickle cell groups (SC and SS). Finally, despite reduced muscle force in sickle cell patients, their local muscle fatigability was similar to that of the healthy subjects. Sickle cell patients have normal resting muscle oxygen consumption and fatigability despite hemorheological alterations and, for SS patients only, reduced muscle microvascular oxygenation and increased microvascular blood flow. Two alternative mechanisms can be proposed for SS patients: 1) the increased muscle microvascular blood flow is a way to compensate for the lower muscle microvascular oxygenation to maintain muscle oxygen consumption to normal values or 2) the reduced microvascular oxygenation coupled with a normal resting muscle oxygen consumption could indicate that there is slight hypoxia within the muscle which is not sufficient to limit mitochondrial respiration but increases muscle microvascular blood flow.

Crosslinked Polyamide

DOEpatents

Huang, Zhi H.; McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

2002-06-04

A crosslinked polyamide material and a process for preparing the crosslinked polyamide material are disclosed. The crosslinked polyamide material comprises a crosslinked chemical combination of (1) a polyamide of the formula: ##STR1## wherein n is between about 50 and 10,000, wherein each R is between 1 and 50 carbon atoms alone and is optionally substituted with heteroatoms, oxygen, nitrogen, sulfur, or phosphorus and combinations thereof, wherein multiple of the R are in vertically aligned spaced relationship along a backbone forming the polyamide, and wherein two or more of the R contain an amino group; and (2) a crosslinking agent containing at least two functional groups capable of reacting with the amino groups of the polyamide. In one embodiment of the invention, the crosslinking agent is an aliphatic or aromatic isocyanate compound having 2 or more --N.dbd.C.dbd.O groups. In another embodiment of the invention, the crosslinking agent is an aliphatic aldehyde or aromatic aldehyde compound having 2 or more --CHO groups. In still another embodiment of the invention, the crosslinking agent is selected from a phosphine having the general formula (A).sub.2 P(B) and mixtures thereof, wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl. In yet another embodiment of the invention, the crosslinking agent is selected from the group consisting of epoxy resins having more than one epoxide group per molecule.

Method of removing nitrogen monoxide from a nitrogen monoxide-containing gas using a water-soluble iron ion-dithiocarbamate, xanthate or thioxanthate

DOEpatents

Liu, David K.; Chang, Shih-Ger

1989-01-01

A method of removing nitrogen monoxide from a nitrogen monoxide-containing gas, which method comprises: (a) contacting a nitrogen oxide-containing gas with an aqueous solution of water soluble organic compound-iron ion chelate of the formula: ##STR1## wherein the water-soluble organic compound is selected from compounds of the formula: ##STR2## wherein: R is selected from hydrogen or an organic moiety having at least one polar functional group; Z is selected from oxygen, sulfur, or --N--A wherein N is nitrogen and A is hydrogen or lower alkyl having from one to four carbon atoms; and M is selected from hydrogen, sodium or potassium; and n is 1 or 2, in a contacting zone for a time and at a temperature effective to reduce the nitrogen monoxide. These mixtures are useful to provide an unexpensive method of removing NO from gases, thus reducing atmospheric pollution from flue gases.

Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

2018-01-01

Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

Characterization and Neutralization of Arsenical-Based WWII Era Chemical Munition Fills

DTIC Science & Technology

2006-08-01

Fluorine 2.23 Hydroxyl Radical 2.06 Atomic Oxygen 1.78 Hydrogen Peroxide 1.31 Perhydroxyl Radical 1.25 Permanganate 1.24 Hypobromous Acid 1.17 Chlorine...containing carbon-carbon double bonds, aldehyde groups or hydroxyl groups. As an electrophile , the permanganate ion is strongly attracted to the

Dissociations between behavioural and functional magnetic resonance imaging-based evaluations of cognitive function after brain injury

PubMed Central

Bardin, Jonathan C.; Fins, Joseph J.; Katz, Douglas I.; Hersh, Jennifer; Heier, Linda A.; Tabelow, Karsten; Dyke, Jonathan P.; Ballon, Douglas J.; Schiff, Nicholas D.

2011-01-01

Functional neuroimaging methods hold promise for the identification of cognitive function and communication capacity in some severely brain-injured patients who may not retain sufficient motor function to demonstrate their abilities. We studied seven severely brain-injured patients and a control group of 14 subjects using a novel hierarchical functional magnetic resonance imaging assessment utilizing mental imagery responses. Whereas the control group showed consistent and accurate (for communication) blood-oxygen-level-dependent responses without exception, the brain-injured subjects showed a wide variation in the correlation of blood-oxygen-level-dependent responses and overt behavioural responses. Specifically, the brain-injured subjects dissociated bedside and functional magnetic resonance imaging-based command following and communication capabilities. These observations reveal significant challenges in developing validated functional magnetic resonance imaging-based methods for clinical use and raise interesting questions about underlying brain function assayed using these methods in brain-injured subjects. PMID:21354974

Fabrication of Polyimide Membrane Incorporated with Functional Graphene Oxide for CO2 Separation: The Effects of GO Surface Modification on Membrane Performance.

PubMed

Wang, Ting; Cheng, Cheng; Wu, Li-Guang; Shen, Jiang-Nan; Van der Bruggen, Bart; Chen, Qian; Chen, Di; Dong, Chun-Ying

2017-06-06

Two kinds of isocyanate were used to modify graphene oxide (GO) samples. Then, polyimide (PI) hybrid membranes containing GO and modified GO were prepared by in situ polymerization. The permeation of CO 2 and N 2 was studied using these novel membranes. The morphology experiments showed that the isocyanate groups were successfully grafted on the surface of GO by replacement of the oxygen-containing functional groups. After modification, the surface polarity of the GO increased, and more defect structures were introduced into the GO surface. This resulted in a good distribution of more modified GO samples in the PI polymer matrix. Thus, the PI hybrid membranes incorporated by modified GO samples showed a high gas permeability and ideal selectivity of membranes. In addition, enhancement of the selectivity due to the solubility of CO 2 played a major role in the increase in the separation performance of the hybrid membranes for CO 2 , although the diffusion coefficients for CO 2 also increased. Both the higher condensability and the strong affinity between CO 2 molecules and GO in the polymer matrix caused an enhancement of the solubility selectivity higher than the diffusion selectivity after GO surface modification.

Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

DOEpatents

Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani

2006-04-04

Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

DOEpatents

Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani; Manivannan, Venkatesan

2004-07-13

Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

Skin oxygen tension is improved by immersion in oxygen-enriched water.

PubMed

Reading, S A; Yeomans, M; Levesque, C

2013-12-01

The perceived health and physiologic functioning of skin depends on adequate oxygen availability. Economical and easily used therapeutic approaches to increase skin oxygenation could improve the subjective appearance of the skin as well as support the management of some cutaneous conditions related to chronic hypoxic ischaemia (e.g. ulcerative wounds). We have tested the hypothesis that the O2 partial pressure of skin (PskO2 ) increases during immersion in water enriched with high levels of dissolved oxygen. A commercially available device was used to produce water containing 45 to 65 mg L(-1) of dissolved O2 . Young adults (YA; n = 7), older adults (OA; n = 13) and older adults with diabetes (OAD; n = 11) completed different experiments that required them to immerse their feet in tap water (<2 mg L(-1) of O2 ; control) or O2 -enriched water (O2 -H2 O; experimental) for 30 min. Transcutaneous oximetry was used to measure PskO2 for 20 min pre- and post-immersion. Pre-immersion mean (standard deviation) PskO2 on the plantar surface of the big toe was 75 (10), 67 (10) and 65 (10) mmHg in YA, OA and OAD, respectively. Post-immersion PskO2 was 244 (25), 193 (28) and 205 (28) mmHg for the same groups. We also show that post-immersion PskO2 varies by location and with advancing age. Water is an effective vehicle for transporting dissolved O2 across the skin surface and could be used as a basis for development of economical therapeutic approaches that improve skin oxygen tension to support skin health and function. © 2013 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Use of impure inert gases in the controlled heating and cooling of mixed conducting metal oxide materials

DOEpatents

Carolan, Michael Francis [Allentown, PA; Bernhart, John Charles [Fleetwood, PA

2012-08-21

Method for processing an article comprising mixed conducting metal oxide material. The method comprises contacting the article with an oxygen-containing gas and either reducing the temperature of the oxygen-containing gas during a cooling period or increasing the temperature of the oxygen-containing gas during a heating period; during the cooling period, reducing the oxygen activity in the oxygen-containing gas during at least a portion of the cooling period and increasing the rate at which the temperature of the oxygen-containing gas is reduced during at least a portion of the cooling period; and during the heating period, increasing the oxygen activity in the oxygen-containing gas during at least a portion of the heating period and decreasing the rate at which the temperature of the oxygen-containing gas is increased during at least a portion of the heating period.

High Temperature Sorbents for Oxygen

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor)

1996-01-01

A sorbent capable of removing trace amounts of oxygen (ppt) from a gas stream at a high temperature above 200 C is introduced. The sorbent comprises a porous alumina silicate support such as zeolite containing from 1 to 10 percent by weight of ion exchanged transition metal such as copper or cobalt ions and 0.05 to 1.0 percent by weight of an activator selected from a platinum group metal such as platinum. The activation temperature, oxygen sorption and reducibility are all improved by the presence of the platinum activator.

Method for oxygen reduction in a uranium-recovery process. [US DOE patent application

DOEpatents

Hurst, F.J.; Brown, G.M.; Posey, F.A.

1981-11-04

An improvement in effecting uranium recovery from phosphoric acid solutions is provided by sparging dissolved oxygen contained in solutions and solvents used in a reductive stripping stage with an effective volume of a nonoxidizing gas before the introduction of the solutions and solvents into the stage. Effective volumes of nonoxidizing gases, selected from the group consisting of argon, carbon dioxide, carbon monoxide, helium, hydrogen, nitrogen, sulfur dioxide, and mixtures thereof, displace oxygen from the solutions and solvents thereby reduce deleterious effects of oxygen such as excessive consumption of elemental or ferrous iron and accumulation of complex iron phosphates or cruds.

Hydrogen production using hydrogenase-containing oxygenic photosynthetic organisms

DOEpatents

Melis, Anastasios; Zhang, Liping; Benemann, John R.; Forestier, Marc; Ghirardi, Maria; Seibert, Michael

2006-01-24

A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

Hydrogen Production Using Hydrogenase-Containing Oxygenic Photosynthetic Organisms

DOEpatents

Melis, A.; Zhang, L.; Benemann, J. R.; Forestier, M.; Ghirardi, M.; Seibert, M.

2006-01-24

A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

Whey protein film with oxygen scavenging function by incorporation of ascorbic acid.

PubMed

Janjarasskul, Theeranun; Tananuwong, Kanitha; Krochta, John M

2011-01-01

Residual O(2) in a package headspace can be removed by an O(2)-absorbing sachet, which can be harmful if swallowed by the consumer, or by a chemically-active plastic packaging film, which is difficult to recycle. An edible, O(2)-absorbing film would avoid these disadvantages. The objective of our research was to assess the O(2)-scavenging potential of an edible whey protein isolate (WPI) film incorporating ascorbic acid (AA). AA at 0.05, 0.1, or 0.2 M was added to 5% (w/w) heat-denatured WPI film-forming solutions with WPI : glycerol (Gly) ratio of 1: 1.00, 1: 0.80, or 1: 0.67. The pH of solutions was then adjusted to 3.5 (below pK(a1) of AA), to stabilize AA against oxidation, before film casting. The mechanical properties, O(2) permeabilities, and thermal transitions of films were measured. Activation of the O(2)-scavenging function of the AA-incorporated films was accomplished by adjustment of the films to pH ≥ 7. O(2)-scavenging ability of AA-incorporated WPI films was determined by measuring residual O(2) in the headspace of a high-barrier container. Incorporation of AA into WPI film decreased film tensile strength and further reduced O(2) permeability at each WPI : Gly ratio. AA-containing films adjusted to pH ≥ 7 demonstrated O(2) absorption proportional to AA content, consistent with theoretical O(2)-scavenging capacity. Thermal transition measurements indicated that AA was involved in WPI structural modification and decreased the degradation temperature of WPI-based film. The demonstrated O(2)-scavenging function, improved O(2) barrier and acceptable mechanical properties of AA-incorporated films indicate potential commercial usefulness. Ascorbic acid-incorporated whey protein film with oxygen scavenging function can be used to extend shelf lives of a wide variety of oxygen-sensitive products by eliminating headspace oxygen as well as oxygen permeating through the packaging wall over time. Edible oxygen-scavenger film has the advantages of avoiding both accidental consumption and nonrecyclability of conventional oxygen scavenger systems. © 2011 Institute of Food Technologists®

Vacuum ultraviolet trimming of oxygenated functional groups from oxidized self-assembled hexadecyl monolayers in an evacuated environment

NASA Astrophysics Data System (ADS)

Soliman, Ahmed I. A.; Utsunomiya, Toru; Ichii, Takashi; Sugimura, Hiroyuki

2017-09-01

Vacuum ultraviolet light irradiation in dry air generates active oxygen species, which have powerful oxidation abilities. These active oxygen species (O) can oxidize the alkyl moieties of polymers, and generate new oxygenated groups such as OH, CHO and COOH groups. Reducing the oxygen content in the exposure environment decreases the rate of oxidation processes. In this study, we examined the influences of the 172 nm VUV irradiation in a high vacuum (HV, < 10-3 Pa) environment on the chemical constituents, surface properties and morphological structure of well-defined VUV/(O)-modified hexadecyl (HD-) self-assembled monolayer (SAM) prepared on hydrogen-terminated silicon (H-Si) substrate. After VUV light irradiation in a HV environment (HV-VUV), the chemical constituents and surface properties were changed in two distinct stages. At short irradiation time (the first stage), the Csbnd O and COO groups decreased rapidly, while the Cdbnd O groups slightly changed. The dissociation of nonderivatizable groups (such as ether (Csbnd Osbnd C) and ester (Csbnd COOsbnd C) groups) compensated the dissociated OH, CHO, Csbnd COsbnd C and COOH groups. With further irradiation (the second stage), the quantities of the oxygenated groups slightly decreased. The carbon skeleton (Csbnd C) of SAM was scarcely dissociated during the HV-VUV treatment. These chemical changes affected the surface properties, such as wettability and morphology.

The role of beaded activated carbon's surface oxygen groups on irreversible adsorption of organic vapors.

PubMed

Jahandar Lashaki, Masoud; Atkinson, John D; Hashisho, Zaher; Phillips, John H; Anderson, James E; Nichols, Mark

2016-11-05

The objective of this study is to determine the contribution of surface oxygen groups to irreversible adsorption (aka heel formation) during cyclic adsorption/regeneration of organic vapors commonly found in industrial systems, including vehicle-painting operations. For this purpose, three chemically modified activated carbon samples, including two oxygen-deficient (hydrogen-treated and heat-treated) and one oxygen-rich sample (nitric acid-treated) were prepared. The samples were tested for 5 adsorption/regeneration cycles using a mixture of nine organic compounds. For the different samples, mass balance cumulative heel was 14 and 20% higher for oxygen functionalized and hydrogen-treated samples, respectively, relative to heat-treated sample. Thermal analysis results showed heel formation due to physisorption for the oxygen-deficient samples, and weakened physisorption combined with chemisorption for the oxygen-rich sample. Chemisorption was attributed to consumption of surface oxygen groups by adsorbed species, resulting in formation of high boiling point oxidation byproducts or bonding between the adsorbates and the surface groups. Pore size distributions indicated that different pore sizes contributed to heel formation - narrow micropores (<7Å) in the oxygen-deficient samples and midsize micropores (7-12Å) in the oxygen-rich sample. The results from this study help explain the heel formation mechanism and how it relates to chemically tailored adsorbent materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison of the Organic Composition of Cometary Samples with Residues Formed from the UV Irradiation of Astrophysical Ice Analogs

NASA Technical Reports Server (NTRS)

Milam, S. N.; Nuevo, M.; Sandford, S. A.; Cody, G. D.; Kilcoyne, A. L. D.; Stroud, R. M.; DeGregorio, B. T.

2010-01-01

The NASA Stardust mission successfully collected material from Comet 81P/Wild 2 [1], including authentic cometary grains [2]. X-ray absorption near-edge structure (XANES) spectroscopy analysis of these samples indicates the presence of oxygen-rich and nitrogen-rich organic materials, which contain a broad variety of functional groups (carbonyls, C=C bonds, aliphatic chains, amines, arnides, etc.) [3]. One component of these organics appears to contain very little aromatic carbon and bears some similarity to the organic residues produced by the irradiation of ices of interstellar/cometary composition, Stardust samples were also recently shown to contain glycine, the smallest biological amino acid [4]. Organic residues produced froth the UV irradiation of astrophysical ice analogs are already known to contain a large suite of organic molecules including amino acids [5-7], amphiphilic compounds (fatty acids) [8], and other complex species. This work presents a comparison between XANES spectra measured from organic residues formed in the laboratory with similar data of cometary samples collected by the Stardust mission

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

Goldfarb, J.L.; Suuberg, E.M.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated derivatives (OPAHs) are ubiquitous environmental pollutants resulting from the incomplete combustion of coal and fossil fuels. Their vapor pressures are key thermodynamic data essential for modeling fate and transport within the environment. The present study involved nine PAHs containing oxygen heteroatoms, including aldehyde, carboxyl, and nitro groups, specifically 2-nitrofluorene, 9-fluorenecarboxylic acid, 2-fluorenecarboxaldehyde, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, 9-anthraldehyde, 1-nitropyrene, 1-pyrenecarboxaldehyde, and 1-bromo-2-naphthoic acid. The vapor pressures of these compounds, with molecular weights ranging from 194 to 251 g/mol, were measured using the isothermal Knudsen effusion technique in the temperature range of 329 to 421more » K. The corresponding enthalpies of sublimation, calculated via the Clausius-Clapeyron equation, are compared to parent, nonoxygenated PAH compound data to determine the effect of the addition of these oxygen-containing heteroatoms. As expected, the addition of -CHO, -COOH, and -NO{sub 2} groups onto these PAHs increases the enthalpy of sublimation and decreases the vapor pressure as compared to the parent PAH; the position of substitution also plays a significant role in determining the vapor pressure of these OPAHs.« less

Polystyrene foam products equation of state as a function of porosity and fill gas

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

Mulford, Roberta N; Swift, Damian C

2009-01-01

An accurate EOS for polystyrene foam is necessary for analysis of numerous experiments in shock compression, inertial confinement fusion, and astrophysics. Plastic to gas ratios vary between various samples of foam, according to the density and cell-size of the foam. A matrix of compositions has been investigated, allowing prediction of foam response as a function of the plastic-to-air ratio. The EOS code CHEETAH allows participation of the air in the decomposition reaction of the foam. Differences between air-filled, Ar-blown, and CO{sub 2}-blown foams are investigated, to estimate the importance of allowing air to react with products of polystyrene decomposition. O{submore » 2}-blown foams are included in some comparisons, to amplify any consequences of reaction with oxygen in air. He-blown foams are included in some comparisons, to provide an extremum of density. Product pressures are slightly higher for oxygen-containing fill gases than for non-oxygen-containing fill gases. Examination of product species indicates that CO{sub 2} decomposes at high temperatures.« less

Space charge characteristics of fluorinated polyethylene: Different effects of fluorine and oxygen

NASA Astrophysics Data System (ADS)

Zhao, Ni; Nie, Yongjie; Li, Shengtao

2018-04-01

Direct fluorination are proved having obvious effect on space charge characteristics of polyethylene. It is believed that fluorine has a positive effect on suppressing space charge injection while oxygen impurity has a negative effect. However, the mechanism for the opposite effect of fluorine and oxygen is still not clear. In this paper, the different effects of fluorine and oxygen on space charge characteristics of fluorinated low density polyethylene (LDPE) are investigated on the basis of dielectric property, chemical constitutes and trap performance of surface fluorinated layers. The results show that direct fluorination has obvious effect on chemical constitutes and dielectric properties of surface fluorinated layer. Introduced fluorine is the main factor for suppressing charge injection from the electrodes, because it seriously changes the chemical constitutes and further the trap properties of the surface fluorinated layer. While introduction of oxygen results in heterocharges and makes space charge distribution complex, due to the ionization of generated small groups like C=O containing groups. Moreover, direct fluorination will result in cleavage of some LDPE molecules whatever there is oxygen impurity or not.

Oxygen analyzer

DOEpatents

Benner, W.H.

1984-05-08

An oxygen analyzer which identifies and classifies microgram quantities of oxygen in ambient particulate matter and for quantitating organic oxygen in solvent extracts of ambient particulate matter. A sample is pyrolyzed in oxygen-free nitrogen gas (N/sub 2/), and the resulting oxygen quantitatively converted to carbon monoxide (CO) by contact with hot granular carbon (C). Two analysis modes are made possible: (1) rapid determination of total pyrolyzable obtained by decomposing the sample at 1135/sup 0/C, or (2) temperature-programmed oxygen thermal analysis obtained by heating the sample from room temperature to 1135/sup 0/C as a function of time. The analyzer basically comprises a pyrolysis tube containing a bed of granular carbon under N/sub 2/, ovens used to heat the carbon and/or decompose the sample, and a non-dispersive infrared CO detector coupled to a mini-computer to quantitate oxygen in the decomposition products and control oven heating.

Adaptive servoventilation versus oxygen therapy for sleep disordered breathing in patients with heart failure: a randomised trial

PubMed Central

Murase, Kimihiko; Ono, Koh; Yoneda, Tomoya; Iguchi, Moritake; Yokomatsu, Takafumi; Mizoguchi, Tetsu; Izumi, Toshiaki; Akao, Masaharu; Miki, Shinji; Nohara, Ryuji; Ueshima, Kenji; Mishima, Michiaki; Kimura, Takeshi; White, David P; Chin, Kazuo

2016-01-01

Background Both adaptive servoventilation (ASV) and nocturnal oxygen therapy improve sleep disordered breathing (SDB), but their effects on cardiac parameters have not been compared systematically. Methods and results 43 patients with chronic heart failure (CHF; left ventricular ejection fraction (LVEF) ≤50%) with SDB were randomly assigned to undergo ASV (n=19, apnoea hypopnoea index (AHI)=34.2±12.1/h) or oxygen therapy (n=24, 36.9±9.9/h) for 3 months. More than 70% of SDB events in both groups were central apnoeas or hypopnoeas. Although nightly adherence was less for the ASV group than for the oxygen group (4.4±2.0 vs 6.2±1.8 h/day, p<0.01), the improvement in AHI was larger in the ASV group than in the oxygen group (−27.0±11.5 vs −16.5±10.2/h, p<0.01). The N-terminal pro-brain natriuretic peptide (NT-proBNP) level in the ASV group improved significantly after titration (1535±2224 to 1251±2003 pg/mL, p=0.01), but increased slightly at follow-up and this improvement was not sustained (1311±1592 pg/mL, p=0.08). Meanwhile, the level of plasma NT-proBNP in the oxygen group did not show a significant change throughout the study (baseline 1071±1887, titration 980±1913, follow-up 1101±1888 pg/mL, p=0.19). The significant difference in the changes in the NT-proBNP level throughout the study between the 2 groups was not found (p=0.30). Neither group showed significant changes in echocardiographic parameters. Conclusions Although ASV produced better resolution of SDB in patients with CHF as compared with oxygen therapy, neither treatment produced a significant improvement in cardiac function in the short term. Although we could not draw a definite conclusion because of the small number of participants, our data do not seem to support the routine use of ASV or oxygen therapy to improve cardiac function in patients with CHF with SDB. Trial registration number NCT01187823 (http://www.clinicaltrials.gov). PMID:27099761

Which side of the balance determines the frequency of vaso-occlusive crises in children with sickle cell anemia: Blood viscosity or microvascular dysfunction?

PubMed

Charlot, Keyne; Romana, Marc; Moeckesch, Berenike; Jumet, Stéphane; Waltz, Xavier; Divialle-Doumdo, Lydia; Hardy-Dessources, Marie-Dominique; Petras, Marie; Tressières, Benoît; Tarer, Vanessa; Hue, Olivier; Etienne-Julan, Maryse; Antoine-Jonville, Sophie; Connes, Philippe

2016-01-01

Vascular resistance and tissue perfusion may be both affected by impaired vascular function and increased blood viscosity. Little is known about the effects of vascular function on the occurrence of painful vaso-occlusive crises (VOC) in children with sickle cell anemia (SCA). The aim of the present study was to determine which side of the balance (blood viscosity or vascular function) is the most deleterious in SCA and increases the risk for frequent hospitalized VOC. Microvascular function, microcirculatory oxygenation and blood viscosity were determined in a group of 22 SCA children/adolescents at steady state and a group of 13 healthy children/adolescents. Univariate analyses demonstrated blunted microvascular reactivity during local thermal heating test and decreased microcirculatory oxygenation in SCA children compared to controls. Multivariate analysis revealed that increased blood viscosity and decreased microcirculatory oxygenation were independent risk factors of frequent VOC in SCA. In contrast, the level of microvascular dysfunction does not predict VOC rate. In conclusion, increased blood viscosity is usually well supported in healthy individuals where vascular function is not impaired. However, in the context of SCA, microvascular function is impaired and any increase of blood viscosity or decrease in microcirculatory oxygenation would increase the risks for frequent VOC. Copyright © 2015 Elsevier Inc. All rights reserved.

Environmental Assessment for the Aeromedical Evacuation Formal Training Unit, Wright-Patterson Air Force Base

DTIC Science & Technology

2012-05-01

adverse health effects (HHS 2010). However, propylene glycol requires oxygen for breakdown, which can deplete surface waters of dissolved oxygen ...and the Human Effectiveness Directorate (RH), plus supporting functions. Facility 20840 contains a high-bay area that houses two C-130 training...aircrew training program that develops and maintains a high state of mission readiness for immediate and effective deployments across the range of

Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

DOE PAGES

Bang, Suhee; Lee, Yong -Min; Hong, Seungwoo; ...

2014-09-14

Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η 2:η 2-O 2)–M n+ (M n+ = Sr 2+, Ca 2+, Zn 2+, Lu 3+, Y 3+ and Sc 3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca 2+ and Sr 2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities ofmore » complexes formed with stronger Lewis acidities were found to be markedly different. In conclusion, complexes that contain Ca 2+ or Sr 2+ ions were oxidized by an electron acceptor to release O 2, whereas the release of O 2 did not occur for complexes that bind stronger Lewis acids. Furthermore, we discuss these results in the light of the functional role of the Ca 2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex.« less

Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

PubMed Central

Bang, Suhee; Lee, Yong-Min; Hong, Seungwoo; Cho, Kyung-Bin; Nishida, Yusuke; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

2014-01-01

Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η2:η2-O2)–Mn+ (Mn+ = Sr2+, Ca2+, Zn2+, Lu3+, Y3+ and Sc3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca2+ and Sr2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities of complexes formed with stronger Lewis acidities were found to be markedly different. Complexes that contain Ca2+ or Sr2+ ions were oxidized by an electron acceptor to release O2, whereas the release of O2 did not occur for complexes that bind stronger Lewis acids. We discuss these results in the light of the functional role of the Ca2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex. PMID:25242490

Direct oxygen supply with polydimethylsiloxane (PDMS) membranes induces a spontaneous organization of thick heterogeneous liver tissues from rat fetal liver cells in vitro.

PubMed

Hamon, Morgan; Hanada, Sanshiro; Fujii, Teruo; Sakai, Yasuyuki

2012-01-01

Oxygen is a vital nutrient for growth and maturation of in vitro cells (e.g., adult hepatocytes). We previously demonstrated that direct oxygenation through a polydimethylsiloxane (PDMS) membrane increases the oxygen supply to cell cultures and improves hepatocyte functions. In this study, we removed limits on oxygen supply to fetal rat liver cells through the use of direct oxygenation through a PDMS membrane to investigate in vitro growth and maturation. We chose fetal liver cells because they are considered a feasible source of liver progenitor cells for regenerative medicine therapy due to their highly efficient maturation and proliferation. Cells from 17-day-old pregnant rats were cultured under 5% and 21% oxygen atmospheres. Some cells were first cultured under 5% oxygen, and then switched to a 21% oxygen atmosphere. When oxygen supply was enhanced by a PDMS membrane, the rat fetal liver cells organized into a complex tissue composed of an epithelium of hepatocytes above a mesenchyme-like tissue. The thickness of this supportive tissue was directly correlated to oxygen concentration and was thicker under 5% oxygen. When cultures were switched from 5% to 21% oxygen, lumen-containing structures were formed in the thick mesenchymal-like tissue and the albumin secretion rate increased. In addition, cells adapted their glycolytic activity to the oxygen concentrations. This system promoted the formation of a functional and organized thick tissue suitable for use in regenerative medicine.

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

PubMed

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

Electrochemical surface modification of carbon mesh anode to improve the performance of air-cathode microbial fuel cells.

PubMed

Luo, Jianmei; Chi, Meiling; Wang, Hongyu; He, Huanhuan; Zhou, Minghua

2013-12-01

A convenient and promising alternative to surface modification of carbon mesh anode was fulfilled by electrochemical oxidation in the electrolyte of nitric acid or ammonium nitrate at ambient temperature. It was confirmed that such an anode modification method was low cost and effective not only in improving the efficiency of power generation in microbial fuel cells (MFCs) for synthetic wastewater treatment, but also helping to reduce the period for MFCs start-up. The MFCs with anode modification in electrolyte of nitric acid performed the best, achieving a Coulombic efficiency enhancement of 71 %. As characterized, the electrochemical modification resulted in the decrease of the anode potential and internal resistance but the increase of current response and nitrogen-containing and oxygen-containing functional groups on the carbon surface, which might contribute to the enhancement on the performances of MFCs.

Modification of polycarbonate surface in oxidizing plasma

NASA Astrophysics Data System (ADS)

Ovtsyn, A. A.; Smirnov, S. A.; Shikova, T. G.; Kholodkov, I. V.

2017-11-01

The properties of the surface of the film polycarbonate Lexan 8010 were experimentally studied after treatment in a DC discharge plasma in oxygen and air at pressures of 50-300 Pa and a discharge current of 80 mA. The contact angles of wetting and surface energies are measured. The topography of the surface was investigated by atomic force microscopy. The chemical composition of the surface was determined from the FT-IR spectroscopy data in the variant of total internal reflection, as well as X-ray photoelectron spectroscopy. Treatment in the oxidizing plasma leads to a change in morphology (average roughness increases), an increase in the surface energy, and the concentration of oxygen-containing groups (hydroxyl groups, carbonyl groups in ketones or aldehydes and in oxyketones) on the surface of the polymer. Possible reasons for the difference in surface properties of polymer under the action of oxygen and air plasma on it are discussed.

Structure and function of enzymes in heme biosynthesis.

PubMed

Layer, Gunhild; Reichelt, Joachim; Jahn, Dieter; Heinz, Dirk W

2010-06-01

Tetrapyrroles like hemes, chlorophylls, and cobalamin are complex macrocycles which play essential roles in almost all living organisms. Heme serves as prosthetic group of many proteins involved in fundamental biological processes like respiration, photosynthesis, and the metabolism and transport of oxygen. Further, enzymes such as catalases, peroxidases, or cytochromes P450 rely on heme as essential cofactors. Heme is synthesized in most organisms via a highly conserved biosynthetic route. In humans, defects in heme biosynthesis lead to severe metabolic disorders called porphyrias. The elucidation of the 3D structures for all heme biosynthetic enzymes over the last decade provided new insights into their function and elucidated the structural basis of many known diseases. In terms of structure and function several rather unique proteins were revealed such as the V-shaped glutamyl-tRNA reductase, the dipyrromethane cofactor containing porphobilinogen deaminase, or the "Radical SAM enzyme" coproporphyrinogen III dehydrogenase. This review summarizes the current understanding of the structure-function relationship for all heme biosynthetic enzymes and their potential interactions in the cell.

Thermal Behaviors and Their Correlations of Mg(BH4)2-Contained Explosives

NASA Astrophysics Data System (ADS)

Yue, Yue; Chen, Liping; Peng, Jinhua

2018-01-01

In order to explore the effect of metal hydride on energetic materials' thermal behaviors and their correlations, we studied the heats of combustion and detonation of RDX, TNT, and Mg(BH4)2-containing explosives both theoretically and experimentally. The results showed that Mg(BH4)2 can significantly improve the energy of explosive. As the mass fraction of Mg(BH4)2 increases, the combustion heat of composite explosives increases gradually, while the combustion efficiency decreases. When its mass fraction is about 30%, the theoretical heats of detonation of RDX/Mg(BH4)2 and TNT/Mg(BH4)2 reach maximum, which are 7418.47 and 7032.46 kJ/kg, respectively. When we compared the errors between calculation and experimental values, we found that L-C method is more accurate in calculating oxygen-enriched and oxygen-balanced explosives, and that minimum free energy method is more suitable for seriously negative oxygen-balanced explosive. For single explosive, there are three kinds of relationships between heat of combustion and detonation according to the oxygen balance. For Mg(BH4)2-containing explosives, the relationship is in accordance with Boltzmann function.

Novel graphene-oxide-coated SPR interfaces for biosensing applications

NASA Astrophysics Data System (ADS)

Volkov, V. S.; Stebunov, Yu. V.; Yakubovsky, D. I.; Fedyanin, D. Yu.; Arsenin, A. V.

2017-09-01

Carbon allotropes-based nanomaterials possess unique physical and chemical properties including high surface area, the possibility of pi-stacking interaction with a wide range of biological objects, rich availability of oxygen-containing functional groups in graphene-oxide (GO), and excellent optical properties, which make them an ideal candidate for use as a universal immobilization platform in SPR biosensing. Here, we propose a new surface plasmon resonance (SPR) biosensing interface for sensitive and selective detection of small molecules. This interface is based on the GO linking layers deposited on the gold/copper surface of SPR sensor chips. To estimate the binding capacity of GO layers, modification of carboxyl groups to N-Hydroxysuccinimide esters was performed in the flow cell of SPR instrument. For comparison, the same procedure was applied to commercial sensor chips based on linking layers of carboxymethylated dextran.

Plasma treatment of polymers for improved adhesion

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

Kelber, J.A.

1988-01-01

A variety of plasma treatments of polymer surfaces for improved adhesion are reviewed: noble and reactive gas treatment of fluoropolymers; noble and reactive treatment of polyolefins, and plasma-induced amination of polymer fibers. The plasma induced surface chemical and morphological changes are discussed, as are the mechanisms of adhesion to polymeric adhesives, particularly epoxy. Noble gas plasma etching of flouropolymers produces a partially defluorinated, textured surface. The mechanical interlocking of this textured surface is the primary cause of improved adhesion to epoxy. Reactive gas plasmas also induce defluorination, but oxygen containing gases cause continual ablation of the fluoropolymer surface. Noble andmore » reactive gas (exept for hydrogen) etching of polyolefins results in surface oxidation and improved adhesion via hydrogen bonding of these oxygen containing groups across the interface. The introduction of amine groups to a polymer surface by amonia or amine plasma treatment generally results in improved adhesion to epoxy. However, amine-epoxy ring interactions can be severely effected by steric factors due to chemical groups surrounding the amine. 41 refs.« less

From artificial red blood cells, oxygen carriers, and oxygen therapeutics to artificial cells, nanomedicine, and beyond

PubMed Central

Chang, Thomas M. S.

2013-01-01

The first experimental artificial red blood cells have all three major functions of red blood cells (rbc). However, the first practical one is a simple polyhemoglobin (PolyHb) that only has an oxygen-carrying function. This is now in routine clinical use in South Africa and Russia. An oxygen carrier with antioxidant functions, PolyHb-catalase-superoxide dismutase, can fulfill two of the three functions of rbc. Even more complete is one with all three functions of rbc in the form of PolyHb-catalase-superoxide dismutase-carbonic anhydrase. The most advanced ones are nanodimension artificial rbc with either PEG-lipid membrane or PEG-PLA polymermembrane. Extensions in to oxygen therapeutics include a PolyHb-tyrosinase that suppresses the growth of melanoma in a mice model. Another is a PolyHb-fibrinogen that is an oxygen carrier with platelet-like function. Research has now extended well beyond the original research on artificial rbc into many areas of artificial cells. These include nanoparticles, nanotubules, lipid vesicles, liposomes, polymer-tethered lipid vesicles, polymersomes, microcapsules, bioencapsulation, nanocapules, macroencapsulation, synthetic cells, and others. These are being used in nanotechnology, nanomedicine, regenerative medicine, enzyme/gene therapy, cell/stem cell therapy, biotechnology, drug delivery, hemoperfusion, nanosensers, and even by some groups in agriculture, industry, aquatic culture, nanocomputers, and nanorobotics. PMID:22409281

Silicone-containing composition

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

Mohamed, Mustafa

A silicone-containing composition comprises the reaction product of a first component and an excess of an isocyanate component relative to the first component to form an isocyanated intermediary. The first component is selected from one of a polysiloxane and a silicone resin. The first component includes a carbon-bonded functional group selected from one of a hydroxyl group and an amine group. The isocyanate component is reactive with the carbon-bonded functional group of the first component. The isocyanated intermediary includes a plurality of isocyanate functional groups. The silicone-containing composition comprises the further reaction product of a second component, which is selectedmore » from the other of the polysiloxane and the silicone resin. The second component includes a plurality of carbon-bonded functional groups reactive with the isocyanate functional groups of the isocyanated intermediary for preparing the silicone-containing composition.« less

Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO 2 (111) surfaces

DOE PAGES

Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; ...

2016-05-12

We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO 2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO 2(111) surface was obtained by annealing the thin film under 2.0 × 10 –5 Torr of oxygen at ~550 °C for 30 min. In order to reduce the CeO 2(111) surface, the thin film was annealed under ~5.0 × 10 –10 Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface.more » The saturated TMAA coverage on the CeO 2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. Furthermore, XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO 2–δ(111) surface through dissociative adsorption.« less

Stabilized metal nanoparticles from organometallic precursors for low temperature fuel cells.

PubMed

Ramirez-Meneses, E; Dominguez-Crespo, M A; Torres-Huerta, A M

2013-01-01

In this work, a review of articles and patents related to the utilization of colloidal metal nanoparticles produced by the decomposition of organometallic precursors as supported electrocatalysts in different electrochemical reactions including hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) is discussed. In the case of stabilized metal nanoparticles, the kind of functional group contained in the stabilizer as well as the metal/stabilizer ratio, to evaluate the effect of particle size on the electrochemical performance, were also debated. Potential applications and perspectives of these electrocatalysts in proton exchange membrane fuel cells (PEMFC) are contended with reference to the role played by the coordination compounds and costs.

Highly Efficient Moisture-Triggered Nanogenerator Based on Graphene Quantum Dots.

PubMed

Huang, Yaxin; Cheng, Huhu; Shi, Gaoquan; Qu, Liangti

2017-11-08

A high-performance moisture triggered nanogenerator is fabricated by using graphene quantum dots (GQDs) as the active material. GQDs are prepared by direct oxidation and etching of natural graphite powder, which have small sizes of 2-5 nm and abundant oxygen-containing functional groups. After the treatment by electrochemical polarization, the GQDs-based moisture triggered nanogenerator can deliver a high voltage up to 0.27 V under 70% relative humidity variation, and a power density of 1.86 mW cm -2 with an optimized load resistor. The latter value is much higher than the moisture-electric power generators reported previously. The GQD moisture triggered nanogenerator is promising for self-power electronics and miniature sensors.

Functionalization of nanocrystalline diamond films with phthalocyanines

NASA Astrophysics Data System (ADS)

Petkov, Christo; Reintanz, Philipp M.; Kulisch, Wilhelm; Degenhardt, Anna Katharina; Weidner, Tobias; Baio, Joe E.; Merz, Rolf; Kopnarski, Michael; Siemeling, Ulrich; Reithmaier, Johann Peter; Popov, Cyril

2016-08-01

Phthalocyanine (Pc) derivatives containing different central metal atoms (Mn, Cu, Ti) and different peripheral chains were synthesized and comprehensively characterized. Their interaction with nanocrystalline diamond (NCD) films, as-grown by hot-filament chemical vapor deposition or after their modification with oxygen plasma to exchange the hydrogen termination with oxygen-containing groups, was studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The elemental composition as determined by XPS showed that the Pc were grafted on both as-grown and O-terminated NCD. Mn, Cu and Ti were detected together with N stemming from the Pc ring and S in case of the Ti-Pc from the peripheral ligands. The results for the elemental surface composition and the detailed study of the N 1s, S 2p and O 1s core spectra revealed that Ti-Pc grafted better on as-grown NCD but Cu-Pc and Mn-Pc on O-terminated films. Samples of Mn-Pc on as-grown and O-terminated NCD were further investigated by NEXAFS spectroscopy. The results showed ordering of the grafted molecules, laying flat on the H-terminated NCD surface while only the macrocycles were oriented parallel to the O-terminated surface with the peripheral chains perpendicular to it.

Functional group composition of organic aerosol from combustion emissions and secondary processes at two contrasted urban environments

NASA Astrophysics Data System (ADS)

El Haddad, Imad; Marchand, Nicolas; D'Anna, Barbara; Jaffrezo, Jean Luc; Wortham, Henri

2013-08-01

The quantification of major functional groups in atmospheric organic aerosol (OA) provides a constraint on the types of compounds emitted and formed in atmospheric conditions. This paper presents functional group composition of organic aerosol from two contrasted urban environments: Marseille during summer and Grenoble during winter. Functional groups were determined using a tandem mass spectrometry approach, enabling the quantification of carboxylic (RCOOH), carbonyl (RCOR‧), and nitro (RNO2) functional groups. Using a multiple regression analysis, absolute concentrations of functional groups were combined with those of organic carbon derived from different sources in order to infer the functional group contents of different organic aerosol fractions. These fractions include fossil fuel combustion emissions, biomass burning emissions and secondary organic aerosol (SOA). Results clearly highlight the differences between functional group fingerprints of primary and secondary OA fractions. OA emitted from primary sources is found to be moderately functionalized, as about 20 carbons per 1000 bear one of the functional groups determined here, whereas SOA is much more functionalized, as in average 94 carbons per 1000 bear a functional group under study. Aging processes appear to increase both RCOOH and RCOR‧ functional group contents by nearly one order of magnitude. Conversely, RNO2 content is found to decrease with photochemical processes. Finally, our results also suggest that other functional groups significantly contribute to biomass smoke and SOA. In particular, for SOA, the overall oxygen content, assessed using aerosol mass spectrometer measurements by an O:C ratio of 0.63, is significantly higher than the apparent O:C* ratio of 0.17 estimated based on functional groups measured here. A thorough examination of our data suggests that this remaining unexplained oxygen content can be most probably assigned to alcohol (ROH), organic peroxides (ROOH), organonitrates (RONO2) and/or organosulfates (ROSO3H).

Carbon-based composite electrocatalysts for low temperature fuel cells

DOEpatents

Popov, Branko N [Columbia, SC; Lee, Jog-Won [Columbia, SC; Subramanian, Nalini P [Kennesaw, GA; Kumaraguru, Swaminatha P [Honeoye Falls, NY; Colon-Mercado, Hector R [Columbia, SC; Nallathambi, Vijayadurga [T-Nagar, IN; Li, Xuguang [Columbia, SC; Wu, Gang [West Columbia, SC

2009-12-08

A process for synthesis of a catalyst is provided. The process includes providing a carbon precursor material, oxidizing the carbon precursor material whereby an oxygen functional group is introduced into the carbon precursor material, and adding a nitrogen functional group into the oxidized carbon precursor material.

Human amniotic fluid mesenchymal stem cells in combination with hyperbaric oxygen augment peripheral nerve regeneration.

PubMed

Pan, Hung-Chuan; Chin, Chun-Shih; Yang, Dar-Yu; Ho, Shu-Peng; Chen, Chung-Jung; Hwang, Shiaw-Min; Chang, Ming-Hong; Cheng, Fu-Chou

2009-07-01

Attenuation of pro-inflammatory cytokines and associated inflammatory cell deposits rescues human amniotic fluid mesenchymal stem cells (AFS) from apoptosis. Hyperbaric oxygen (HBO) suppressed stimulus-induced pro-inflammatory cytokine production in blood-derived monocyte-macrophages. Herein, we evaluate the beneficial effect of hyperbaric oxygen on transplanted AFS in a sciatic nerve injury model. Peripheral nerve injury was produced in Sprague-Dawley rats by crushing the left sciatic nerve using a vessel clamp. The AFS were embedded in fibrin glue and delivered to the injured site. Hyperbaric oxygen (100% oxygen, 2 ATA, 60 min/day) was administered 12 h after operation for seven consecutive days. Transplanted cell apoptosis, oxidative stress, inflammatory cell deposits and associated chemokines, pro-inflammatory cytokines, motor function, and nerve regeneration were evaluated 7 and 28 days after injury. Crush injury induced an inflammatory response, disrupted nerve integrity, and impaired nerve function in the sciatic nerve. However, crush injury-provoked inflammatory cytokines, deposits of inflammatory cytokines, and associated macrophage migration chemokines were attenuated in groups receiving hyperbaric oxygen but not in the AFS-only group. No significant increase in oxidative stress was observed after administration of HBO. In transplanted AFS, marked apoptosis was detected and this event was reduced by HBO treatment. Increased nerve myelination and improved motor function were observed in AFS-transplant, HBO-administrated, and AFS/HBO-combined treatment groups. Significantly, the AFS/HBO combined treatment showed the most beneficial effect. AFS in combination with HBO augment peripheral nerve regeneration, which may involve the suppression of apoptotic death in implanted AFS and the attenuation of an inflammatory response detrimental to peripheral nerve regeneration.

Connectivity of glass structure. Oxygen number

NASA Astrophysics Data System (ADS)

Medvedev, E. F.; Min'ko, N. I.

2018-03-01

With reference to mathematics, crystal chemistry and chemical technology of synthesis of glass structures in the solution (sol-gel technology), the paper is devoted to the study of the degree of connectivity of a silicon-oxygen backbone (fSi) and the oxygen number (R) [1]. It reveals logical contradictions and uncertainty of mathematical expressions of parameters, since fSi is not similar to the oxygen number. The connectivity of any structure is a result of various types of bonds: ion-covalent, donor-acceptor, hydrogen bonds, etc. Besides, alongside with SiO2, many glass compositions contain other glass-forming elements due to tetrahedral sites thus formed. The connectivity function of a glassy network with any set of glass-forming elements is roughly ensured by connectivity factor Y [2], which has monovalent elements loosening a glassy network. The paper considers the existence of various structural motives in hydrogen-impermeable glasses containing B2O3, Al2O3, PbO, Na2O, K2O and rare-earth elements. Hence, it also describes gradual nucleation, change of crystal forms, and structure consolidation in the process of substance intake from a matrix solution according to sol-gel technology. The crystal form varied from two-dimensional plates to three-dimensional and dendritical ones [3]. Alternative parameters, such as the oxygen number (O) and the structure connectivity factor (Y), were suggested. Functional dependence of Y=f(O) to forecast the generated structures was obtained for two- and multicomponent glass compositions.

Purification, crystallization and preliminary X-ray analysis of haemoglobin from ostrich (Struthio camelus).

PubMed

Sundaresan, S S; Ramesh, P; Sivakumar, K; Ponnuswamy, M N

2009-07-01

Haemoglobin is a tetrameric protein that carries oxygen from the lungs to tissues and carbon dioxide from tissues back to the lungs. The oxygen-binding properties of haemoglobin are regulated through the binding of allosteric effectors. The respiratory system of avian species is unique and complex in nature when compared with that of mammals. In avian species, inositol pentaphosphate (inositol-P(5)) is present in the erythrocytes of the adult and is thought to be the major factor responsible for the relatively high oxygen affinity of the whole blood. The ostrich (Struthio camelus) is a large flightless bird which contains inositol tetrakisphosphate (inositol-P(4)) in its erythrocytes and its whole blood oxygen affinity is higher. Efforts have been made to explore the structure-function relationship of ostrich haemoglobin. Ostrich haemoglobin was purified using ion-exchange chromatography. Haemoglobin crystals were grown by the hanging-drop vapour-diffusion method using PEG 3350 as the precipitant in 50 mM phosphate buffer pH 7.2. Data were collected using a MAR345 image-plate detector system. The crystals of ostrich haemoglobin diffracted to 2.2 A resolution. They belonged to the orthorhombic space group P2(1)2(1)2(1) with one whole biological molecule in the asymmetric unit; the unit-cell parameters were a = 80.93, b = 81.68, c = 102.05 A.

Genomics Review of Holocellulose Deconstruction by Aspergilli

PubMed Central

Segato, Fernando; Damásio, André R. L.; de Lucas, Rosymar C.; Squina, Fabio M.

2014-01-01

SUMMARY Biomass is constructed of dense recalcitrant polymeric materials: proteins, lignin, and holocellulose, a fraction constituting fibrous cellulose wrapped in hemicellulose-pectin. Bacteria and fungi are abundant in soil and forest floors, actively recycling biomass mainly by extracting sugars from holocellulose degradation. Here we review the genome-wide contents of seven Aspergillus species and unravel hundreds of gene models encoding holocellulose-degrading enzymes. Numerous apparent gene duplications followed functional evolution, grouping similar genes into smaller coherent functional families according to specialized structural features, domain organization, biochemical activity, and genus genome distribution. Aspergilli contain about 37 cellulase gene models, clustered in two mechanistic categories: 27 hydrolyze and 10 oxidize glycosidic bonds. Within the oxidative enzymes, we found two cellobiose dehydrogenases that produce oxygen radicals utilized by eight lytic polysaccharide monooxygenases that oxidize glycosidic linkages, breaking crystalline cellulose chains and making them accessible to hydrolytic enzymes. Among the hydrolases, six cellobiohydrolases with a tunnel-like structural fold embrace single crystalline cellulose chains and cooperate at nonreducing or reducing end termini, splitting off cellobiose. Five endoglucanases group into four structural families and interact randomly and internally with cellulose through an open cleft catalytic domain, and finally, seven extracellular β-glucosidases cleave cellobiose and related oligomers into glucose. Aspergilli contain, on average, 30 hemicellulase and 7 accessory gene models, distributed among 9 distinct functional categories: the backbone-attacking enzymes xylanase, mannosidase, arabinase, and xyloglucanase, the short-side-chain-removing enzymes xylan α-1,2-glucuronidase, arabinofuranosidase, and xylosidase, and the accessory enzymes acetyl xylan and feruloyl esterases. PMID:25428936

MOLECULAR OXYGEN AND THE ADSORPTION OF PHENOLS - EFFECT OF FUNCTIONAL GROUPS

EPA Science Inventory

This study reveals that the presence of molecular oxygen (oxic conditions) has a significant impact on the exhibited adsorptive capacity of granular activated carbon (GAC) for several phenolic compounds. The increase in the GAC adsorptive capacity under oxic conditions results f...

Impedimetric investigation of dual electrical properties of reduced graphene-oxide-based biosensors in the detection of dopamine.

PubMed

Shu-Ping Lin; Jhong-Yi Ciou; Tung-Yen Lai; Tsung-Wu Lin

2017-07-01

Because of the properties of high charge mobility, large detection area and chemical stability of graphene, it has been applied in many biomedical applications. Graphene oxide (GO) with abundant oxygenated functional groups is easily to form an aqueous suspension by sonication. Here, the exposed areas on the patterned-circuit silicon-based chips were first modified by (3-aminopropyl) trimethoxysilane (APTMS) for later chemically immobilized GO. After that, solution-based reduction process using hydrazine was used to gain reduced GO (RGO)-based biosensors. ESCA survey spectra showed oxygen-containing functional groups of GO decreased from 47% to 5.7%, 4.1%, 3.8%, and 3.6% under varied reduction times of 30 min, 40 min, 50 min, and 60 min, respectively. D/G intensity ratio (I D /I G ) in Raman spectra showed 1.03 after 60-min reduction process. The 60-min reduction process was further used in the electrical sensing experiments. Since different deposited layers of graphene were obtained in our experimental processes, 60-min-RGO-based biosensors have been found that those immobilized RGO possessed semiconductive property as the layers are less than 11. By contrary, when the layers were above 11, the immobilized RGO would resemble metallic material. In addition, the impedimetric analyses indicated obvious signal responses above 86 kHz and showed a concentration-dependent trend in dopamine sensing in physiological phosphate buffered saline (PBS) using 60-min-RGO-based biosensors which were feature of semiconductor.

Antioxidant Chemistry of Graphene-Based Materials and its Role in Oxidation Protection Technology

PubMed Central

Qiu, Yang; Wang, Zhongying; Owens, Alisa C.E.; Kulaots, Indrek; Chen, Yantao; Kane, Agnes B.; Hurt, Robert H.

2015-01-01

Two-dimensional nanomaterials have potential as a new class of antioxidants that combine physical barrier function with ultrahigh surface area for free radical scavenging. This work presents the first measurements of the chemical reactivities of graphene-based materials toward a set of model free radicals and reactive oxygen species using electron paramagnetic resonance spectroscopy (EPR) and sacrificial dye protection assays. Graphene-based materials are shown to protect a variety of molecular targets from oxidation by these species, and to be highly effective as hydroxyl-radical scavengers. When hydroxyl radical is produced photolytically, the overall antioxidant effect is a combination of preventative antioxidant activity (UV absorption) and ·OH radical scavenging. Few-layer graphene is more active than monolayer graphene oxide, despite its lower surface area, which indicates that the primary scavenging sites are associated with the sp2-carbon network rather than oxygen-containing functional groups. To explain this trend, we propose that GO is a weak hydrogen donor, due to the non-phenolic nature of most OH groups on GO, which reside at basal sp3-carbon sites that do not allow for radical resonance stabilization following hydrogen donation. As an example application of graphene antioxidant behavior, we show that encapsulation of TiO2 nanoparticles in graphene nanosacks reduces undesired photo-oxidative damage to nearby organic target molecules, which suggests graphene encapsulation as a new approach to managing adverse environmental or health impacts of redox-active nanomaterials. PMID:25157875

Molecular simulation insights on the in vacuo adsorption of amino acids on graphene oxide surfaces with varying surface oxygen densities

NASA Astrophysics Data System (ADS)

Rahmani, Farzin; Nouranian, Sasan; Mahdavi, Mina; Al-Ostaz, Ahmed

2016-11-01

In this fundamental study, a series of molecular dynamics simulations were performed in vacuo to investigate the energetics and select geometries of 20 standard amino acids (AAs) on pristine graphene (PG) and graphene oxide (GO) surfaces as a function of graphene surface oxygen density. These interactions are of key interest to graphene/biomolecular systems. Our results indicate that aromatic AAs exhibit the strongest total interactions with the PG surfaces due to π-π stacking. Tryptophan (Trp) has the highest aromaticity due to its indole side chain and, hence, has the strongest interaction among all AAs (-16.66 kcal/mol). Aliphatic, polar, and charged AAs show various levels of affinity to the PG sheets depending on the strength of their side chain hydrophobic interactions. For example, arginine (Arg) with its guanidinium side chain exhibits the strongest interaction with the PG sheets (-13.81 kcal/mol) following aromatic AAs. Also, glycine (Gly; a polar AA) has the weakest interaction with the PG sheets (-7.29 kcal/mol). When oxygen-containing functional groups are added to the graphene sheets, the π-π stacking in aromatic AAs becomes disrupted and perfect parallelism of the aromatic rings is lost. Moreover, hydrogen bonding and/or electrostatic interactions become more pronounced. Charged AAs exhibit the strongest interactions with the GO surfaces. In general, the AA-GO interactions increase with increasing surface oxygen density, and the effect is more pronounced at higher O/C ratios. This study provides a quantitative measure of AA-graphene interactions for the design and tuning of biomolecular systems suitable for biosensing, drug delivery, and gene delivery applications.

IMPORTANCE OF ACTIVATED CARBON'S OXYGEN SURFACE FUNCTIONAL GROUPS ON ELEMENTAL MERCURY ADSORPTION

EPA Science Inventory

The effect of varying physical and chemical properties of activated carbons on adsorption of elemental mercury [Hg(0)] was studied by treating two activated carbons to modify their surface functional groups and pore structures. Heat treatment (1200 K) in nitrogen (N2), air oxidat...

Modifying optical properties of reduced/graphene oxide with controlled ozone and thermal treatment in aqueous suspensions.

PubMed

Hasan, Md Tanvir; Senger, Brian J; Mulford, Price; Ryan, Conor; Doan, Hung; Gryczynski, Zygmunt; Naumov, Anton V

2017-02-10

Graphene possesses a number of advantageous properties, however, does not exhibit optical emission, which limits its use in optoelectronics. Unlike graphene, its functional derivative, graphene oxide (GO) exhibits fluorescence emission throughout the visible. Here, we focus on controlled methods for tuning the optical properties of GO. We introduce ozone treatment of reduced graphene oxide (RGO) in order to controllably transform it from non-emissive graphene-like material into GO with a specific fluorescence emission response. Solution-based treatment of RGO for 5-45 min with ∼1.2 g l -1 ozone/oxygen gas mixture yields a drastic color change, bleaching of the absorption in the visible and the stepwise increase in fluorescence intensity and lifetime. This is attributed to the introduction of oxygen-containing functional groups to RGO graphitic platform as detected by the infrared spectroscopy. A reverse process: controllable quenching of this fluorescence is achieved by the thermal treatment of GO in aqueous suspension up to 90 °C. This methodology allows for the wide range alteration of GO optical properties starting from the dark-colored non-emissive RGO material up to nearly transparent highly ozone-oxidized GO showing substantial fluorescence emission. The size of the GO flakes is concomitantly altered by oxidation-induced scission. Semi-empirical PM3 theoretical calculations on HyperChem models are utilized to explore the origins of optical response from GO. Two models are considered, attributing the induced emission either to the localized states produced by oxygen-containing addends or the islands of graphitic carbon enclosed by such addends. Band gap values calculated from the models are in the agreement with experimentally observed transition peak maxima. The controllable variation of GO optical properties in aqueous suspension by ozone and thermal treatments shown in this work provides a route to tune its optical response for particular optoelectronics or biomedical applications.

Modifying optical properties of reduced/graphene oxide with controlled ozone and thermal treatment in aqueous suspensions

NASA Astrophysics Data System (ADS)

Tanvir Hasan, Md; Senger, Brian J.; Mulford, Price; Ryan, Conor; Doan, Hung; Gryczynski, Zygmunt; Naumov, Anton V.

2017-02-01

Graphene possesses a number of advantageous properties, however, does not exhibit optical emission, which limits its use in optoelectronics. Unlike graphene, its functional derivative, graphene oxide (GO) exhibits fluorescence emission throughout the visible. Here, we focus on controlled methods for tuning the optical properties of GO. We introduce ozone treatment of reduced graphene oxide (RGO) in order to controllably transform it from non-emissive graphene-like material into GO with a specific fluorescence emission response. Solution-based treatment of RGO for 5-45 min with ˜1.2 g l-1 ozone/oxygen gas mixture yields a drastic color change, bleaching of the absorption in the visible and the stepwise increase in fluorescence intensity and lifetime. This is attributed to the introduction of oxygen-containing functional groups to RGO graphitic platform as detected by the infrared spectroscopy. A reverse process: controllable quenching of this fluorescence is achieved by the thermal treatment of GO in aqueous suspension up to 90 °C. This methodology allows for the wide range alteration of GO optical properties starting from the dark-colored non-emissive RGO material up to nearly transparent highly ozone-oxidized GO showing substantial fluorescence emission. The size of the GO flakes is concomitantly altered by oxidation-induced scission. Semi-empirical PM3 theoretical calculations on HyperChem models are utilized to explore the origins of optical response from GO. Two models are considered, attributing the induced emission either to the localized states produced by oxygen-containing addends or the islands of graphitic carbon enclosed by such addends. Band gap values calculated from the models are in the agreement with experimentally observed transition peak maxima. The controllable variation of GO optical properties in aqueous suspension by ozone and thermal treatments shown in this work provides a route to tune its optical response for particular optoelectronics or biomedical applications.

Effects of a preemptive alveolar recruitment strategy on arterial oxygenation during one-lung ventilation with different tidal volumes in patients with normal pulmonary function test.

PubMed

Jung, Jong Dal; Kim, Sang Hun; Yu, Byung Sik; Kim, Hye Ji

2014-08-01

Hypoxemia during one-lung ventilation (OLV) remains a major concern. The present study compared the effect of alveolar recruitment strategy (ARS) on arterial oxygenation during OLV at varying tidal volumes (Vt) with or without positive end-expiratory pressure (PEEP). In total, 120 patients undergoing wedge resection by video assisted thoracostomy were randomized into four groups comprising 30 patients each: those administered a 10 ml/kg tidal volume with or without preemptive ARS (Group H and Group H-ARS, respectively) and those administered a 6 ml/kg tidal volume and a 8 cmH2O PEEP with or without preemptive ARS (Group L and Group L-ARS, respectively). ARS was performed using pressure-controlled ventilation with a 40 cmH2O plateau airway pressure and a 15 cmH2O PEEP for at least 10 breaths until OLV began. Preemptive ARS significantly improved the PaO2/FiO2 ratio compared to the groups that did not receive ARS (P < 0.05). The H-ARS group showed a highest PaO2/FiO2 ratio during OLV, the L-ARS and H groups showed similarly improved arterial oxygenation, which was significantly higher than in group L (P < 0.05). The plateau airway pressure in group H-ARS was significantly higher than in group L-ARS (P < 0.05). Preemptive ARS can improve arterial oxygenation during OLV. Furthermore, a 6 ml/kg tidal volume combined with 8 cmH2O PEEP after preemptive ARS may reduce the risk of pulmonary injury caused by high tidal volume during one-lung ventilation in patients with normal pulmonary function.

Prevention of ischemia-reperfusion lung injury during static cold preservation by supplementation of standard preservation solution with HEMO2life® in pig lung transplantation model.

PubMed

Glorion, M; Polard, V; Favereau, F; Hauet, T; Zal, F; Fadel, E; Sage, E

2017-10-25

We describe the results of adding a new biological agent HEMO 2 life ® to a standard preservation solution for hypothermic static lung preservation aiming to improve early functional parameters after lung transplantation. HEMO 2 life ® is a natural oxygen carrier extracted from Arenicola marina with high oxygen affinity developed as an additive to standard organ preservation solutions. Standard preservation solution (Perfadex ® ) was compared with Perfadex ® associated with HEMO 2 life ® and with sham animals after 24 h of hypothermic preservation followed by lung transplantation. During five hours of lung reperfusion, functional parameters and biomarkers expression in serum and in bronchoalveolar lavage fluid (BALF) were measured. After five hours of reperfusion, HEMO 2 life ® group led to significant improvement in functional parameters: reduction of graft vascular resistance (p < .05) and increase in graft oxygenation ratio (p < .05). Several ischemia-reperfusion related biomarkers showed positive trends in the HEMO 2 life ® group: expression of HMG B1 in serum tended to be lower in comparison (2.1 ± 0.8 vs. 4.6 ± 1.5) with Perfadex ® group, TNF-α and IL-8 in BALF were significantly higher in the two experimental groups compared to control (p < .05). During cold ischemia, expression of HIF1α and histology remained unchanged and similar to control. Supplementation of the Perfadex ® solution by an innovative oxygen carrier HEMO 2 life ® during hypothermic static preservation improves early graft function after prolonged cold ischemia in lung transplantation.

Normal Muscle Oxygen Consumption and Fatigability in Sickle Cell Patients Despite Reduced Microvascular Oxygenation and Hemorheological Abnormalities

PubMed Central

Waltz, Xavier; Pichon, Aurélien; Lemonne, Nathalie; Mougenel, Danièle; Lalanne-Mistrih, Marie-Laure; Lamarre, Yann; Tarer, Vanessa; Tressières, Benoit; Etienne-Julan, Maryse; Hardy-Dessources, Marie-Dominique; Hue, Olivier; Connes, Philippe

2012-01-01

Background/Aim Although it has been hypothesized that muscle metabolism and fatigability could be impaired in sickle cell patients, no study has addressed this issue. Methods We compared muscle metabolism and function (muscle microvascular oxygenation, microvascular blood flow, muscle oxygen consumption and muscle microvascular oxygenation variability, which reflects vasomotion activity, maximal muscle force and local muscle fatigability) and the hemorheological profile at rest between 16 healthy subjects (AA), 20 sickle cell-hemoglobin C disease (SC) patients and 16 sickle cell anemia (SS) patients. Results Muscle microvascular oxygenation was reduced in SS patients compared to the SC and AA groups and this reduction was not related to hemorhelogical abnormalities. No difference was observed between the three groups for oxygen consumption and vasomotion activity. Muscle microvascular blood flow was higher in SS patients compared to the AA group, and tended to be higher compared to the SC group. Multivariate analysis revealed that muscle oxygen consumption was independently associated with muscle microvascular blood flow in the two sickle cell groups (SC and SS). Finally, despite reduced muscle force in sickle cell patients, their local muscle fatigability was similar to that of the healthy subjects. Conclusions Sickle cell patients have normal resting muscle oxygen consumption and fatigability despite hemorheological alterations and, for SS patients only, reduced muscle microvascular oxygenation and increased microvascular blood flow. Two alternative mechanisms can be proposed for SS patients: 1) the increased muscle microvascular blood flow is a way to compensate for the lower muscle microvascular oxygenation to maintain muscle oxygen consumption to normal values or 2) the reduced microvascular oxygenation coupled with a normal resting muscle oxygen consumption could indicate that there is slight hypoxia within the muscle which is not sufficient to limit mitochondrial respiration but increases muscle microvascular blood flow. PMID:23285055

Right heart function during simulated altitude in patients with pulmonary arterial hypertension

PubMed Central

Seccombe, Leigh M; Chow, Vincent; Zhao, Wei; Lau, Edmund M T; Rogers, Peter G; Ng, Austin C C; Veitch, Elizabeth M; Peters, Matthew J; Kritharides, Leonard

2017-01-01

Objective Patients with pulmonary arterial hypertension (PAH) are often recommended supplemental oxygen for altitude travel due to the possible deleterious effects of hypoxia on pulmonary haemodynamics and right heart function. This includes commercial aircraft travel; however, the direct effects and potential risks are unknown. Methods Doppler echocardiography and gas exchange measures were investigated in group 1 patients with PAH and healthy patients at rest breathing room air and while breathing 15.1% oxygen, at rest for 20 min and during mild exertion. Results The 14 patients with PAH studied were clinically stable on PAH-specific therapy, with functional class II (n=11) and III (n=3) symptoms when tested. Measures of right ventricular size and function were significantly different in the PAH group at baseline as compared to 7 healthy patients (p<0.04). There was no evidence of progressive right ventricular deterioration during hypoxia at rest or under exertion. Pulmonary arterial systolic pressure (PASP) increased in both groups during hypoxia (p<0.01). PASP in hypoxia correlated strongly with baseline PASP (p<0.01). Pressure of arterial oxygen correlated with PASP in hypoxia (p<0.03) but not at baseline, with three patients with PAH experiencing significant desaturation. The duration and extent of hypoxia in this study was tolerated well despite a mild increase in symptoms of breathlessness (p<0.01). Conclusions Non-invasive measures of right heart function in group 1 patients with PAH on vasodilator treatment demonstrated a predictable rise in PASP during short-term simulated hypoxia that was not associated with a deterioration in right heart function. PMID:28123765

Surface Chemical Conversion of Organosilane Self-Assembled Monolayers with Active Oxygen Species Generated by Vacuum Ultraviolet Irradiation of Atmospheric Oxygen Molecules

NASA Astrophysics Data System (ADS)

Kim, Young-Jong; Lee, Kyung-Hwang; Sano, Hikaru; Han, Jiwon; Ichii, Takashi; Murase, Kuniaki; Sugimura, Hiroyuki

2008-01-01

The chemical conversion of the top surface of n-octadecyltrimethoxy silane self-assembled monolayers (ODS-SAMs) on oxide-covered Si substrates using active oxygen species generated from atmospheric oxygen molecules irradiated with vacuum ultraviolet (VUV) light at 172 nm in wavelength has been studied on the basis of water contact angle measurements, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy. An ODS-SAM whose water contact angle was 104° on average was prepared using chemical vapor deposition with substrate and vapor temperatures of 150 °C. The VUV treatment of an ODS-SAM sample was carried out by placing the sample in air and then irradiating the sample surface with a Xe-excimer lamp. The distance between the lamp and the sample was regulated so that the VUV light emitted from the lamp was almost entirely absorbed by atmospheric oxygen molecules to generate active oxygen species, such as ozone and atomic oxygen before reaching the sample surface. Hence, the surface chemical conversion of the ODS-SAM was primarily promoted through chemical reactions with the active oxygen species. Photochemical changes in the ODS-SAM were found to be the generation of polar functional groups, such as -COOH, -CHO, and -OH, on the surface and the subsequent etching of the monolayer. Irradiation parameters, such as irradiation time, were optimized to achieve a better functionalization of the SAM top surface while minimizing the etching depth of the ODS-SAM. The ability to graft another SAM onto the modified ODS-SAM bearing polar functional groups was demonstrated by the formation of alkylsilane bilayers.

Metal-air cells comprising collapsible foam members and means for minimizing internal pressure buildup

NASA Technical Reports Server (NTRS)

Putt, Ronald A. (Inventor); Woodruff, Glenn (Inventor)

1994-01-01

This invention provides a prismatic zinc-air cell including, in general, a prismatic container having therein an air cathode, a separator and a zinc anode. The container has one or more oxygen access openings, and the air cathode is disposed in the container in gaseous communication with the oxygen access openings so as to allow access of oxygen to the cathode. The separator has a first side in electrolytic communication with the air cathode and a second side in electrolytic communication with the zinc anode. The separator isolates the cathode and the zinc anode from direct electrical contact and allows passage of electrolyte therebetween. An expansion chamber adjacent to the zinc anode is provided which accommodates expansion of the zinc anode during discharge of the cell. A suitable collapsible foam member generally occupies the expansion space, providing sufficient resistance tending to oppose movement of the zinc anode away from the separator while collapsing upon expansion of the zinc anode during discharge of the cell. One or more vent openings disposed in the container are in gaseous communication with the expansion space, functioning to satisfactorily minimize the pressure buildup within the container by venting gasses expelled as the foam collapses during cell discharge.

Geoarchaeota: a new candidate phylum in the Archaea from high-temperature acidic iron mats in Yellowstone National Park

PubMed Central

Kozubal, Mark A; Romine, Margaret; Jennings, Ryan deM; Jay, Zack J; Tringe, Susannah G; Rusch, Doug B; Beam, Jacob P; McCue, Lee Ann; Inskeep, William P

2013-01-01

Geothermal systems in Yellowstone National Park (YNP) provide an outstanding opportunity to understand the origin and evolution of metabolic processes necessary for life in extreme environments including low pH, high temperature, low oxygen and elevated concentrations of reduced iron. Previous phylogenetic studies of acidic ferric iron mats from YNP have revealed considerable diversity of uncultivated and undescribed archaea. The goal of this study was to obtain replicate de novo genome assemblies for a dominant archaeal population inhabiting acidic iron-oxide mats in YNP. Detailed analysis of conserved ribosomal and informational processing genes indicates that the replicate assemblies represent a new candidate phylum within the domain Archaea referred to here as ‘Geoarchaeota' or ‘novel archaeal group 1 (NAG1)'. The NAG1 organisms contain pathways necessary for the catabolism of peptides and complex carbohydrates as well as a bacterial-like Form I carbon monoxide dehydrogenase complex likely used for energy conservation. Moreover, this novel population contains genes involved in the metabolism of oxygen including a Type A heme copper oxidase, a bd-type terminal oxidase and a putative oxygen-sensing protoglobin. NAG1 has a variety of unique bacterial-like cofactor biosynthesis and transport genes and a Type3-like CRISPR system. Discovery of NAG1 is critical to our understanding of microbial community structure and function in extant thermophilic iron-oxide mats of YNP, and will provide insight regarding the evolution of Archaea in early Earth environments that may have important analogs active in YNP today. PMID:23151644

Reduced global brain metabolism but maintained vascular function in amnestic mild cognitive impairment.

PubMed

Thomas, Binu P; Sheng, Min; Tseng, Benjamin Y; Tarumi, Takashi; Martin-Cook, Kristen; Womack, Kyle B; Cullum, Munro C; Levine, Benjamin D; Zhang, Rong; Lu, Hanzhang

2017-04-01

Amnestic mild cognitive impairment represents an early stage of Alzheimer's disease, and characterization of physiological alterations in mild cognitive impairment is an important step toward accurate diagnosis and intervention of this condition. To investigate the extent of neurodegeneration in patients with mild cognitive impairment, whole-brain cerebral metabolic rate of oxygen in absolute units of µmol O 2 /min/100 g was quantified in 44 amnestic mild cognitive impairment and 28 elderly controls using a novel, non-invasive magnetic resonance imaging method. We found a 12.9% reduction ( p = 0.004) in cerebral metabolic rate of oxygen in mild cognitive impairment, which was primarily attributed to a reduction in the oxygen extraction fraction, by 10% ( p = 0.016). Global cerebral blood flow was not found to be different between groups. Another aspect of vascular function, cerebrovascular reactivity, was measured by CO 2 -inhalation magnetic resonance imaging and was found to be equivalent between groups. Therefore, there seems to be a global, diffuse diminishment in neural function in mild cognitive impairment, while their vascular function did not show a significant reduction.

Triiodothyronine activates lactate oxidation without impairing fatty acid oxidation and improves weaning from extracorporeal membrane oxygenation.

PubMed

Kajimoto, Masaki; Ledee, Dolena R; Xu, Chun; Kajimoto, Hidemi; Isern, Nancy G; Portman, Michael A

2014-01-01

Extracorporeal membrane oxygenation (ECMO) provides a rescue for children with severe cardiac failure. It has previously been shown that triiodothyronine (T3) improves cardiac function by modulating pyruvate oxidation during weaning. This study focused on fatty acid (FA) metabolism modulated by T3 for weaning from ECMO after cardiac injury. METHODS AND RESULTS: Nineteen immature piglets (9.1-15.3 kg) were separated into 3 groups with ECMO (6.5 h) and wean: normal circulation (Group-C); transient coronary occlusion (10 min) for ischemia-reperfusion (IR) followed by ECMO (Group-IR); and IR with T3 supplementation (Group-IR-T3). 13-Carbon ((13)C)-labeled lactate, medium-chain and long-chain FAs, was infused as oxidative substrates. Substrate fractional contribution (FC) to the citric acid cycle was analyzed by(13)C-nuclear magnetic resonance. ECMO depressed circulating T3 levels to 40% of the baseline at 4 h and were restored in Group-IR-T3. Group-IR decreased cardiac power, which was not fully restorable and 2 pigs were lost because of weaning failure. Group-IR also depressed FC-lactate, while the excellent contractile function and energy efficiency in Group-IR-T3 occurred along with a marked FC-lactate increase and [adenosine triphosphate]/[adenosine diphosphate] without either decreasing FC-FAs or elevating myocardial oxygen consumption over Group-C or -IR. T3 releases inhibition of lactate oxidation following IR injury without impairing FA oxidation. These findings indicate that T3 depression during ECMO is maladaptive, and that restoring levels improves metabolic flux and enhances contractile function during weaning.

Effect of cefodizime and ceftriaxone on phagocytic function in patients with severe infections.

PubMed Central

Wenisch, C; Parschalk, B; Hasenhündl, M; Wiesinger, E; Graninger, W

1995-01-01

Thirty patients with severe bacterial infections were treated with 50 mg of cefodizime per kg of body weight once daily or 50 mg of ceftriaxone per kg once daily for 10 +/- 3 days. The effect of cefodizime and ceftriaxone on the phagocytic capacity and generation of reactive oxygen intermediates after phagocytosis by granulocytes was assessed prior to, during, and after therapy. Flow cytometry was used to study phagocytic capacity by measuring the uptake of fluorescein-labeled bacteria. The generation of reactive oxygen intermediates after phagocytosis was estimated by the quantification of the intracellular conversion of dihydrorhodamine 123 to rhodamine 123. Prior to therapy, patients in both groups exhibited a decreased capacity to phagocytize Escherichia coli and subsequently to generate reactive oxygen intermediates. Granulocyte function increased after the initiation of therapy and normalized within 7 days for the ceftriaxone-treated patients and within 3 days for the cefodizime group (P < 0.05). In the cefodizime group, an enhancement of phagocytic capacity was observed 14 days after the initiation of therapy (P < 0.05). Prior to therapy, phagocytic capacity was significantly correlated with the generation of reactive oxygen products (r = 0.674 and P < 0.005). PMID:7793871

Ex vivo rehabilitation of non-heart-beating donor lungs in preclinical porcine model: delayed perfusion results in superior lung function.

PubMed

Mulloy, Daniel P; Stone, Matthew L; Crosby, Ivan K; Lapar, Damien J; Sharma, Ashish K; Webb, David V; Lau, Christine L; Laubach, Victor E; Kron, Irving L

2012-11-01

Ex vivo lung perfusion (EVLP) is a promising modality for the evaluation and treatment of marginal donor lungs. The optimal timing of EVLP initiation and the potential for rehabilitation of donor lungs with extended warm ischemic times is unknown. The present study compared the efficacy of different treatment strategies for uncontrolled non-heart-beating donor lungs. Mature swine underwent hypoxic arrest, followed by 60 minutes of no-touch warm ischemia. The lungs were harvested and flushed with 4°C Perfadex. Three groups (n = 5/group) were stratified according to the preservation method: cold static preservation (CSP; 4 hours of 4°C storage), immediate EVLP (I-EVLP: 4 hours EVLP at 37°C), and delayed EVLP (D-EVLP; 4 hours of CSP followed by 4 hours of EVLP). The EVLP groups were perfused with Steen solution supplemented with heparin, methylprednisolone, cefazolin, and an adenosine 2A receptor agonist. The lungs then underwent allotransplantation and 4 hours of recipient reperfusion before allograft assessment for resultant ischemia-reperfusion injury. The donor blood oxygenation (partial pressure of oxygen/fraction of inspired oxygen ratio) before death was not different between the groups. The oxygenation after transplantation was significantly greater in the D-EVLP group than in the I-EVLP or CSP groups. The mean airway pressure, pulmonary artery pressure, and expression of interleukin-8, interleukin-1β, and tumor necrosis factor-α were all significantly reduced in the D-EVLP group. Post-transplant oxygenation exceeded the acceptable clinical levels only in the D-EVLP group. Uncontrolled non-heart-beating donor lungs with extended warm ischemia can be reconditioned for successful transplantation. The combination of CSP and EVLP in the D-EVLP group was necessary to obtain optimal post-transplant function. This finding, if confirmed clinically, will allow expanded use of nonheart-beating donor lungs. Copyright © 2012 The American Association for Thoracic Surgery. Published by Mosby, Inc. All rights reserved.

Vibrational Excitations and Low Energy Electronic Structure of Epoxide-decorated Graphene.

PubMed

Mattson, E C; Johns, J E; Pande, K; Bosch, R A; Cui, S; Gajdardziska-Josifovska, M; Weinert, M; Chen, J H; Hersam, M C; Hirschmugl, C J

2014-01-02

We report infrared studies of adsorbed atomic oxygen (epoxide functional groups) on graphene. Two different systems are used as a platform to explore these interactions, namely, epitaxial graphene/SiC(0001) functionalized with atomic oxygen (graphene epoxide, GE) and chemically reduced graphene oxide (RGO). In the case of the model GE system, IR reflectivity measurements show that epoxide groups distort the graphene π bands around the K-point, imparting a finite effective mass and contributing to a band gap. In the case of RGO, epoxide groups are found to be present following the reduction treatment by a combination of polarized IR reflectance and transmittance measurements. Similar to the GE system, a band gap in the RGO sample is observed as well.

Vibrational Excitations and Low Energy Electronic Structure of Epoxide-decorated Graphene

PubMed Central

Mattson, E.C.; Johns, J.E.; Pande, K.; Bosch, R.A.; Cui, S.; Gajdardziska-Josifovska, M.; Weinert, M.; Chen, J.H.; Hersam, M.C.; Hirschmugl, C.J.

2014-01-01

We report infrared studies of adsorbed atomic oxygen (epoxide functional groups) on graphene. Two different systems are used as a platform to explore these interactions, namely, epitaxial graphene/SiC(0001) functionalized with atomic oxygen (graphene epoxide, GE) and chemically reduced graphene oxide (RGO). In the case of the model GE system, IR reflectivity measurements show that epoxide groups distort the graphene π bands around the K-point, imparting a finite effective mass and contributing to a band gap. In the case of RGO, epoxide groups are found to be present following the reduction treatment by a combination of polarized IR reflectance and transmittance measurements. Similar to the GE system, a band gap in the RGO sample is observed as well. PMID:24563725

Surface Functionalization of WO3 Thin Films with (3-Aminopropyl)triethoxysilane and Succinic Anhydride

NASA Astrophysics Data System (ADS)

Ta, Thi Kieu Hanh; Tran, Thi Nhu Hoa; Tran, Quang Minh Nhat; Pham, Duy Phong; Pham, Kim Ngoc; Cao, Thi Thanh; Kim, Yong Soo; Tran, Dai Lam; Ju, Heongkyu; Phan, Bach Thang

2017-06-01

We report effects of oxygen plasma treatment on the surface functionalization of WO3 thin films with (3-aminopropyl)triethoxysilane (APTES) and succinic anhydride (SA). X-ray diffraction and x-ray photoelectron spectroscopy results indicate the existence of the WO3 phase. Fourier transform infrared spectroscopy measurement shows clear bands at 1040 cm-1 (Si-O-Si), 1556 cm-1 (N-H), 1655 cm-1 (C=O), 2937 cm-1 (C-H) and 3298 cm-1 (N-H), confirming the surface functionalization efficiency enhanced by prior treatment of oxygen plasma. It thus follows that the prior oxygen plasma treatment activates hydroxylation with more -OH groups on the WO3 surface, which can pave a highly efficient way to the surface functionalization by APTES and SA.

A theoretical and experimental study on the molecular and electronic structures of artemisinin and related drug molecules

NASA Astrophysics Data System (ADS)

Galasso, V.; Kovač, B.; Modelli, A.

2007-06-01

The equilibrium structures of artemisinin and a selection of its derivatives (potent antimalarial drugs) have been studied with the density functional theory ansatz B3LYP. Of the five rings of the artemisinin framework, it is only the pyranose ring B that exhibits a marked conformational flexibility, especially on addition of a pendant side chain at C-10. For the derivatives, the β isomer with the axial substituent group is found to be energetically more stable than the α isomer with the equatorial group. The assignment of the vibrational fundamentals has been supported by calculations on related model molecules and a normal coordinate analysis. This allows for a reliable characterization of the normal modes, mainly involving the peroxide linkage, in the claimed fingerprint region of 1,2,4-trioxanes. The electronic structures have also been studied by measuring and calculating significant features of the NMR, photoelectron and electron transmission spectra. In particular, a representative set of NMR chemical shifts and nuclear spin-spin coupling constants, obtained with DFT formalisms, compares favourably with experiment and fits expectation in terms of stereoelectronic effects of the vicinal oxygen lone pairs. Based on ab initio outer valence Green's function calculations, a consistent interpretation of the uppermost bands in the photoelectron spectra of artemisinin and derivatives has been advanced. The top ionization energies reflect a complex interaction of the various oxygen lone pair orbitals. Electron transmission spectroscopy is applied for the first time to compounds containing the peroxide bond and elucidates the empty level electronic structure of artemisinin and derivatives in the 0-6 eV energy range, with the support of MO calculations and comparison with the spectra of reference molecules. Electron attachment to the lowest-lying empty σ∗ MO, mainly localized on the O-O bridge, occurs at an energy (1.7 eV) exceptionally low for compounds not containing third-row or heavier elements.

Oxidation-induced water-solubilization and chemical functionalization of fullerenes C60, Gd@C60 and Gd@C82: atomistic insights into the formation mechanisms and structures of fullerenols synthesized by different methods.

PubMed

Wang, Zhenzhen; Lu, Zhanghui; Zhao, Yuliang; Gao, Xingfa

2015-02-21

Water-solubilization is the prerequisite to endow the pristinely hydrophobic fullerenes with biocompatibility and biofunctionality, which has been widely applied to derive fullerene-based nanomaterials for biomedical applications. Oxidation reactions using O2 and H2O2 are the most commonly used approaches to this end, through which fullerenols with different structural features can be obtained. Despite the progress in the syntheses and bioapplications of fullerenols, their formation mechanisms and structures at the atomic level, which substantialize their physical properties and biofunctions, have been little understood. Using density functional theory calculations, we comparatively study the mechanisms and product structures for the oxidations of C60, Gd@C60 and Gd@C82 using both O2 and H2O2 as oxidizing agents under both neutral and alkaline aqueous conditions. We predict the formation mechanisms and product structures corresponding to the different synthetic conditions. Briefly, the H2O2 oxidations of C60, Gd@C60 and Gd@C82 under neutral conditions do not occur readily at room temperature because of the high energy barriers, whereas the H2O2 oxidations can readily proceed under alkaline conditions. The oxygen-containing groups of the fullerenols obtained under these conditions include hydroxyl, carbonyl, hemiacetal and deprotonated vic-diol. In contrast, through O2 oxidation under alkaline conditions, the most probable oxygen-containing groups for C60 fullerenols are epoxide and deprotonated vic-diol, and those for Gd@C60 and Gd@C82 fullerenols are hydroxyls and carbonyls. The results explain a wide range of experimental findings reported before. More importantly, they provide atomistic-level insights into the formation mechanisms and structures for various fullerenols, which are of fundamental interest for understanding their biomedical applications in the future.

Controllably Inducing and Modeling Optical Response from Graphene Oxide

NASA Astrophysics Data System (ADS)

Lombardo, Nicholas; Naumov, Anton

Graphene, a novel 2-dimensional sp2-hybridized allotrope of Carbon, has unique electrical and mechanical properties. While it is naturally a highly conductive zero band gap semiconductor, graphene does not exhibit optical emission. It has been shown that functionalization with oxygen-containing groups elicits an opening of band gap in graphene. In this work, we aim to induce an optical response in graphene via controlled oxidation, and then explore potential origins of its photoluminescence through mathematical modeling. We employ timed ozone treatment of initially non-fluorescent reduced graphene oxide (RGO) to produce graphene oxide (GO) with specific optical properties. Oxidized material exhibits substantial changes in the absorption spectra and a broad photoluminescence feature, centered at 532 nm, which suggests the appearance of a band gap. We then explore a number of possible mechanisms for the origin of GO photoluminescence via PM3 and ab initio calculations on a functionalized single sheet of graphene. By adjusting modeling parameters to fit experimentally obtained optical transition energies we estimate the size of the sp2 graphitic regions in GO and the arrangement of functional groups that could be responsible for the observed emission.

PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells.

PubMed

Cui, Zhiming; Li, Chang Ming; Jiang, San Ping

2011-09-28

A simple self-assembly approach has been developed to functionalize carbon nanotubes (CNTs) with chitosan (CS) and heteropolyacids (HPAs) of phosphomolybdic acid (H(3)PMo(12)O(40), HPMo) and phosphotungstic acid (H(3)PW(12)O(40), HPW). The non-covalent functionalization method, which introduces homogenous surface functional groups with no detrimental effect on graphene structures of CNTs, can be carried out at room temperature without the use of corrosive acids. The PtRu nanoparticles supported on HPAs-CS-CNTs have a uniform distribution and much smaller size as compared to those of the PtRu nanoparticles supported on conventional acid treated CNTs (PtRu/AO-CNTs). The onset and peak potentials for CO(ad) oxidation on PtRu/HPAs-CS-CNTs catalysts are more negative than those on PtRu/AO-CNTs, indicating that HPAs facilitate the electro-oxidation of CO. The PtRu/HPMo-CS-CNTs catalyst has a higher electrocatalytic activity for methanol oxidation and higher tolerance toward CO poisoning than PtRu/HPW-CS-CNTs. The better electrocatalytic enhancement of HPMo on the PtRu/HPAs-CS-CNTs catalyst is most likely related to the fact that molybdenum-containing HPAs such as HPMo have more labile terminal oxygen to provide additional active oxygen sites while accelerating the CO and methanol oxidation in a similar way to that of Ru in the PtRu binary alloy system.

Interplay between Oxygen and Fe–S Cluster Biogenesis: Insights from the Suf Pathway

PubMed Central

2015-01-01

Iron–sulfur (Fe–S) cluster metalloproteins conduct essential functions in nearly all contemporary forms of life. The nearly ubiquitous presence of Fe–S clusters and the fundamental requirement for Fe–S clusters in both aerobic and anaerobic Archaea, Bacteria, and Eukarya suggest that these clusters were likely integrated into central metabolic pathways early in the evolution of life prior to the widespread oxidation of Earth’s atmosphere. Intriguingly, Fe–S cluster-dependent metabolism is sensitive to disruption by oxygen because of the decreased bioavailability of ferric iron as well as direct oxidation of sulfur trafficking intermediates and Fe–S clusters by reactive oxygen species. This fact, coupled with the ubiquity of Fe–S clusters in aerobic organisms, suggests that organisms evolved with mechanisms that facilitate the biogenesis and use of these essential cofactors in the presence of oxygen, which gradually began to accumulate around 2.5 billion years ago as oxygenic photosynthesis proliferated and reduced minerals that buffered against oxidation were depleted. This review highlights the most ancient of the Fe–S cluster biogenesis pathways, the Suf system, which likely was present in early anaerobic forms of life. Herein, we use the evolution of the Suf pathway to assess the relationships between the biochemical functions and physiological roles of Suf proteins, with an emphasis on the selective pressure of oxygen toxicity. Our analysis suggests that diversification into oxygen-containing environments disrupted iron and sulfur metabolism and was a main driving force in the acquisition of accessory Suf proteins (such as SufD, SufE, and SufS) by the core SufB–SufC scaffold complex. This analysis provides a new framework for the study of Fe–S cluster biogenesis pathways and Fe–S cluster-containing metalloenzymes and their complicated patterns of divergence in response to oxygen. PMID:25153801

Energetic features of copper and lead sorption by innovative aminoalcohol-functionalized cobalt phyllosilicates.

PubMed

Melo, Maurício Alves; Airoldi, Claudio

2010-11-14

Inorganic-organic cobalt phyllosilicate hybrids were synthesized by the sol-gel procedure under mild non-hydrothermal conditions with a silicon precursor, formed through individual reactions between the silane 3-glycidoxypropyltriethoxysilane and the aminoalcohols ethanol- or diethanolamine. These procedures generated talc-like phyllosilicates containing pendant organic chains with nitrogen and oxygen basic centres located in the interlamellar region. For organofunctionalized phyllosilicates the lamellar structure obtained through the sol-gel method was confirmed by X-ray powder diffraction, while elemental analysis indicated that the densities of the organic groups attached to the new matrices were 3.31 ± 0.05 and 3.08 ± 0.07 mmol g(-1) for hybrids functionalized with ethanol- and diethanolamines, respectively. Infrared spectroscopy and nuclear magnetic resonance in the solid state for (13)C and (29)Si showed that the organic groups are indeed covalently bonded to the inorganic structures and the process of functionalization did not affect the original structures of the silylating agents employed. The thermally stable hybrids presented well-formed particles with a homogeneous distribution of cobalt and nitrogen atoms. Their abilities for copper removal from aqueous solutions gave maximum capacities of sorption of 2.01 ± 0.11 and 2.55 ± 0.15 mmol g(-1) for phyllosilicates containing ethanol- and diethanolamine groups, respectively. For lead sorption the values of 2.59 ± 0.11 and 2.43 ± 0.12 mmol g(-1) were found for this same sequence. These sorption data were adjusted to the non-linear regression of the Langmuir equation. Energetic features related to the interactions between the cations and the pendant basic centres were determined through calorimetric titrations. The acid-basic interactions reflect the spontaneity of the reactions, which are also enthalpically and entropically favourable for these chelating processes at the solid-liquid interface.

Alkoxide-based magnesium electrolyte compositions for magnesium batteries

DOEpatents

Dai, Sheng; Sun, Xiao-Guang; Liao, Chen; Guo, Bingkun

2018-01-30

Alkoxide magnesium halide compounds having the formula: RO--Mg--X (1) wherein R is a saturated or unsaturated hydrocarbon group that is unsubstituted, or alternatively, substituted with one or more heteroatom linkers and/or one or more heteroatom-containing groups comprising at least one heteroatom selected from fluorine, nitrogen, oxygen, sulfur, and silicon; and X is a halide atom. Also described are electrolyte compositions containing a compound of Formula (1) in a suitable polar aprotic or ionic solvent, as well as magnesium batteries in which such electrolytes are incorporated.

Development of Low Cost Gas Atomization of Precursor Powders for Simplified ODS Alloy Production

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

Anderson, Iver

2014-08-05

A novel gas atomization reaction synthesis (GARS) method was developed in this project to enable production (at our partner’s facility) a precursor Ni-Cr-Y-Ti powder with a surface oxide and an internal rare earth (RE) containing intermetallic compound (IMC) phase. Consolidation and heat-treatment experiments were performed at Ames Lab to promote the exchange of oxygen from the surface oxide to the RE intermetallic to form nano-metric oxide dispersoids. Alloy selection was aided by an internal oxidation and serial grinding experiments at Ames Lab and found that Hf-containing alloys may form more stable dispersoids than Ti-containing alloy, i.e., the Hf-containing system exhibitedmore » five different oxide phases and two different intermetallics compared to the two oxide phases and one intermetallic in the Ti-containing alloys. Since the simpler Ti-containing system was less complex to characterize, and make observations on the effects of processing parameters, the Ti-containing system was selected by Ames Lab for experimental atomization trials at our partner. An internal oxidation model was developed at Ames Lab and used to predict the heat treatment times necessary for dispersoid formation as a function of powder size and temperature. A new high-pressure gas atomization (HPGA) nozzle was developed at Ames Lab with the aim of promoting fine powder production at scales similar to that of the high gas-flow and melt-flow of industrial atomizers. The atomization nozzle was characterized using schlieren imaging and aspiration pressure testing at Ames Lab to determine the optimum melt delivery tip geometry and atomization pressure to promote enhanced secondary atomization mechanisms. Six atomization trials were performed at our partner to investigate the effects of: gas atomization pressure and reactive gas concentration on the particle size distribution (PSD) and the oxygen content of the resulting powder. Also, the effect on the rapidly solidified microstructure (as a function of powder size) was investigated at Ames Lab as a function of reactive gas composition and bulk alloy composition. The results indicated that the pulsatile gas atomization mechanism and a significantly enhanced yield of fine powders reported in the literature for this type of process were not observed. Also it was determined that reactive gas may marginally improve the fine powder yield but further experiments are required. The oxygen content in the gas also did not have any detrimental effect on the microstructure (i.e. did not significantly reduce undercooling). On the contrary, the oxygen addition to the atomization gas may have mitigated some potent catalytic nucleation sites, but not enough to significantly alter the microstructure vs. particle size relationship. Overall the downstream injection of oxygen was not found to significantly affect either the particle size distribution or undercooling (as inferred from microstructure and XRD observations) but injection further upstream, including in the gas atomization nozzle, remains to be investigated in later work.« less

Residual oxygen releasing time from dental structure after carbamide peroxide exposure: study of the effects of a neutralizer gel.

PubMed

Salome, Paloma; Bueno, Renata Pla Rizzolo; Nascimento, Paulo Cicero; Pozzobon, Roselaine Terezinha

2012-01-01

The purpose of this article was to assess in vitro the effects of a catalase-based neutralizer gel in the release of residual oxygen in permanent human teeth specimens exposed to 10% carbamide peroxide. Thirty teeth specimens (5.0 x 5.0 x 3.0 mm3) were randomly divided into three groups (n = 10): Group 1, nonbleached negative control specimens; Group 2, bleached positive control specimens; and Group 3, bleached specimens exposed to a catalase-based gel. The bleaching treatment was performed six hours per day for 14 days. At the end of the bleaching treatment, Group 3 specimens were immersed in a receptacle containing the catalase-based experimental gel for three minutes. Titrations were performed to determine the quantity of residual oxygen that each test specimen released, starting immediately after the end of the bleaching treatment and exposure (or not) to the catalase-based gel, and repeated on days 1-5, 10, and 15. The values obtained were statistically analyzed by ANOVA and a Tukey post hoc test (P < 0.05). The release values of residual O2 for Group 2 were equal to those of Group 1 after 10 days and to those of Group 3 after five days. The use of a catalase-based experimental neutralizer gel, applied for three minutes, reduced by half the time required for complete release of residual oxygen from tooth structure after exposure to a 10% carbamide peroxide bleaching agent.

Computed Regioselectivity and Conjectured Biological Activity of Ene Reactions of Singlet Oxygen with the Natural Product Hyperforin.

PubMed

Abramova, Inna; Rudshteyn, Benjamin; Liebman, Joel F; Greer, Alexander

2017-03-01

Hyperforin is a constituent of St. John's wort and coexists with the singlet oxygen sensitizer hypericin. Density functional theory, molecular mechanics and Connolly surface calculations show that accessibility in the singlet oxygen "ene" reaction favors the hyperforin "southwest" and "southeast" prenyl (2-methyl-2-butenyl) groups over the northern prenyl groups. While the southern part of hyperforin is initially more susceptible to oxidation, up to 4 "ene" reactions of singlet oxygen can take place. Computational results assist in predicting the fate of adjacent hydroperoxides in hyperforin, where the loss of hydrogen atoms may lead to the formation of a hydrotrioxide and a carbonyl instead of a Russell reaction. © 2017 The American Society of Photobiology.

DFT studies on the heterogeneous oxidation of SO2 by oxygen functional groups on graphene.

PubMed

He, Guangzhi; He, Hong

2016-11-23

The heterogeneous oxidation of SO 2 has been the subject of intense scrutiny in atmospheric chemistry because of the adverse effects of sulfate particles. Although it has been found that the soot particles with a graphene-like structure play an important role in the oxidation of SO 2 , little is known about the atomic-level mechanism involved. Here, we studied the oxidation of SO 2 on oxygen-functionalized graphene using density functional theory (DFT) calculation. The results showed that SO 2 is oxidized by the epoxide group via a two-step mechanism, where the C-O bond away from the SO 2 is broken first, followed by the breaking of the other C-O bond and the synchronous formation of a new S-O bond. The energy barriers are significantly decreased when solvation free energies are involved, suggesting that humidity is favorable for promoting the oxidation by reducing the reaction barrier. The energy barriers for H 2 SO 3 oxidation are much higher than that for SO 2 oxidation, indicating that the direct conversion of SO 2 to SO 3 is the main pathway for the oxidation of SO 2 by oxygen-functionalized graphene sheets in both the gas phase and solution. The reduced density gradient (RDG) analysis showed that the hydrogen bond formed between H 2 SO 3 and epoxide groups enhances the stability of the reaction complex, and is responsible for the high energy barrier that has to be overcome for the reaction to proceed. These atomistic studies proposed a two-step mechanism for the oxidation of SO 2 on the oxygen-functionalized graphene-like carbonaceous surfaces under ambient conditions.

Positive selection in octopus haemocyanin indicates functional links to temperature adaptation.

PubMed

Oellermann, Michael; Strugnell, Jan M; Lieb, Bernhard; Mark, Felix C

2015-07-05

Octopods have successfully colonised the world's oceans from the tropics to the poles. Yet, successful persistence in these habitats has required adaptations of their advanced physiological apparatus to compensate impaired oxygen supply. Their oxygen transporter haemocyanin plays a major role in cold tolerance and accordingly has undergone functional modifications to sustain oxygen release at sub-zero temperatures. However, it remains unknown how molecular properties evolved to explain the observed functional adaptations. We thus aimed to assess whether natural selection affected molecular and structural properties of haemocyanin that explains temperature adaptation in octopods. Analysis of 239 partial sequences of the haemocyanin functional units (FU) f and g of 28 octopod species of polar, temperate, subtropical and tropical origin revealed natural selection was acting primarily on charge properties of surface residues. Polar octopods contained haemocyanins with higher net surface charge due to decreased glutamic acid content and higher numbers of basic amino acids. Within the analysed partial sequences, positive selection was present at site 2545, positioned between the active copper binding centre and the FU g surface. At this site, methionine was the dominant amino acid in polar octopods and leucine was dominant in tropical octopods. Sites directly involved in oxygen binding or quaternary interactions were highly conserved within the analysed sequence. This study has provided the first insight into molecular and structural mechanisms that have enabled octopods to sustain oxygen supply from polar to tropical conditions. Our findings imply modulation of oxygen binding via charge-charge interaction at the protein surface, which stabilize quaternary interactions among functional units to reduce detrimental effects of high pH on venous oxygen release. Of the observed partial haemocyanin sequence, residue 2545 formed a close link between the FU g surface and the active centre, suggesting a role as allosteric binding site. The prevalence of methionine at this site in polar octopods, implies regulation of oxygen affinity via increased sensitivity to allosteric metal binding. High sequence conservation of sites directly involved in oxygen binding indicates that functional modifications of octopod haemocyanin rather occur via more subtle mechanisms, as observed in this study.

Comparative Study of Chromium(VI) Removal from Simulated Industrial Wastewater with Ion Exchange Resins

NASA Astrophysics Data System (ADS)

Li, Xiaofan; Shi, Shaoyuan; Cao, Hongbin; Li, Yuping; Xu, Dongyao

2018-06-01

Ion exchange process is an alternative technique for removal of heavy metal ions from industrial wastewater. The main aim of this paper is to evaluate the performance of different ion exchange resins in removing Cr(VI) from wastewater. The effects of resin types and dosage, initial pH were examined systemically. The results showed that the performance of different resins had obvious difference for the removal of the Cr(VI) ions, in which the type of functional groups of the resin was the main factor. The SEM images indicated that the micro-morphology of resins before and after adsorption of the Cr(VI) presented a little difference. The EDS analysis showed that the adsorbed Cr(VI) was uniformly distributed at the surface of the resins with formation of oxygen-containing groups. The adsorption isotherms and kinetics of Cr(VI) by the different resins are also discussed.

Tunneling in green tea: understanding the antioxidant activity of catechol-containing compounds. A variational transition-state theory study.

PubMed

Tejero, Ismael; Gonzalez-García, Núria; Gonzalez-Lafont, Angels; Lluch, José M

2007-05-09

The catechol functionality present in the catechins is responsible for the protective effects exerted by green tea against a wide range of human diseases. High-level electronic structure calculations and canonical variational transition-state theory including multidimensional tunneling corrections have allowed us to understand the key factors of the antioxidant effectiveness of the catechol group. This catechol group forms two hydrogen bonds with the two oxygen atoms of the lipid peroxyl radical, leading to a very compact reactant complex. This fact produces an extremely narrow adiabatic potential-energy profile corresponding to the hydrogen abstraction by the peroxyl radical, which makes it possible for a huge tunneling contribution to take place. So, quantum-mechanical tunneling highly increases the corresponding rate constant value, in such a way that catechins become able to trap the lipid peroxyl radicals in a dominant competition with the very damaging free-radical chain-lipid peroxidation reaction.

Leveraging zinc interstitials and oxygen vacancies for sensitive biomolecule detection through selective surface functionalization

NASA Astrophysics Data System (ADS)

Radha Shanmugam, Nandhinee; Muthukumar, Sriram; Chaudhry, Shajee; Prasad, Shalini

2015-03-01

In this study, functionally engineered EIS technique was implemented to investigate the influence of surface functionalization on sensitivity of biomolecule detection using nanostructured ZnO platform. Organic molecules with thiol and carboxylic functional groups were chosen to control biomolecule immobilization on zinc and oxygen-terminated 2D planar and 1D nanostructured ZnO surfaces. The amount of functionalization and its influence on charge perturbations at the ZnO-electrolyte interface were studied using fluorescence and EIS measurements. We observed the dependence of charge transfer on both the polarity of platform and concentration of cross-linker molecules. Such selectively modified surfaces were used for detection of cortisol, a major stress indicator. Results demonstrated preferential binding of thiol groups to Zn terminations and thus leveraging ZnO interstitials increases the sensitivity of detection over larger dynamic range with detection limit at 10fg/mL.

Assessment of pedophilia using hemodynamic brain response to sexual stimuli.

PubMed

Ponseti, Jorge; Granert, Oliver; Jansen, Olav; Wolff, Stephan; Beier, Klaus; Neutze, Janina; Deuschl, Günther; Mehdorn, Hubertus; Siebner, Hartwig; Bosinski, Hartmut

2012-02-01

Accurately assessing sexual preference is important in the treatment of child sex offenders. Phallometry is the standard method to identify sexual preference; however, this measure has been criticized for its intrusiveness and limited reliability. To evaluate whether spatial response pattern to sexual stimuli as revealed by a change in the blood oxygen level-dependent signal facilitates the identification of pedophiles. During functional magnetic resonance imaging, pedophilic and nonpedophilic participants were briefly exposed to same- and opposite-sex images of nude children and adults. We calculated differences in blood oxygen level-dependent signals to child and adult sexual stimuli for each participant. The corresponding contrast images were entered into a group analysis to calculate whole-brain difference maps between groups. We calculated an expression value that corresponded to the group result for each participant. These expression values were submitted to 2 different classification algorithms: Fisher linear discriminant analysis and κ -nearest neighbor analysis. This classification procedure was cross-validated using the leave-one-out method. Section of Sexual Medicine, Medical School, Christian Albrechts University of Kiel, Kiel, Germany. We recruited 24 participants with pedophilia who were sexually attracted to either prepubescent girls (n = 11) or prepubescent boys (n = 13) and 32 healthy male controls who were sexually attracted to either adult women (n = 18) or adult men (n = 14). Sensitivity and specificity scores of the 2 classification algorithms. The highest classification accuracy was achieved by Fisher linear discriminant analysis, which showed a mean accuracy of 95% (100% specificity, 88% sensitivity). Functional brain response patterns to sexual stimuli contain sufficient information to identify pedophiles with high accuracy. The automatic classification of these patterns is a promising objective tool to clinically diagnose pedophilia.

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

Sokhansanj, Shahabaddine; Kuang, Xingya; Shankar, T.S.

Few papers have been published in the open literature on the emissions from biomass fuels, including wood pellets, during the storage and transportation and their potential health impacts. The purpose of this study is to provide data on the concentrations, emission factors, and emission rate factors of CO2, CO, and CH4 from wood pellets stored with different headspace to container volume ratios with different initial oxygen levels, in order to develop methods to reduce the toxic off-gas emissions and accumulation in storage spaces. Metal containers (45 l, 305 mm diameter by 610 mm long) were used to study the effectmore » of headspace and oxygen levels on the off-gas emissions from wood pellets. Concentrations of CO2, CO, and CH4 in the headspace were measured using a gas chromatograph as a function of storage time. The results showed that the ratio of the headspace ratios and initial oxygen levels in the storage space significantly affected the off-gas emissions from wood pellets stored in a sealed container. Higher peak emission factors and higher emission rates are associated with higher headspace ratios. Lower emissions of CO2 and CO were generated at room temperature under lower oxygen levels, whereas CH4 emission is insensitive to the oxygen level. Replacing oxygen with inert gases in the storage space is thus a potentially effective method to reduce the biomass degradation and toxic off-gas emissions. The proper ventilation of the storage space can also be used to maintain a high oxygen level and low concentrations of toxic off-gassing compounds in the storage space, which is especially useful during the loading and unloading operations to control the hazards associated with the storage and transportation of wood pellets.« less

[Blood oxygen transport, prooxidant -- antioxidant status, and vasoactive characteristics of vascular endothelium in rats treated with endotoxin and taurine].

PubMed

Milosh, T S; Maksimovich, N E

2014-01-01

Experiments on a group of 74 pregnant rats upon intramuscular introduction of E. coli lipopolysaccharides during pregnancy revealed the correction effect of taurine on the blood oxygen transport function, prooxidant - antioxidant status, and vasoactive characteristics of vascular endothelium.

Understanding Trends in Autoignition of Biofuels: Homologous Series of Oxygenated C5 Molecules

DOE PAGES

Ciesielski, Peter N.; Robichaud, David J.; Kim, Seonah; ...

2017-07-05

Oxygenated biofuels provide a renewable, domestic source of energy that can enable adoption of advanced, high-efficiency internal combustion engines, such as those based on homogeneously charged compression ignition (HCCI). Of key importance to such engines is the cetane number (CN) of the fuel, which is determined by the autoignition of the fuel under compression at relatively low temperatures (550-800 K). For the plethora of oxygenated biofuels possible, it is desirable to know the ignition delay times and the CN of these fuels to help guide conversion strategies so as to focus efforts on the most desirable fuels. For alkanes, themore » chemical pathways leading to radical chain-branching reactions giving rise to low-temperature autoignition are well-known and are highly coincident with the buildup of reactive radicals such as OH. Key in the mechanisms leading to chain branching are the addition of molecular oxygen to alkyl radicals and the rearrangement and dissociation of the resulting peroxy radials. Prediction of the temperature and pressure dependence of reactions that lead to the buildup of reactive radicals requires a detailed understanding of the potential energy surfaces (PESs) of these reactions. In this study, we used quantum mechanical modeling to systematically compare the effects of oxygen functionalities on these PESs and associated kinetics so as to understand how they affect experimental trends in autoignition and CN. The molecules studied here include pentane, pentanol, pentanal, 2-heptanone, methylpentyl ether, methyl hexanoate, and pentyl acetate. All have a saturated five-carbon alkyl chain with an oxygen functional group attached to the terminal carbon atom. The results of our systematic comparison may be summarized as follows: (1) Oxygen functionalities activate C-H bonds by lowering the bond dissociation energy (BDE) relative to alkanes. (2) The R-OO bonds in peroxy radicals adjacent to carbonyl groups are weaker than corresponding alkyl systems, leading to dissociation of ROO radicals and reducing reactivity and hence CN. (3) Hydrogen atom transfer in peroxy radicals is important in autoignition, and low barriers for ethers and aldehydes lead to high CN. (4) Peroxy radicals formed from alcohols have low barriers to form aldehydes, which reduce the reactivity of the alkyl radical. In conclusion, these findings for the formation and reaction of alkyl radicals with molecular oxygen explain the trend in CN for these common biofuel functional groups.« less

Understanding Trends in Autoignition of Biofuels: Homologous Series of Oxygenated C5 Molecules

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

Ciesielski, Peter N.; Robichaud, David J.; Kim, Seonah

Oxygenated biofuels provide a renewable, domestic source of energy that can enable adoption of advanced, high-efficiency internal combustion engines, such as those based on homogeneously charged compression ignition (HCCI). Of key importance to such engines is the cetane number (CN) of the fuel, which is determined by the autoignition of the fuel under compression at relatively low temperatures (550-800 K). For the plethora of oxygenated biofuels possible, it is desirable to know the ignition delay times and the CN of these fuels to help guide conversion strategies so as to focus efforts on the most desirable fuels. For alkanes, themore » chemical pathways leading to radical chain-branching reactions giving rise to low-temperature autoignition are well-known and are highly coincident with the buildup of reactive radicals such as OH. Key in the mechanisms leading to chain branching are the addition of molecular oxygen to alkyl radicals and the rearrangement and dissociation of the resulting peroxy radials. Prediction of the temperature and pressure dependence of reactions that lead to the buildup of reactive radicals requires a detailed understanding of the potential energy surfaces (PESs) of these reactions. In this study, we used quantum mechanical modeling to systematically compare the effects of oxygen functionalities on these PESs and associated kinetics so as to understand how they affect experimental trends in autoignition and CN. The molecules studied here include pentane, pentanol, pentanal, 2-heptanone, methylpentyl ether, methyl hexanoate, and pentyl acetate. All have a saturated five-carbon alkyl chain with an oxygen functional group attached to the terminal carbon atom. The results of our systematic comparison may be summarized as follows: (1) Oxygen functionalities activate C-H bonds by lowering the bond dissociation energy (BDE) relative to alkanes. (2) The R-OO bonds in peroxy radicals adjacent to carbonyl groups are weaker than corresponding alkyl systems, leading to dissociation of ROO radicals and reducing reactivity and hence CN. (3) Hydrogen atom transfer in peroxy radicals is important in autoignition, and low barriers for ethers and aldehydes lead to high CN. (4) Peroxy radicals formed from alcohols have low barriers to form aldehydes, which reduce the reactivity of the alkyl radical. In conclusion, these findings for the formation and reaction of alkyl radicals with molecular oxygen explain the trend in CN for these common biofuel functional groups.« less

Adsorption of Pb(II) ions onto biomass from Trifolium resupinatum: equilibrium and kinetic studies

NASA Astrophysics Data System (ADS)

Athar, Makshoof; Farooq, Umar; Aslam, Muhammad; Salman, M.

2013-09-01

The present study provides information about the binding of Pb(II) ions on an eco-friendly and easily available biodegradable biomass Trifolium resupinatum. The powdered biomass was characterized by FTIR, potentiometric titration and surface area analyses. The FTIR spectrum showed the presence of hydroxyl, carbonyl and amino functional groups and Pb(II) ions bound with the oxygen- and nitrogen-containing sites (hydroxyl and amino groups). The acidic groups were also confirmed by titrations. Effects of various environmental parameters (time, pH and concentration) have been studied. The biosorption process achieved equilibrium in a very short period of time (25 min). Non-linear approach for Langmuir and Freundlich models was used to study equilibrium process and root mean-square error was used as an indicator to decide the fitness of the mathematical model. The biosorption process was found to follow pseudo-second-order kinetics and was very fast. Thus, the biomass can be cost-effectively used for the binding of Pb(II) ions from aqueous solutions.

Multi-functional magnesium alloys containing interstitial oxygen atoms.

PubMed

Kang, H; Choi, H J; Kang, S W; Shin, S E; Choi, G S; Bae, D H

2016-03-15

A new class of magnesium alloys has been developed by dissolving large amounts of oxygen atoms into a magnesium lattice (Mg-O alloys). The oxygen atoms are supplied by decomposing titanium dioxide nanoparticles in a magnesium melt at 720 °C; the titanium is then completely separated out from the magnesium melt after solidification. The dissolved oxygen atoms are located at the octahedral sites of magnesium, which expand the magnesium lattice. These alloys possess ionic and metallic bonding characteristics, providing outstanding mechanical and functional properties. A Mg-O-Al casting alloy made in this fashion shows superior mechanical performance, chemical resistance to corrosion, and thermal conductivity. Furthermore, a similar Mg-O-Zn wrought alloy shows high elongation to failure (>50%) at room temperature, because the alloy plastically deforms with only multiple slips in the sub-micrometer grains (<300 nm) surrounding the larger grains (~15 μm). The metal/non-metal interstitial alloys are expected to open a new paradigm in commercial alloy design.

In-situ micro-FTIR Study of Thermal Changes of Organics in Tagish Lake Meteorite: Behavior of Aliphatic Oxygenated Functions and Effects of Minerals

NASA Technical Reports Server (NTRS)

Kebukawa, Yoko; Nakashima, Satoru; Nakamura-Messenger, Keiko; Zolensky, Michael E.

2007-01-01

Systematic in-situ FTIR heating experiments of Tagish Lake meteorite grains have been performed in order to study thermal stability of chondritic organics. Some aliphatic model organic substances have also been used to elucidate effects of hydrous phyllosilicate minerals on the thermal stability of organics. The experimental results indicated that organic matter in the Tagish Lake meteorite might contain oxygenated aliphatic hydrocarbons which are thermally stable carbonyls such as ester and/or C=O in ring compounds. The presence of hydrous phyllosilicate minerals has a pronounced effect on the increase of the thermal stability of aliphatic and oxygenated functions. These oxygenated aliphatic organics in Tagish Lake can be formed during the aqueous alteration in the parent body and the formation temperature condition might be less than 200 C, based especially on the thermal stability of C-O components. The hydrous phyllosilicates might provide sites for organic globule formation and protected some organic decomposition

Multi-functional magnesium alloys containing interstitial oxygen atoms

PubMed Central

Kang, H.; Choi, H. J.; Kang, S. W.; Shin, S. E.; Choi, G. S.; Bae, D. H.

2016-01-01

A new class of magnesium alloys has been developed by dissolving large amounts of oxygen atoms into a magnesium lattice (Mg-O alloys). The oxygen atoms are supplied by decomposing titanium dioxide nanoparticles in a magnesium melt at 720 °C; the titanium is then completely separated out from the magnesium melt after solidification. The dissolved oxygen atoms are located at the octahedral sites of magnesium, which expand the magnesium lattice. These alloys possess ionic and metallic bonding characteristics, providing outstanding mechanical and functional properties. A Mg-O-Al casting alloy made in this fashion shows superior mechanical performance, chemical resistance to corrosion, and thermal conductivity. Furthermore, a similar Mg-O-Zn wrought alloy shows high elongation to failure (>50%) at room temperature, because the alloy plastically deforms with only multiple slips in the sub-micrometer grains (<300 nm) surrounding the larger grains (~15 μm). The metal/non-metal interstitial alloys are expected to open a new paradigm in commercial alloy design. PMID:26976372

Method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide

DOEpatents

Clawson, Lawrence G.; Mitchell, William L.; Bentley, Jeffrey M.; Thijssen, Johannes H. J.

2000-01-01

A method for converting hydrocarbon fuel into hydrogen gas and carbon dioxide within a reformer 10 is disclosed. According to the method, a stream including an oxygen-containing gas is directed adjacent to a first vessel 18 and the oxygen-containing gas is heated. A stream including unburned fuel is introduced into the oxygen-containing gas stream to form a mixture including oxygen-containing gas and fuel. The mixture of oxygen-containing gas and unburned fuel is directed tangentially into a partial oxidation reaction zone 24 within the first vessel 18. The mixture of oxygen-containing gas and fuel is further directed through the partial oxidation reaction zone 24 to produce a heated reformate stream including hydrogen gas and carbon monoxide. Steam may also be mixed with the oxygen-containing gas and fuel, and the reformate stream from the partial oxidation reaction zone 24 directed into a steam reforming zone 26. High- and low-temperature shift reaction zones 64,76 may be employed for further fuel processing.

Molecular Evolution of the Oxygen-Binding Hemerythrin Domain

PubMed Central

Alvarez-Carreño, Claudia; Becerra, Arturo; Lazcano, Antonio

2016-01-01

Background The evolution of oxygenic photosynthesis during Precambrian times entailed the diversification of strategies minimizing reactive oxygen species-associated damage. Four families of oxygen-carrier proteins (hemoglobin, hemerythrin and the two non-homologous families of arthropodan and molluscan hemocyanins) are known to have evolved independently the capacity to bind oxygen reversibly, providing cells with strategies to cope with the evolutionary pressure of oxygen accumulation. Oxygen-binding hemerythrin was first studied in marine invertebrates but further research has made it clear that it is present in the three domains of life, strongly suggesting that its origin predated the emergence of eukaryotes. Results Oxygen-binding hemerythrins are a monophyletic sub-group of the hemerythrin/HHE (histidine, histidine, glutamic acid) cation-binding domain. Oxygen-binding hemerythrin homologs were unambiguously identified in 367/2236 bacterial, 21/150 archaeal and 4/135 eukaryotic genomes. Overall, oxygen-binding hemerythrin homologues were found in the same proportion as single-domain and as long protein sequences. The associated functions of protein domains in long hemerythrin sequences can be classified in three major groups: signal transduction, phosphorelay response regulation, and protein binding. This suggests that in many organisms the reversible oxygen-binding capacity was incorporated in signaling pathways. A maximum-likelihood tree of oxygen-binding hemerythrin homologues revealed a complex evolutionary history in which lateral gene transfer, duplications and gene losses appear to have played an important role. Conclusions Hemerythrin is an ancient protein domain with a complex evolutionary history. The distinctive iron-binding coordination site of oxygen-binding hemerythrins evolved first in prokaryotes, very likely prior to the divergence of Firmicutes and Proteobacteria, and spread into many bacterial, archaeal and eukaryotic species. The later evolution of the oxygen-binding hemerythrin domain in both prokaryotes and eukaryotes led to a wide variety of functions, ranging from protection against oxidative damage in anaerobic and microaerophilic organisms, to oxygen supplying to particular enzymes and pathways in aerobic and facultative species. PMID:27336621

Functional electrolyte for lithium-ion batteries

DOEpatents

Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

2015-04-14

Functional electrolyte solvents include compounds having at least one aromatic ring with 2, 3, 4 or 5 substituents, at least one of which is a substituted or unsubstituted methoxy group, at least one of which is a tert-butyl group and at least one of which is a substituted or unsubstituted polyether or poly(ethylene oxide) (PEO) group bonded through oxygen to the aromatic ring, are provided.

Characterization of Platinum Nanoparticles Deposited on Functionalized Graphene Sheets

PubMed Central

Chiang, Yu-Chun; Liang, Chia-Chun; Chung, Chun-Ping

2015-01-01

Due to its special electronic and ballistic transport properties, graphene has attracted much interest from researchers. In this study, platinum (Pt) nanoparticles were deposited on oxidized graphene sheets (cG). The graphene sheets were applied to overcome the corrosion problems of carbon black at operating conditions of proton exchange membrane fuel cells. To enhance the interfacial interactions between the graphene sheets and the Pt nanoparticles, the oxygen-containing functional groups were introduced onto the surface of graphene sheets. The results showed the Pt nanoparticles were uniformly dispersed on the surface of graphene sheets with a mean Pt particle size of 2.08 nm. The Pt nanoparticles deposited on graphene sheets exhibited better crystallinity and higher oxygen resistance. The metal Pt was the predominant Pt chemical state on Pt/cG (60.4%). The results from the cyclic voltammetry analysis showed the value of the electrochemical surface area (ECSA) was 88 m2/g (Pt/cG), much higher than that of Pt/C (46 m2/g). The long-term test illustrated the degradation in ECSA exhibited the order of Pt/C (33%) > Pt/cG (7%). The values of the utilization efficiency were calculated to be 64% for Pt/cG and 32% for Pt/C. PMID:28793577

Optical Band Gap Alteration of Graphene Oxide via Ozone Treatment.

PubMed

Hasan, Md Tanvir; Senger, Brian J; Ryan, Conor; Culp, Marais; Gonzalez-Rodriguez, Roberto; Coffer, Jeffery L; Naumov, Anton V

2017-07-25

Graphene oxide (GO) is a graphene derivative that emits fluorescence, which makes GO an attractive material for optoelectronics and biotechnology. In this work, we utilize ozone treatment to controllably tune the band gap of GO, which can significantly enhance its applications. Ozone treatment in aqueous GO suspensions yields the addition/rearrangement of oxygen-containing functional groups suggested by the increase in vibrational transitions of C-O and C=O moieties. Concomitantly it leads to an initial increase in GO fluorescence intensity and significant (100 nm) blue shifts in emission maxima. Based on the model of GO fluorescence originating from sp 2 graphitic islands confined by oxygenated addends, we propose that ozone-induced functionalization decreases the size of graphitic islands affecting the GO band gap and emission energies. TEM analyses of GO flakes confirm the size decrease of ordered sp 2 domains with ozone treatment, whereas semi-empirical PM3 calculations on model addend-confined graphitic clusters predict the inverse dependence of the band gap energies on sp 2 cluster size. This model explains ozone-induced increase in emission energies yielding fluorescence blue shifts and helps develop an understanding of the origins of GO fluorescence emission. Furthermore, ozone treatment provides a versatile approach to controllably alter GO band gap for optoelectronics and bio-sensing applications.

Adsorption Behavior of Surfactant on Lignite Surface: A Comparative Experimental and Molecular Dynamics Simulation Study

PubMed Central

He, Meng; Zhang, Wei; Cao, Xiaoqiang; You, Xiaofang; Li, Lin

2018-01-01

Experimental and computational simulation methods are used to investigate the adsorption behavior of the surfactant nonylphenol ethoxylate (NPEO10), which contains 10 ethylene oxide groups, on the lignite surface. The adsorption of NPEO10 on lignite follow a Langmuir-type isotherm. The thermodynamic parameters of the adsorption process show that the whole process is spontaneous. X-ray photoelectron spectroscopic (XPS) analysis indicates that a significant fraction of the oxygen-containing functional groups on the lignitic surface were covered by NPEO10. Molecular dynamics (MD) simulations show that the NPEO10 molecules were found to adsorb at the water-coal interface. Moreover, polar interactions are the main effect in the adsorption process. The density distributions of coal, NPEO10, and water molecules along the Z axis show that the remaining hydrophobic portions of the surfactant extend into the solution, creating a more hydrophobic coal surface that repels water molecules. The negative interaction energy calculated from the density profiles of the head and tail groups along the three spatial directions between the surfactant and the lignitic surface suggest that the adsorption process is spontaneous. The self-diffusion coefficients show that the presence of NPEO10 causes higher water mobility by improving the hydrophobicity of lignite. PMID:29389899

Catalytic conversion of aliphatic alcohols on carbon nanomaterials: The roles of structure and surface functional groups

NASA Astrophysics Data System (ADS)

Tveritinova, E. A.; Zhitnev, Yu. N.; Chernyak, S. A.; Arkhipova, E. A.; Savilov, S. V.; Lunin, V. V.

2017-03-01

Carbon nanomaterials with the structure of graphene and different compositions of the surface groups are used as catalysts for the conversion of C2-C4 aliphatic alcohols. The conversions of ethanol, propanol- 1, propanol-2, butanol-1, butanol-2, and tert-butanol on carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are investigated. Oxidized and nonoxidized multiwalled carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are synthesized. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning and transmission electronic microscopies, Brunauer-Emmett-Teller method, derivatographic analyses, and the pulsed microcatalytic method are used to characterize comprehensively the prepared catalysts. It was established that all of the investigated carbon nanomaterials (with the exception of nondoped carbon nanoflakes) are bifunctional catalysts for the conversion of aliphatic alcohols, and promote dehydration reactions with the formation of olefins and dehydrogenation reactions with the formation of aldehydes or ketones. Nanoflakes doped with nitrogen are inert with respect to secondary alcohols and tert-butanol. The role of oxygen-containing and nitrogen-containing surface groups, and of the geometrical structure of the carbon matrix of graphene nanocarbon materials in the catalytic conversion of aliphatic alcohols, is revealed. Characteristics of the conversion of aliphatic alcohols that are associated with their structure are identified.

Near-infrared spectroscopy of the bladder: a new technique for studying lower urinary tract function in health and disease

NASA Astrophysics Data System (ADS)

Shadgan, Babak; Afshar, Kourosh; Stothers, Lynn; Macnab, Andrew

2010-02-01

Background: Continuous wave near-infrared spectroscopy (NIRS) can monitor chromophore change in the bladder detrusor muscle during voiding; oxygenation and hemodynamic data derived differ in health and disease. Application of wireless NIRS for evaluation of voiding dysfunction would benefit children. Methods: Subjects: 20 children (4-17 yrs) [5 normal, 15 with urinary tract pathology]. Instrumentation: self-contained device weight 84 gm; 3 paired light emitting diodes (760/850 nm) in a spatially resolved configuration; source-detector separation distances (30, 35 and 40 mm); silicon photodiode detector; and Bluetooth®. Procedure: Transcutaneous monitoring (midline abdominal skin 2 cm above pubis) during spontaneous voiding (bladder contraction) of oxygenated (O2Hb), deoxygenated (HHb) and total hemoglobin (tHb) and tissue oxygen saturation index (TSI %) at 10 Hz. Results: All 20 trials produced clear graphic data with no movement effect evident. Comparison of patterns of chromophore change between normal and symptomatic subjects revealed trend differences in O2Hb and tHb. (Normal positive; Symptomatic negative, and TSI% fell in symptomatic group). Conclusions: Wireless NIRS is technically feasible in ambulant children. Negative trends in chromophore concentration and falls in TSI% suggest a hemodynamic impairment may underlie some forms of voiding dysfunction, with abnormal physiology involving the microcirculation possibly resulting in muscle fatigue during voiding.

Preparation of a bonelike apatite-polymer fiber composite using a simple biomimetic process.

PubMed

Yokoyama, Yoshiro; Oyane, Ayako; Ito, Atsuo

2008-08-01

A bonelike apatite-polymer fiber composite may be useful as an implant material to replace bone, the enthesis of a tendon, and the joint part of a ligament. We treated an ethylene-vinyl alcohol copolymer (EVOH) plate and knitted EVOH fibers with an oxygen plasma to produce oxygen-containing functional groups on their surfaces. The plasma-treated samples were alternately dipped in alcoholic calcium and phosphate ion solutions three times to deposit apatite precursors onto their surfaces. The surface-modified samples formed a dense and uniform bonelike surface apatite layer after immersion for 24 h in a simulated body fluid with ion concentrations approximately equal to those of human blood plasma. The adhesive strength between the apatite layer and the sample's surface increased with increasing power density of the oxygen plasma. The apatite-EVOH fiber composite obtained by our process has similarities to natural bone in that apatite crystals are deposited on organic polymer fibers. The resulting composite would possess osteoconductivity due to the apatite phase. With proper polymer selection and optimized synthesis techniques, a composite could be made that would have bonelike mechanical properties. Hence, the present surface modification and coating process would be a promising route to obtain new implant materials with bonelike mechanical properties and osteoconductivity. (c) 2007 Wiley Periodicals, Inc.

Method of removing nitrogen monoxide from a nitrogen monoxide-containing gas using a water-soluble iron ion-dithiocarbamate, xanthate or thioxanthate

DOEpatents

Liu, D. Kwok-Keung; Chang, Shih-Ger

1987-08-25

The present invention relates to a method of removing of nitrogen monoxide from a nitrogen monoxide-containing gas which method comprises contacting a nitrogen oxide-containing gas with an aqueous solution of water soluble organic compound-iron ion chelate complex. The NO absorption efficiency of ferrous urea-dithiocarbamate and ferrous diethanolamine-xanthate as a function of time, oxygen content and solution ph is presented. 3 figs., 1 tab.

Effects of exercise program on physiological functions in postmenopausal women with metabolic syndrome.

PubMed

Heli, Valkeinen; Ihab, Hajjar; Kun, Hu; Brad, Manor; Jessica, Wisocky; Vera, Novak

2013-12-01

The purpose of this study was to examine effects of mixed interval aerobic and strength training (MAST) program on physiological functions in older women with metabolic syndrome. 12 subjects were randomly assigned to the exercise group (16-week MAST program) or the control group. Outcomes included oxygen uptake (VO 2max ), cerebral blood flow velocity (BFV) and cognitive functions. The exercise group demonstrated increased VO 2max and certain improvements in cognitive functions. No changes were observed in BFV for both groups. These results can be used as a preliminary data for planning larger studies.

Effects of Hyperbaric Oxygen Treatment on Renal System.

PubMed

Tezcan, Orhan; Caliskan, Ahmet; Demirtas, Sinan; Yavuz, Celal; Kuyumcu, Mahir; Nergiz, Yusuf; Guzel, Abdulmenap; Karahan, Oguz; Ari, Seyhmus; Soker, Sevda; Yalinkilic, Ibrahim; Turkdogan, Kenan Ahmet

2017-01-01

Hyperbaric oxygen (HBO) treatment is steadily increasing as a therapeutic modality for various types of diseases. Although good clinical outcomes were reported with HBO treatment for various diseases, the multisystemic effects of this modality are still unclear. This study aimed to investigate the renal effects of HBO experimentally. Fourteen New Zealand White rabbits were divided into 2 groups randomly as the control group and the study group. The study group received HBO treatment for 28 days (100% oxygen at 2.5 atmospheres for 90 minutes daily) and the control group was used to obtain normal renal tissue of the animal genus. After the intervention period, venous blood samples were obtained, and renal tissue samples were harvested for comparisons. Normal histological morphology was determined with Masson trichrome staining and periodic acid-Schiff staining in the control group. Atrophic glomerular structures, vacuolated tubule cells, and degeneration were detected in the renal samples of the study group with Masson trichrome staining. Additionally, flattening was observed on the brush borders of the proximal tubules, and tubular dilatation was visualized with periodic acid-Schiff staining. The histopathologic disruption of renal morphology was verified with detection of significantly elevated kidney function laboratory biomarkers in the study group. Our findings suggests that HBO has adverse effects on renal glomerulus and proximal tubules. However, the functional effects of this alteration should be investigated with further studies.

In situ chemical synthesis of ruthenium oxide/reduced graphene oxide nanocomposites for electrochemical capacitor applications.

PubMed

Kim, Ji-Young; Kim, Kwang-Heon; Yoon, Seung-Beom; Kim, Hyun-Kyung; Park, Sang-Hoon; Kim, Kwang-Bum

2013-08-07

An in situ chemical synthesis approach has been developed to prepare ruthenium oxide/reduced graphene oxide (RGO) nanocomposites. It is found that as the C/O ratio increases, the number density of RuO2 nanoparticles decreases, because the chemical interaction between the Ru ions and the oxygen-containing functional groups provides anchoring sites where the nucleation of particles takes place. For electrochemical capacitor applications, the microwave-hydrothermal process was carried out to improve the conductivity of RGO in RuO2/RGO nanocomposites. The significant improvement in capacitance and high rate capability might result from the RuO2 nanoparticles used as spacers that make the interior layers of the reduced graphene oxide electrode available for electrolyte access.

Exploring the Chemistry and Biology of Vanadium-dependent Haloperoxidases*

PubMed Central

Winter, Jaclyn M.; Moore, Bradley S.

2009-01-01

Nature has developed an exquisite array of methods to introduce halogen atoms into organic compounds. Most of these enzymes are oxidative and require either hydrogen peroxide or molecular oxygen as a cosubstrate to generate a reactive halogen atom for catalysis. Vanadium-dependent haloperoxidases contain a vanadate prosthetic group and utilize hydrogen peroxide to oxidize a halide ion into a reactive electrophilic intermediate. These metalloenzymes have a large distribution in nature, where they are present in macroalgae, fungi, and bacteria, but have been exclusively characterized in eukaryotes. In this minireview, we highlight the chemistry and biology of vanadium-dependent haloperoxidases from fungi and marine algae and the emergence of new bacterial members that extend the biological function of these poorly understood halogenating enzymes. PMID:19363038

Effect of simulated commercial flight on oxygenation in patients with interstitial lung disease and chronic obstructive pulmonary disease

PubMed Central

Seccombe, L; Kelly, P; Wong, C; Rogers, P; Lim, S; Peters, M

2004-01-01

Background: Commercial aircraft cabins provide a hostile environment for patients with underlying respiratory disease. Although there are algorithms and guidelines for predicting in-flight hypoxaemia, these relate to chronic obstructive pulmonary disease (COPD) and data for interstitial lung disease (ILD) are lacking. The purpose of this study was to evaluate the effect of simulated cabin altitude on subjects with ILD at rest and during a limited walking task. Methods: Fifteen subjects with ILD and 10 subjects with COPD were recruited. All subjects had resting arterial oxygen pressure (PaO2) of >9.3 kPa. Subjects breathed a hypoxic gas mixture containing 15% oxygen with balance nitrogen for 20 minutes at rest followed by a 50 metre walking task. Pulse oximetry (SpO2) was monitored continuously with testing terminated if levels fell below 80%. Arterial blood gas tensions were taken on room air at rest and after the resting and exercise phases of breathing the gas mixture. Results: In both groups there was a statistically significant decrease in arterial oxygen saturation (SaO2) and PaO2 from room air to 15% oxygen at rest and from 15% oxygen at rest to the completion of the walking task. The ILD group differed significantly from the COPD group in resting 15% oxygen SaO2, PaO2, and room air pH. Means for both groups fell below recommended levels at both resting and when walking on 15% oxygen. Conclusion: Even in the presence of acceptable arterial blood gas tensions at sea level, subjects with both ILD and COPD fall below recommended levels of oxygenation when cabin altitude is simulated. This is exacerbated by minimal exercise. Resting sea level arterial blood gas tensions are similarly poor in both COPD and ILD for predicting the response to simulated cabin altitude. PMID:15516473

Capacitive behavior of highly-oxidized graphite

NASA Astrophysics Data System (ADS)

Ciszewski, Mateusz; Mianowski, Andrzej

2014-09-01

Capacitive behavior of a highly-oxidized graphite is presented in this paper. The graphite oxide was synthesized using an oxidizing mixture of potassium chlorate and concentrated fuming nitric acid. As-oxidized graphite was quantitatively and qualitatively analyzed with respect to the oxygen content and the species of oxygen-containing groups. Electrochemical measurements were performed in a two-electrode symmetric cell using KOH electrolyte. It was shown that prolonged oxidation causes an increase in the oxygen content while the interlayer distance remains constant. Specific capacitance increased with oxygen content in the electrode as a result of pseudo-capacitive effects, from 0.47 to 0.54 F/g for a scan rate of 20 mV/s and 0.67 to 1.15 F/g for a scan rate of 5 mV/s. Better cyclability was observed for the electrode with a higher oxygen amount.

Computational Investigation of Amine–Oxygen Exciplex Formation

PubMed Central

Haupert, Levi M.; Simpson, Garth J.; Slipchenko, Lyudmila V.

2012-01-01

It has been suggested that fluorescence from amine-containing dendrimer compounds could be the result of a charge transfer between amine groups and molecular oxygen [Chu, C.-C.; Imae, T. Macromol. Rapid Commun. 2009, 30, 89.]. In this paper we employ equation-of-motion coupled cluster computational methods to study the electronic structure of an ammonia–oxygen model complex to examine this possibility. The results reveal several bound electronic states with charge transfer character with emission energies generally consistent with previous observations. However, further work involving confinement, solvent, and amine structure effects will be necessary for more rigorous examination of the charge transfer fluorescence hypothesis. PMID:21812447

Impact of chronic obstructive pulmonary disease on family functioning.

PubMed

Kanervisto, Merja; Paavilainen, Eija; Astedt-Kurki, Päivi

2003-01-01

The purpose of this study was to ascertain family dynamics of Finnish patients with severe chronic obstructive pulmonary disease (COPD) on the basis of Barnhill's framework for healthy family functioning. This study used description and comparison and an interview-administered questionnaire and survey. Participants were patients with COPD and their family members (n = 65) living in the Tampere University Hospital catchment area. The sample consisted of families of home oxygen therapy patients (n = 36) and families of inpatients (n = 29). Families consisted of patients and their family members. Data were collected from patients by interview-administered questionnaires and from family members by survey. The instrument used was the Family Dynamics Measure 2, operationalized and tested by the American Family Research Group. Families of home oxygen therapy patients experienced significantly more mutuality (P =.03) and made decisions about their illness and life significantly more independently (P =.05) than families of inpatients. Families of home oxygen therapy patients handled change significantly more flexibly (P =.03) than families of inpatients. For the most part, families of both patient groups functioned well, but overall family functioning was clearly better in families of home oxygen therapy patients. The sample included some dysfunctional and even severely dysfunctional families. The results of this study cannot be generalized beyond the study sample because of the small sample size, but they provide suggestions for developing the care of patients with COPD and their families.

Analysis of oxidised heavy paraffininc products by high temperature comprehensive two-dimensional gas chromatography.

PubMed

Potgieter, H; Bekker, R; Beigley, J; Rohwer, E

2017-08-04

Heavy petroleum fractions are produced during crude and synthetic crude oil refining processes and they need to be upgraded to useable products to increase their market value. Usually these fractions are upgraded to fuel products by hydrocracking, hydroisomerization and hydrogenation processes. These fractions are also upgraded to other high value commercial products like lubricant oils and waxes by distillation, hydrogenation, and oxidation and/or blending. Oxidation of hydrogenated heavy paraffinic fractions produces high value products that contain a variety of oxygenates and the characterization of these heavy oxygenates is very important for the control of oxidation processes. Traditionally titrimetric procedures are used to monitor oxygenate formation, however, these titrimetric procedures are tedious and lack selectivity toward specific oxygenate classes in complex matrices. Comprehensive two-dimensional gas chromatography (GC×GC) is a way of increasing peak capacity for the comprehensive analysis of complex samples. Other groups have used HT-GC×GC to extend the carbon number range attainable by GC×GC and have optimised HT-GC×GC parameters for the separation of aromatics, nitrogen-containing compounds as well as sulphur-containing compounds in heavy petroleum fractions. HT-GC×GC column combinations for the separation of oxygenates in oxidised heavy paraffinic fractions are optimised in this study. The advantages of the HT-GC×GC method in the monitoring of the oxidation reactions of heavy paraffinic fraction samples are illustrated. Copyright © 2017 Elsevier B.V. All rights reserved.

Early sepsis does not stimulate reactive oxygen species production and does not reduce cardiac function despite an increased inflammation status.

PubMed

Léger, Thibault; Charrier, Alice; Moreau, Clarisse; Hininger-Favier, Isabelle; Mourmoura, Evangelia; Rigaudière, Jean-Paul; Pitois, Elodie; Bouvier, Damien; Sapin, Vincent; Pereira, Bruno; Azarnoush, Kasra; Demaison, Luc

2017-07-01

If it is sustained for several days, sepsis can trigger severe abnormalities of cardiac function which leads to death in 50% of cases. This probably occurs through activation of toll-like receptor-9 by bacterial lipopolysaccharides and overproduction of proinflammatory cytokines such as TNF- α and IL-1 β In contrast, early sepsis is characterized by the development of tachycardia. This study aimed at determining the early changes in the cardiac function during sepsis and at finding the mechanism responsible for the observed changes. Sixty male Wistar rats were randomly assigned to two groups, the first one being made septic by cecal ligation and puncture (sepsis group) and the second one being subjected to the same surgery without cecal ligation and puncture (sham-operated group). The cardiac function was assessed in vivo and ex vivo in standard conditions. Several parameters involved in the oxidative stress and inflammation were determined in the plasma and heart. As evidenced by the plasma level of TNF- α and gene expression of IL-1 β and TNF- α in the heart, inflammation was developed in the sepsis group. The cardiac function was also slightly stimulated by sepsis in the in vivo and ex vivo situations. This was associated with unchanged levels of oxidative stress, but several parameters indicated a lower cardiac production of reactive oxygen species in the septic group. In conclusion, despite the development of inflammation, early sepsis did not increase reactive oxygen species production and did not reduce myocardial function. The depressant effect of TNF- α and IL-1 β on the cardiac function is known to occur at very high concentrations. The influence of low- to moderate-grade inflammation on the myocardial mechanical behavior must thus be revisited. © 2017 French National Institute of Agronomical Research (INRA). Physiological Reports published by Wiley Periodicals, Inc. on behalf of The Physiological Society and the American Physiological Society.

[Hemoglobin, from microorganisms to man: a single structural motif, multiple functions].

PubMed

Wajcman, Henri; Kiger, Laurent

2002-12-01

Haemoglobins from unicellular organisms, plants or animals, share a common structure, which results from the folding, around the heme group, of a polypeptide chain made from 6-8 helices. Nowadays, deciphering the genome of several species allows one to draw the evolutionary tree of this protein going back to 1800 millions of years, at a time when oxygen began to accumulate in the atmosphere. This permits to follow the evolution of the ancestral gene and of its product. It is likely that, only in complex multicellular species, transport and storage of oxygen became the main physiological function of this molecule. In addition, in unicellular organisms and small invertebrates, it is likely that the main function of this protein was to protect the organism from the toxic effect of O2, CO and NO*. The very high oxygen affinity of these molecules, leading them to act rather as a scavenger as an oxygen carrier, supports this hypothesis. Haemoglobins from microorganisms, which may probably be the closest vestiges to the ancestral molecules, are divided into three families. The first one is made from flavohaemoglobins, a group of chimerical proteins carrying a globin domain and an oxido-reduction FAD-dependant domain. The second corresponds to truncated haemoglobins, which are hexacoordinated with very high oxygen-affinity molecules, 20-40 residues shorter than classical haemoglobins. The third group is made from bacterial haemoglobins such as that of Vitreoscilla. Some specific structural arrangements in the region surrounding the heme are cause of their high oxygen affinity. In plants, two types of haemoglobins are present (non-symbiotic and symbiotic), that arose from duplication of an ancestral vegetal gene. Non-symbiotic haemoglobins, which are probably the oldest, are scarcely distributed within tissues having high energetic consumption. Conversely, symbiotic haemoglobins (also named leghaemoglobins) are present at a high concentration (mM) mostly in the rhizomes of legumes, where they are involved in nitrogen metabolism. In some species, haemoglobin was proposed to be an oxygen sensor bringing to the organism information to adjust metabolism or biosynthesis to the oxygen requirement. Elsewhere haemoglobin may act as final electron acceptors in oxido-reduction pathways. Evolution of haemoglobin in invertebrates followed a large variety of scenarios. Some surprising functions as sulphide acquisition in invertebrates living near hydrothermal vents, or a role in the phototrophism of worm need to be mentioned. In invertebrates, the size of haemoglobin varies from monomers to giant molecules associating up to 144 subunits, while in vertebrates it is always a tetramer. In some species, several haemoglobins, with completely different structure and function, may coexist. This demonstrates how hazardous may be to extrapolate the function of a protein from only structural data.

Triiodothyronine Activates Lactate Oxidation Without Impairing Fatty Acid Oxidation and Improves Weaning From Extracorporeal Membrane Oxygenation

PubMed Central

Kajimoto, Masaki; Ledee, Dolena R.; Xu, Chun; Kajimoto, Hidemi; Isern, Nancy G.; Portman, Michael A.

2017-01-01

Background Extracorporeal membrane oxygenation (ECMO) provides a rescue for children with severe cardiac failure. It has previously been shown that triiodothyronine (T3) improves cardiac function by modulating pyruvate oxidation during weaning. This study focused on fatty acid (FA) metabolism modulated by T3 for weaning from ECMO after cardiac injury. Methods and Results Nineteen immature piglets (9.1–15.3 kg) were separated into 3 groups with ECMO (6.5 h) and wean: normal circulation (Group-C); transient coronary occlusion (10 min) for ischemia-reperfusion (IR) followed by ECMO (Group-IR); and IR with T3 supplementation (Group-IR-T3). 13-Carbon (13C)-labeled lactate, medium-chain and long-chain FAs, was infused as oxidative substrates. Substrate fractional contribution (FC) to the citric acid cycle was analyzed by 13C-nuclear magnetic resonance. ECMO depressed circulating T3 levels to 40% of the baseline at 4 h and were restored in Group-IR-T3. Group-IR decreased cardiac power, which was not fully restorable and 2 pigs were lost because of weaning failure. Group-IR also depressed FC-lactate, while the excellent contractile function and energy efficiency in Group-IR-T3 occurred along with a marked FC-lactate increase and [adenosine triphosphate]/[adenosine diphosphate] without either decreasing FC-FAs or elevating myocardial oxygen consumption over Group-C or -IR. Conclusions T3 releases inhibition of lactate oxidation following IR injury without impairing FA oxidation. These findings indicate that T3 depression during ECMO is maladaptive, and that restoring levels improves metabolic flux and enhances contractile function during weaning. PMID:25421230

Modulatory effects of dietary inclusion of garlic (Allium sativum) on gentamycin-induced hepatotoxicity and oxidative stress in rats.

PubMed

Ademiluyi, Adedayo O; Oboh, Ganiyu; Owoloye, Tosin R; Agbebi, Oluwaseun J

2013-06-01

To investigate the ameliorative effect of dietary inclusion of garlic (Allium sativum) on gentamycin-induced hepatotoxicity in rats. Adult male rats were randomly divided into four groups with six animals in each group. Groups 1 and 2 were fed basal diet while Groups 3 and 4 were fed diets containing 2% and 4% garlic respectively for 27 d prior to gentamycin administration. Hepatotoxicity was induced by the intraperitoneal administration of gentamycin (100 mg/kg body weight) for 3 d. The liver and plasma were studied for hepatotoxicity and antioxidant indices. Gentamycin induces hepatic damage as revealed by significant (P<0.05) elevation of liver damage marker enzymes (aspartate transaminase and alanine aminotransferase) and reduction in plasma albumin level. Gentamycin also caused a significant (P<0.05) alteration in plasma and liver enzymatic (catalase, glutathione and super oxygen dehydrogenises) and non-enzymatic (glutathione and vitamin C) antioxidant indices with concomitant increase in the malondialdehyde content; however, there was a significant (P<0.05) restoration of the antioxidant status coupled with significant (P<0.05) decrease in the tissues' malondialdehyde content, following consumption of diets containing garlic. These results suggest that dietary inclusion of garlic powder could protect against gentamycin-induced hepatotoxicity, improve antioxidant status and modulate oxidative stress; a function attributed to their phenolic constituents.

Drug abusers have impaired cerebral oxygenation and cognition during exercise

PubMed Central

Soares Rachetti, Vanessa; Quirino Alves da Silva, Weslley; Aranha Rego Cabral, Daniel; Gomes da Silva Machado, Daniel; Caldas Costa, Eduardo; Forti, Rodrigo Menezes; Mesquita, Rickson Coelho; Elsangedy, Hassan Mohamed; Hideki Okano, Alexandre; Bodnariuc Fontes, Eduardo

2017-01-01

Background Individuals with Substance Use Disorder (SUD) have lower baseline metabolic activity of the prefrontal cortex (PFC) associated with impairment of cognitive functions in decision-making and inhibitory control. Aerobic exercise has shown to improve PFC function and cognitive performance, however, its effects on SUD individuals remain unclear. Purpose To verify the cognitive performance and oxygenation of the PFC during an incremental exercise in SUD individuals. Methods Fourteen individuals under SUD treatment performed a maximum graded exercise test on a cycle ergometer with continuous measurements of oxygen consumption, PFC oxygenation, and inhibitory control (Stroop test) every two minutes of exercise at different intensities. Fifteen non-SUD individuals performed the same protocol and were used as control group. Results Exercise increased oxyhemoglobin (O2Hb) and total hemoglobin (tHb) by 9% and 7%, respectively. However, when compared to a non-SUD group, this increase was lower at high intensities (p<0.001), and the inhibitory cognitive control was lower at rest and during exercise (p<0.007). In addition, PFC hemodynamics during exercise was inversely correlated with inhibitory cognitive performance (reaction time) (r = -0.62, p = 0.001), and a lower craving perception for the specific abused substance (p = 0.0189) was reported immediately after exercise. Conclusion Despite SUD individuals having their PFC cerebral oxygenation increased during exercise, they presented lower cognition and oxygenation when compared to controls, especially at elevated intensities. These results may reinforce the role of exercise as an adjuvant treatment to improve PFC function and cognitive control in individuals with SUD. PMID:29125875

Athletes and Sedentary Individuals: An Intergroup Comparison Utilizing a Pulmonary Function Ratio Obtained During Submaximal Exercise.

ERIC Educational Resources Information Center

Maud, Peter J.

A pulmonary function ratio describing oxygen extraction from alveolar ventilation was used for an intergroup comparison between three groups of athletes (rugby, basketball, and football players) and one group of sedentary subjects during steady-state submaximal exercise. The ratio and its component parts are determined from only three gas…

Strongly coupled inorganic-nano-carbon hybrid materials for energy storage.

PubMed

Wang, Hailiang; Dai, Hongjie

2013-04-07

The global shift of energy production from fossil fuels to renewable energy sources requires more efficient and reliable electrochemical energy storage devices. In particular, the development of electric or hydrogen powered vehicles calls for much-higher-performance batteries, supercapacitors and fuel cells than are currently available. In this review, we present an approach to synthesize electrochemical energy storage materials to form strongly coupled hybrids (SC-hybrids) of inorganic nanomaterials and novel graphitic nano-carbon materials such as carbon nanotubes and graphene, through nucleation and growth of nanoparticles at the functional groups of oxidized graphitic nano-carbon. We show that the inorganic-nano-carbon hybrid materials represent a new approach to synthesize electrode materials with higher electrochemical performance than traditional counterparts made by simple physical mixtures of electrochemically active inorganic particles and conducting carbon materials. The inorganic-nano-carbon hybrid materials are novel due to possible chemical bonding between inorganic nanoparticles and oxidized carbon, affording enhanced charge transport and increased rate capability of electrochemical materials without sacrificing specific capacity. Nano-carbon with various degrees of oxidation provides a novel substrate for nanoparticle nucleation and growth. The interactions between inorganic precursors and oxidized-carbon substrates provide a degree of control over the morphology, size and structure of the resulting inorganic nanoparticles. This paper reviews the recent development of inorganic-nano-carbon hybrid materials for electrochemical energy storage and conversion, including the preparation and functionalization of graphene sheets and carbon nanotubes to impart oxygen containing groups and defects, and methods of synthesis of nanoparticles of various morphologies on oxidized graphene and carbon nanotubes. We then review the applications of the SC-hybrid materials for high performance lithium ion batteries, rechargeable Li-S and Li-O2 batteries, supercapacitors and ultrafast Ni-Fe batteries, and new electrocatalysts for oxygen reduction, oxygen evolution and hydrogen evolution reactions.

Application of atmospheric pressure plasma in polymer and composite adhesion

NASA Astrophysics Data System (ADS)

Yu, Hang

An atmospheric pressure helium and oxygen plasma was used to investigate surface activation and bonding in polymer composites. This device was operated by passing 1.0-3.0 vol% of oxygen in helium through a pair of parallel plate metal electrodes powered by 13.56 or 27.12 MHz radio frequency power. The gases were partially ionized between the capacitors where plasma was generated. The reactive species in the plasma were carried downstream by the gas flow to treat the substrate surface. The temperature of the plasm gas reaching the surface of the substrate did not exceed 150 °C, which makes it suitable for polymer processing. The reactive species in the plasma downstream includes ~ 1016-1017 cm-3 atomic oxygen, ~ 1015 cm-3 ozone molecule, and ~ 10 16 cm-3 metastable oxygen molecule (O2 1Deltag). The substrates were treated at 2-5 mm distance from the exit of the plasma. Surface properties of the substrates were characterized using water contact angle (WCA), atomic force microscopy (AFM), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS). Subsequently, the plasma treated samples were bonded adhesively or fabricated into composites. The increase in mechanical strength was correlated to changes in the material composition and structure after plasma treatment. The work presented hereafter establishes atmospheric pressure plasma as an effective method to activate and to clean the surfaces of polymers and composites for bonding. This application can be further expanded to the activation of carbon fibers for better fiber-resin interactions during the fabrication of composites. Treating electronic grade FR-4 and polyimide with the He/O2 plasma for a few seconds changed the substrate surface from hydrophobic to hydrophilic, which allowed complete wetting of the surface by epoxy in underfill applications. Characterization of the surface by X-ray photoelectron spectroscopy shows formation of oxygenated functional groups, including hydroxyl, carbonyl, and carboxyl groups, on the polymer surface after plasma treatment. The resulting strength of the bond based on lap-shear and T-peel tests correlates well with the concentration of oxygen on the polymer surface. The failure modes observed for lap-shear and T-peel tests changed from interfacial to cohesive after the plasma activation. Treating carbon-fiber-reinforced epoxy composites with the atmospheric plasma resulted in the removal of fluorinated contaminants in shallow surface layers. For contaminants that diffused deeply into the composite surface, mechanical abrasion was needed in addition to the plasma treatment to remove the impurities. While cleaning the composite, plasma also generated active oxygen groups on the substrate surface. The presence of these groups improved the adhesive bonding strength of the composite even in the presence of residual fluorine contaminants. Thus, it was speculated that plasma treatment can promote better polymer adhesion with or without fluorine contamination. Carbon nanotube sheets were also treated by the helium oxygen plasma, and the CNT surface turn from super hydrophobic to hydrophilic after a few seconds of exposure. The nanotube surface contained 15% of oxygen in the form of hydroxyl groups. Chemical coupling agents were added to the plasma activated CNT surfaces in order to crosslink the CNTs and to create bonding sites for the resin matrix. Stretched, activated and functionalized CNT was cured with dicyclopentadiene (DCPD) to produce a sheet composite with a tensile strength of 636 MPa, a modulus of 28 GPa, and a density of 1.4 g/cm 3. This may be compared to aerospace-grade aluminum with tensile strength of 572 MPa, modulus of 72 GPa, and density of 2.7 g/cm3. This work demonstrates that new high-strength composite can be produced with the use of atmospheric plasma activation and chemical crosslinking of the fiber matrix.

Feed gas contaminant removal in ion transport membrane systems

DOEpatents

Underwood, Richard Paul [Allentown, PA; Makitka, III, Alexander; Carolan, Michael Francis [Allentown, PA

2012-04-03

An oxygen ion transport membrane process wherein a heated oxygen-containing gas having one or more contaminants is contacted with a reactive solid material to remove the one or more contaminants. The reactive solid material is provided as a deposit on a support. The one or more contaminant compounds in the heated oxygen-containing gas react with the reactive solid material. The contaminant-depleted oxygen-containing gas is contacted with a membrane, and oxygen is transported through the membrane to provide transported oxygen.

Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

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

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.

2015-09-01

The noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The findings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. The structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogen bonding with terminalmore » hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. These results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.« less

Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

DOE PAGES

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.; ...

2015-09-01

For the noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The fi ndings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. Moreover, the structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogenmore » bonding with terminal hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. Finally, these results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.« less

Determination of the origin and magnitude of Al/Si ordering enthalpy in framework aluminosilicates from ab initio calculations

NASA Astrophysics Data System (ADS)

McConnell, J. D. C.; De Vita, A.; Kenny, S. D.; Heine, V.

Ab initio total energy calculations based on a new optimised oxygen pseudopotential has been used to determine the enthalpy of disorder for the exchange of Al and Si in tetrahedral coordination in simple derivative aluminosilicate structures based on the high temperature tridymite structure. The problem has been studied as a function of defect interaction, and defect concentration, and the results indicate that the energy for Al/Al neighbouring tetrahedra can be assigned primarily to two effects, the first, a coulombic effect, associated with the disturbed charge distribution, and the second associated with the strain related to misfit due to the very different dimensions of the Si and Al containing tetrahedra. In practice each of these effects contributes approximately 0.2 eV per Al-Al neighbour to the overal disorder enthalpy. These simple results were obtained after a careful study of possible chemical interaction between adjacent Al/Si containing tetrahedra which showed that chemical interaction was effectively absent. Since individual Al/Si tetrahedra proved to be discrete entities that are individually heavily screened by the shared oxygens it follows that coulombic and strain effects in disorder effectively account for the whole of the disorder enthalpy. The complete set of results have been used to establish new criteria for the structure and disorder enthalpies of the feldspar group of minerals and their long period derivatives.

The synthesis of chlorophyll-a biosynthetic precursors and methyl substituted iron porphyrins

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

Matera, K.M.

1988-01-01

The biosynthetic intermediates were incubated in a plant system. The activity levels calculated show that magnesium 6-acrylate porphyrins and one of the magnesium 6-{beta}-hydroxypropionate porphyrins are not intermediates. In addition, plant systems incubated with {sup 18}O{sub 2} were found to synthesize magnesium 2,4-divinyl pheoporphyrin-a{sub 5} incorporated with {sup 18}O at the 9-carbonyl oxygen. Mass spectroscopy confirmed the presence of the oxygen label, thus eliminating one of two hypothesized pathways to chlorophyll-a. An overall description is given of iron porphyrins and iron porphyrin containing proteins. The function of the propionic side chains of the heme prosthetic group during electron transport reactionsmore » will be investigated. The synthesis of a series of iron(III) hexamethyl porphyrins with increasingly longer substituents in the remaining two peripheral positions of the porphyrin is described. Models for NMR studies of iron chlorin containing enzymes are discussed. Iron(III) pyropheophorbide-a and methyl pyropheophorbide-a were synthesized in addition to 5-CD{sub 3}, 10-CD{sub 2} iron(III) pyropheophorbide-a and methyl pyropheophorbide-a. Together, these pyropheophorbides were used to assign NMR resonances and ultimately provide a model for other iron chlorins. The synthesis of nickel(II) anhydro-mesorhodoporphyrin from zinc(III) anhydromesorhodochlorin is described; this nickel porphyrin was used as a standard for ring current calculations of reduced nickel analogs of anhydromesorhodoporphyrin.« less

Neutron diffraction study of water freezing on aircraft engine combustor soot.

PubMed

Tishkova, V; Demirdjian, B; Ferry, D; Johnson, M

2011-12-14

The study of the formation of condensation trails and cirrus clouds on aircraft emitted soot particles is important because of its possible effects on climate. In the present work we studied the freezing of water on aircraft engine combustor (AEC) soot particles under conditions of pressure and temperature similar to the upper troposphere. The microstructure of the AEC soot was found to be heterogeneous containing both primary particles of soot and metallic impurities (Fe, Cu, and Al). We also observed various surface functional groups such as oxygen-containing groups, including sulfate ions, that can act as active sites for water adsorption. Here we studied the formation of ice on the AEC soot particles by using neutron diffraction. We found that for low amount of adsorbed water, cooling even up to 215 K did not lead to the formation of hexagonal ice. Whereas, larger amount of adsorbed water led to the coexistence of liquid water (or amorphous ice) and hexagonal ice (I(h)); 60% of the adsorbed water was in the form of ice I(h) at 255 K. Annealing of the system led to the improvement of the crystal quality of hexagonal ice crystals as demonstrated from neutron diffraction.

Well-Defined Metal-O6 in Metal-Catecholates as a Novel Active Site for Oxygen Electroreduction.

PubMed

Liu, Xuan-He; Hu, Wei-Li; Jiang, Wen-Jie; Yang, Ya-Wen; Niu, Shuai; Sun, Bing; Wu, Jing; Hu, Jin-Song

2017-08-30

Metal-nitrogen coordination sites, M-N x (M = Fe, Co, Ni, etc.), have shown great potential to replace platinum group materials as electrocatalysts for oxygen reduction reaction (ORR). However, the real active site in M-N x is still vague to date due to their complicated structure and composition. It is therefore highly desirable but challenging to develop ORR catalysts with novel and clear active sites, which could meet the needs of comprehensive understanding of structure-function relationships and explore new cost-effective and efficient ORR electrocatalysts. Herein, well-defined M-O 6 coordination in metal-catecholates (M-CATs, M = Ni or Co) is discovered to be catalytically active for ORR via a four-electron-dominated pathway. In view of no pyrolysis involved and unambiguous crystalline structure of M-CATs, the M-O 6 octahedral coordination site with distinct structure is determined as a new type of active site for ORR. These findings extend the scope of metal-nonmetal coordination as an active site for ORR and pave a way for bottom-up design of novel electrocatalysts containing M-O 6 coordination.

Propolis as a green corrosion inhibitor for bronze in weakly acidic solution

NASA Astrophysics Data System (ADS)

Varvara, Simona; Bostan, Roxana; Bobis, Otilia; Găină, Luiza; Popa, Florin; Mena, Vicente; Souto, Ricardo M.

2017-12-01

In the present work, the inhibitive action of natural propolis on bronze corrosion in a weakly acidic solution containing Na2SO4 and NaHCO3 at pH 5 was evaluated using multiscale electrochemical techniques, namely potentiodynamic polarization, electrochemical impedance spectroscopy and scanning vibrating electrode technique measurements. The major constituents of propolis were identified by HPLC. Surface characterization was performed by SEM-EDX and AFM analysis. Experiments were performed as a function of the propolis concentration and immersion time in the corrosive electrolyte. The obtained results showed that propolis presents good anticorrosive properties on bronze, acting as a mixed-type inhibitor, but its protective effectiveness is time-dependent. The highest inhibiting efficiency of 98.9% was obtained in the presence of 100 ppm propolis, after about 12 h of exposure to inhibitor-containing electrolyte through the stabilization of Cu2O on the bronze surface. The inhibitive properties of propolis on bronze corrosion are likely due to the adsorption of its main constituents (flavonoids and phenolic compounds), through the oxygen atoms in their functional groups and aromatic rings, which have been evidenced by FT-IR spectra. The adsorption of propolis on bronze was found to follow Langmuir adsorption isotherm.

Updating of working memory in ecstasy polydrug users: Findings from fNIRS.

PubMed

Montgomery, Catharine; Fisk, John E; Roberts, Carl A

2017-05-01

Cognitive deficits are now well documented in ecstasy (MDMA) users with type and relative demand of task emerging as important factors. The updating component of executive processes appears to be particularly affected. The study reported here used functional near infrared spectroscopy imaging to investigate changes in cortical haemodynamics during memory updating. Twenty ecstasy users and 20 non-users completed verbal and spatial memory updating tasks and brain blood oxygenation and deoxygenation change was measured using functional near infrared spectroscopy. There was no interaction between group and difficulty on the updating tasks, though there was a significant main effect of difficulty on both tasks. The effects of group approached significance on the verbal updating task. There were significant differences in blood oxygenation and deoxygenation change at optodes centred over the right and left dorsolateral prefrontal cortex, with ecstasy users showing greater blood oxygenation than the other groups. The lack of a behavioural difference on both tasks but presence of blood oxygenation and deoxygenation changes in letter updating provides support for the notion that ecstasy-polydrug users are investing more effort to achieve the same behavioural output. Total lifetime dose was high, and recency of use was significantly related to most changes, suggesting that heavy and recent use may be particularly detrimental. Copyright © 2017 John Wiley & Sons, Ltd.

Predict the glass transition temperature and plasticization of β-cyclodextrin/water binary system by molecular dynamics simulation.

PubMed

Zhou, Guohui; Zhao, Tianhai; Wan, Jie; Liu, Chengmei; Liu, Wei; Wang, Risi

2015-01-12

The glass transition temperature, diffusion behavior and plasticization of β-cyclodextrin (β-CD), and three amorphous β-CD/water mixtures (3%, 5% and 10% [w/w] water, respectively) were investigated by molecular dynamics simulation, which were performed using Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) force field and isothermal-isobaric ensembles. The specific volumes of four amorphous cells were obtained as a function of temperature. The glass transition temperatures (T(g)) were estimated to be 334.25 K, 325.12 K, 317.32 K, and 305.41 K for amorphous β-CD containing 0%, 3%, 5% and 10% w/w water, respectively, which compares well with the values observed in published literature. The radial distribution function was computed to elucidate the intermolecular interactions between amorphous β-CD and water, which acts as a plasticizer. These results indicate that the hydrogen bond interactions of oxygen in hydroxyl ions was higher than oxygen in acetal groups in β-CD amorphous mixtures with that in water, due to less accessibility of ring oxygens to the surrounding water molecules. The mobility of water molecules was investigated over various temperature ranges, including the rubbery and glassy phases of the β-CD/water mixtures, by calculating the diffusion coefficients and the fractional free volume. In β-CD amorphous models, the higher mobility of water molecules was observed at temperatures above Tg, and almost no change was observed at temperatures below T(g). Copyright © 2014 Elsevier Ltd. All rights reserved.

Cuticular gas exchange by Antarctic sea spiders.

PubMed

Lane, Steven J; Moran, Amy L; Shishido, Caitlin M; Tobalske, Bret W; Woods, H Arthur

2018-04-25

Many marine organisms and life stages lack specialized respiratory structures, like gills, and rely instead on cutaneous respiration, which they facilitate by having thin integuments. This respiratory mode may limit body size, especially if the integument also functions in support or locomotion. Pycnogonids, or sea spiders, are marine arthropods that lack gills and rely on cutaneous respiration but still grow to large sizes. Their cuticle contains pores, which may play a role in gas exchange. Here, we examined alternative paths of gas exchange in sea spiders: (1) oxygen diffuses across pores in the cuticle, a common mechanism in terrestrial eggshells, (2) oxygen diffuses directly across the cuticle, a common mechanism in small aquatic insects, or (3) oxygen diffuses across both pores and cuticle. We examined these possibilities by modeling diffusive oxygen fluxes across all pores in the body of sea spiders and asking whether those fluxes differed from measured metabolic rates. We estimated fluxes across pores using Fick's law parameterized with measurements of pore morphology and oxygen gradients. Modeled oxygen fluxes through pores closely matched oxygen consumption across a range of body sizes, which means the pores facilitate oxygen diffusion. Furthermore, pore volume scaled hypermetrically with body size, which helps larger species facilitate greater diffusive oxygen fluxes across their cuticle. This likely presents a functional trade-off between gas exchange and structural support, in which the cuticle must be thick enough to prevent buckling due to external forces but porous enough to allow sufficient gas exchange. © 2018. Published by The Company of Biologists Ltd.

29 CFR 1910.104 - Oxygen.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., section VII—Unfired Pressure Vessels—1968. Insulation surrounding the liquid oxygen container shall be... in § 1910.6. (iv) Insulation. Insulation casings on liquid oxygen containers shall be equipped with... oxygen and heating medium sections with safety relief devices. (iii) Heating. Heat used in an oxygen...

29 CFR 1910.104 - Oxygen.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., section VII—Unfired Pressure Vessels—1968. Insulation surrounding the liquid oxygen container shall be... in § 1910.6. (iv) Insulation. Insulation casings on liquid oxygen containers shall be equipped with... oxygen and heating medium sections with safety relief devices. (iii) Heating. Heat used in an oxygen...

29 CFR 1910.104 - Oxygen.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., section VII—Unfired Pressure Vessels—1968. Insulation surrounding the liquid oxygen container shall be... in § 1910.6. (iv) Insulation. Insulation casings on liquid oxygen containers shall be equipped with... oxygen and heating medium sections with safety relief devices. (iii) Heating. Heat used in an oxygen...

29 CFR 1910.104 - Oxygen.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., Section VII—Unfired Pressure Vessels—1968. Insulation surrounding the liquid oxygen container shall be... in § 1910.6. (iv) Insulation. Insulation casings on liquid oxygen containers shall be equipped with... oxygen and heating medium sections with safety relief devices. (iii) Heating. Heat used in an oxygen...

29 CFR 1910.104 - Oxygen.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., section VII—Unfired Pressure Vessels—1968. Insulation surrounding the liquid oxygen container shall be... in § 1910.6. (iv) Insulation. Insulation casings on liquid oxygen containers shall be equipped with... oxygen and heating medium sections with safety relief devices. (iii) Heating. Heat used in an oxygen...

Artificial oxygen transport protein

DOEpatents

Dutton, P. Leslie

2014-09-30

This invention provides heme-containing peptides capable of binding molecular oxygen at room temperature. These compounds may be useful in the absorption of molecular oxygen from molecular oxygen-containing atmospheres. Also included in the invention are methods for treating an oxygen transport deficiency in a mammal.

Activated Carbon Preparation and Modification for Adsorption

NASA Astrophysics Data System (ADS)

Cao, Yuhe

Butanol is considered a promising, infrastructure-compatible biofuel. Butanol has a higher energy content than ethanol and can be used in conventional gas engines without modifications. Unfortunately, the fermentation pathway for butanol production is restricted by its toxicity to the microbial strains used in the process. Butanol is toxic to the microbes, and this can slow fermentation rates and reduce butanol yields. Gas stripping technology can efficiently remove butanol from the fermentation broth as it is produced, thereby decreasing its inhibitory effects. Traditional butanol separation heavily depends on the energy intensive distillation method. One of the main issues in acetone-butanol-ethanol fermentation is that butanol concentrations in the fermentation broth are low, ranging from 1 to 1.2 percent in weight, because of its toxicity to the microorganisms. Therefore distillation of butanol is even worse than distillation of corn ethanol. Even new separation methods, such as solid- extraction methods involve adding substances, such as polymer resin and zeolite or activated carbon, to biobutanol fermentatioon broth did not achieve energy efficient separation of butanol due to low adsorption selectivity and fouling in broth. Gas-stripping - condensation is another new butanol recovery method, however, the butanol in gas-stripping stream is too low to be condensed without using expensive and energy intensive liquid nitrogen. Adsorption can then be used to recover butanol from the vapor phase. Activated carbon (AC) samples and zeolite were investigated for their butanol vapor adsorption capacities. Commercial activated carbon was modified via hydrothermal H2O2 treatment, and the specific surface area and oxygen-containing functional groups of activated carbon were tested before and after treatment. Hydrothermal H2O 2 modification increased the surface oxygen content, Brunauer-Emmett-Teller surface area, micropore volume, and total pore volume of active carbon. The adsorption capacities of these active carbon samples were almost three times that of zeolite. However, the un-modified active carbon had the highest adsorption capacity for butanol vapor (259.6 mg g-1), compared to 222.4 mg g-1 after 10% H2O2 hydrothermal treatment. Both modified and un-modified active carbon can be easily regenerated for repeatable adsorption by heating to 150 °C. Therefore, surface oxygen groups significantly reduced the adsorption capacity of active carbons for butanol vapor. In addition, original active carbon and AC samples modified by nitric acid hydrothermal modification were assessed for their ability to adsorb butanol vapor. The specific surface area and oxygen-containing functional groups of AC were tested before and after modification. The adsorption capacity of unmodified AC samples were the highest. Hydrothermal oxidation of AC with HNO3 increased the surface oxygen content, Brunauer-Emmett-Teller (BET) surface area, micropore, mesopore and total pore volume of AC. Although the pore structure and specific surface area were greatly improved after hydrothermal oxidization with 4 M HNO3, the increased oxygen on the surface of AC decreased the dynamic adsorption capacity. In order to get high adsorption capacity adsorbents, we used corn stalk as precursor to fabricate porous carbon. ACs were prepared through chemical activation of biochar from whole corn stalk (WCS) and corn stalk pith (CSP) at varying temperatures using potassium hydroxide as the activating agent. ACs were characterized via pore structural analysis and scanning electron microscopy (SEM). These adsorbents were then assessed for their adsorption capacity for butanol vapor. It was found that WCS activated at 900 °C for 1 h (WCS-900) had optimal butanol adsorption characteristics. The BET surface area and total pore volume of the WCS-900 were 2330 m2 g-1 and 1.29 cm3 g-1, respectively. The dynamic adsorption capacity of butanol vapor was 410.0 mg g-1, a 185.1 % increase compared to charcoal-based commercial AC (143.8 mg g -1). Based on the adsorption experiments of butanol vapor, we found the chemical properties of the AC surface play an important role in adsorbing molecules. The adsorption of creatinine on active carbons was also studied, which is a toxic compound generated by human. High levels of creatinine in the blood stream is normally caused by malfunction or failure of the kidneys. Activated carbons is taken by the patients orally to reduce creatinine level. In order to figure out whether chemical modification could increase the adsorption capacity of creatinine, AC samples modified by nitric acid hydrothermal modification were assessed for their ability to adsorb creatinine. The pore structure and surface properties of the AC samples were characterized by N 2 adsorption, temperature programmed desorption (TPD), Fourier Transform Infrared spectroscopy (FTIR), and X-ray photoelectron spectrometer (XPS). It indicated that 4M HNO3 hydrothermal modification with 180 °C was an efficient method in improvement of the creatinine adsorption. The improved adsorption capacity can be attributed mainly to an increase in the acidic oxygen-containing functional groups. The adsorption of creatinine over AC may involve an interaction with the acidic oxygen-containing groups on AC. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherm and isotherm constants. Equilibrium data fitted very well to the Freundlich model in the entire saturation range (3.58-59.08 mg L-1 ). The maximum adsorption capacities of AC modified with 180 °C is 62.5 mg g-1 according to the Langmuir model. Pseudo first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicates that the chemical adsorption was the rate-limiting step, instead of mass transfer. (Abstract shortened by ProQuest.).

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Generation of singlet oxygen in fullerene-containing media: 1. Photodesorption of singlet oxygen from fullerene-containing surfaces

NASA Astrophysics Data System (ADS)

Belousova, I. M.; Belousov, V. P.; Danilov, O. B.; Ermakov, A. V.; Kiselev, V. M.; Kislyakov, I. M.; Sosnov, E. N.

2008-03-01

It is shown that upon irradiation of fullerene-containing surfaces by laser or flashlamp pulses, oxygen adsorbed by these surfaces efficiently escapes to the gas phase. The observation of luminescence pulses in the spectral region of 762 and 1268 nm confirms the presence of oxygen molecules in the excited singlet state in the desorbed oxygen. The conditions for optimisation of the efficiency of singlet-oxygen production are studied. It is shown that singlet oxygen at the concentration sufficient for obtaining operation of a fullerene-oxygen-iodine laser can be produced in this way.

Study of the tritium behavior on the surface of Li 2O by means of work function measurement

NASA Astrophysics Data System (ADS)

Yokota, Toshihiko; Suzuki, Atsushi; Yamaguchi, Kenji; Terai, Takayuki; Yamawaki, Michio

2000-12-01

In the present study, the work function change of Li 2O due to change of oxygen potential of sweep gas was investigated by measuring the contact potential difference (CPD) between Li 2O and Pt electrodes with a so-called `high temperature Kelvin probe'. The CPD change for Li 2O was generally insensitive to the oxygen partial pressure in the sweep gas. A similar insensitivity was also observed for LiAlO 2. Although the CPD change of Li 2O was about 200 mV when the oxygen partial pressure was changed by as much as 15 orders of magnitude, such was not the case for LiAlO 2. By comparing with the results obtained for other Li-bearing ceramics, it was estimated to be caused by the adsorption/desorption processes of water vapor contained in the sweep gas.

Chemically-modified graphenes for oxidation of DNA bases: analytical parameters.

PubMed

Goh, Madeline Shuhua; Bonanni, Alessandra; Ambrosi, Adriano; Sofer, Zdeněk; Pumera, Martin

2011-11-21

We studied the electroanalytical performances of chemically-modified graphenes (CMGs) containing different defect densities and amounts of oxygen-containing groups, namely graphite oxide (GPO), graphene oxide (GO), thermally reduced graphene oxide (TR-GO) and electrochemically reduced graphene oxide (ER-GO) by comparing the sensitivity, selectivity, linearity and repeatability towards the oxidation of DNA bases. We have observed that for differential pulse voltammetric (DPV) detection of adenine and cytosine, all CMGs showed enhanced sensitivity to oxidation, while for guanine and thymine, ER-GO and TR-GO exhibited much improved sensitivity over bare glassy carbon (GC) as well as over GPO and GO. There is also significant selectivity enhancement when using GPO for adenine and TR-GO for thymine. Our results have uncovered that the differences in surface functionalities, structure and defects of various CMGs largely influence their electrochemical behaviour in detecting the oxidation of DNA bases. The findings in this report will provide a useful guide for the future development of label-free electrochemical devices for DNA analysis.

Reactivity of amine antioxidants relative to OH and anti e

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

Minkhadzhidinova, D.R.; Nikiforov, G.A.; Khrapova, N.G.

1986-06-20

An ESR study was carried out on the reactivity of various types of amines relative to OH/sup ./ and anti e. The selection of these compounds having anti-oxidant properties was also based on the circumstance that amine molecules contain a set of functional groups which may be potential sites for the attack of both OH and anti e radicals. A sample of 6 M H/sub 3/PO/sub 4/ was used for the matrix solutions and forms a glass upon rapid insertion into liquid nitrogen. The phosphoric acid solutions of these compounds taken in concentrations from 0.025 to 0.05 M were flushedmore » with argon to remove oxygen. Ampules containing the solutions were inserted into liquid nitrogen and irradiated from a cobalt source. The ESR spectra of the irradiated solutions clearly show the components of the atomic hydrogen doublet with a = 50 mT and of H/sub 2/PO/sub 4//sup ./ radicals in the central region of the spectrum.« less

[Association between oxygen saturation and cognitive function in older adults from longevity areas in China].

PubMed

Su, L Q; Yin, Z X; Xu, N; Lyu, Y B; Luo, J S; Shi, X M

2016-07-06

To explore the relationship between oxygen saturation (SpO2) and cognitive function in older adults from longevity areas in China. A total of 2 285 participants aged ≥65 years according to the 2012 Chinese Longitudinal Healthy Longevity Survey were included in this study. Among them, 1 739 participants aged 65-99 years were randomly selected, and 546 participants aged ≥100 years were totally involved. A standardized questionaire was used to collect the information of demographic characteristics, life styles, disease history, etc. Cognitive function was evaluated using the Mini Mental State Examination Scale. Arterial oxygen saturation and heart rate were measured by pulse oximetry. Differences in cognitive function between the low SpO2 group (<0.94) and normal SpO2 group (≥0.94) were analyzed, and logistic regression models were used to analyze the relationship between SpO2 and cognitive function. The total score of cognitive function was 22.6±9.7 for the 1 922 participants in the normal SpO2 group, and 18.8 ± 11.0 for the 363 participants in the low SpO2 group (t=6.11, P<0.001). The proportion of cognitive impairment in the low SpO2 group was 36.6% (n=133), and 22.9% (n=441) in the normal SpO2 group (χ(2)=30.44, P<0.001). RESULTS from stepwise logistic regression analysis showed that the risk of cognitive impairment increased with each year of increased age (OR 1.07; (95% CI: 1.05-1.09), P<0.001). Low SpO2, vision disorders, impaired activities of daily living, dyslipidemia, unmarried status, and lack of exercise were also associated with increased risk of cognitive impairment (OR 1.64; (95% CI: 1.11-2.43), OR 1.73; (95% CI: 1.27-2.35), OR 3.54; (95% CI: 2.62-4.79), OR 1.38; (95% CI: 1.02-1.86), OR 2.05; (95% CI: 1.34-3.13), OR 1.83; (95% CI: 1.13-2.97), respectively, P<0.05). Stratified analysis by age group showed that the association between SpO2 and cognitive impairment was most significant in participants aged ≥90 years (OR 1.58; (95% CI: 1.09-2.28), P=0.016). Low oxygen saturation was associated with higher risk of cognitive impairment in our population of elderly adults.

Radiation polymerisable compositions containing 3-sorboyloxy-2-hydroxypropyl groups

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

Green, G.E.

1976-02-03

Compounds having at least three 3-sorboyloxy-2-hydroxypropyl groups directly attached to ether oxygen atoms are polymerised by exposure to actinic radiation, preferably in the presence of a sensitizer such as Michler's ketone or benzoin. The compounds may be obtained by the reaction either of sorbic acid with a substance having at least three glycidyl ether groups or of glycidyl sorbate with a substance having at least three phenolic or alcoholic hydroxyl groups: if desired, not all of the glycidyl groups may be consumed, so that, after actinically induced polymerisation, the epoxide-containing polymer may be cross-linked by reaction with a curing agentmore » for epoxide resins. The compounds are useful in making printed circuits or printing plates for offset printing.« less

Effects of group exercise on functional abilities: Differences between physically active and physically inactive women.

PubMed

Cokorilo, Nebojsa; Mikalacki, Milena; Satara, Goran; Cvetkovic, Milan; Marinkovic, Dragan; Zvekic-Svorcan, Jelena; Obradovic, Borislav

2018-03-30

Aerobic exercises to music can have a positive effect on functional and motor skills of an exerciser, their health, as well as an aesthetic and socio-psychological component. The objective of this study was to determine the effects of reactive exercising in a group on functional capabilities in physically active and physically inactive women. A prospective study included 64 healthy women aged 40-60 years. The sample was divided into the experimental group (n= 36), i.e. physically active women who have been engaged in recreational group exercises at the Faculty of Sport and Physical Education, University of Novi Sad, Serbia, and the control group (n= 28), which consisted of physically inactive women. All the participants were monitored using the same protocol before and after the implementation of the research. All women had their height, weight, body mass index measured as well as spiroergometric parameters determined according to the Bruce protocol. A univariate analysis of variance has shown that there is a statistically significant difference between the experimental group and the control group in maximum speed, the total duration of the test, relative oxygen consumption, absolute oxygen consumption and ventilation during the final measurement. After the training intervention, the experimental group showed improvements in all the parameters analyzed compared with pretest values. The recreational group exercise model significantly improves aerobic capacity and functioning of the cardiovascular system. Therefore, it is essential for women to be involved more in any form of recreational group exercising in order to improve functional capacity and health.

Identification of a flavin-containing S-oxygenating monooxygenase involved in alliin biosynthesis in garlic.

PubMed

Yoshimoto, Naoko; Onuma, Misato; Mizuno, Shinya; Sugino, Yuka; Nakabayashi, Ryo; Imai, Shinsuke; Tsuneyoshi, Tadamitsu; Sumi, Shin-ichiro; Saito, Kazuki

2015-09-01

S-Alk(en)yl-l-cysteine sulfoxides are cysteine-derived secondary metabolites highly accumulated in the genus Allium. Despite pharmaceutical importance, the enzymes that contribute to the biosynthesis of S-alk-(en)yl-l-cysteine sulfoxides in Allium plants remain largely unknown. Here, we report the identification of a flavin-containing monooxygenase, AsFMO1, in garlic (Allium sativum), which is responsible for the S-oxygenation reaction in the biosynthesis of S-allyl-l-cysteine sulfoxide (alliin). Recombinant AsFMO1 protein catalyzed the stereoselective S-oxygenation of S-allyl-l-cysteine to nearly exclusively yield (RC SS )-S-allylcysteine sulfoxide, which has identical stereochemistry to the major natural form of alliin in garlic. The S-oxygenation reaction catalyzed by AsFMO1 was dependent on the presence of nicotinamide adenine dinucleotide phosphate (NADPH) and flavin adenine dinucleotide (FAD), consistent with other known flavin-containing monooxygenases. AsFMO1 preferred S-allyl-l-cysteine to γ-glutamyl-S-allyl-l-cysteine as the S-oxygenation substrate, suggesting that in garlic, the S-oxygenation of alliin biosynthetic intermediates primarily occurs after deglutamylation. The transient expression of green fluorescent protein (GFP) fusion proteins indicated that AsFMO1 is localized in the cytosol. AsFMO1 mRNA was accumulated in storage leaves of pre-emergent nearly sprouting bulbs, and in various tissues of sprouted bulbs with green foliage leaves. Taken together, our results suggest that AsFMO1 functions as an S-allyl-l-cysteine S-oxygenase, and contributes to the production of alliin both through the conversion of stored γ-glutamyl-S-allyl-l-cysteine to alliin in storage leaves during sprouting and through the de novo biosynthesis of alliin in green foliage leaves. © 2015 The Authors The Plant Journal © 2015 John Wiley & Sons Ltd.

Absolute iron deficiency without anaemia in patients with chronic systolic heart failure is associated with poorer functional capacity.

PubMed

Pozzo, Joffrey; Fournier, Pauline; Delmas, Clément; Vervueren, Paul-Louis; Roncalli, Jérôme; Elbaz, Meyer; Galinier, Michel; Lairez, Olivier

2017-02-01

Functional status is one of the main concerns in the management of heart failure (HF). Recently, the FAIR-HF and CONFIRM-HF trials showed that correcting anaemia using intravenous iron supplementation improved functional variables in patients with absolute or relative iron deficiency. Relative iron deficiency is supposed to be a marker of HF severity, as ferritin concentration increases with advanced stages of HF, but little is known about the impact of absolute iron deficiency (AID). To study the impact of AID on functional variables and survival in patients with chronic systolic HF. One hundred and thirty-eight non-anaemic patients with chronic systolic HF were included retrospectively. Patients were divided into two groups according to iron status: the AID group, defined by a ferritin concentration<100μg/L and the non-AID group, defined by a ferritin concentration≥100μg/L. Functional, morphological and biological variables were collected, and survival was assessed. Patients in the AID group had a poorer 6-minute walking test (342 vs. 387m; P=0.03) and poorer peak exercise oxygen consumption (13.8 vs. 16.0mL/min/kg; P=0.01). By multivariable analysis, ferritin<100μg/L was associated with impaired capacity of effort, assessed by peak exercise oxygen consumption. By multivariable analysis, there was no difference in total mortality between groups, with a mean follow-up of 5.1±1.1 years. The poorer functional evaluations in iron-deficient patients previously reported are not caused by the merging of two different populations (i.e. patients with absolute or relative iron deficiency). Our study has confirmed that non-anaemic HF patients with AID have poorer peak oxygen consumption. However, AID has no impact on the survival of these patients. Copyright © 2017. Published by Elsevier Masson SAS.

Comparative analysis of COPD associated with tobacco smoking, biomass smoke exposure or both.

PubMed

Olloquequi, Jordi; Jaime, Sergio; Parra, Viviana; Cornejo-Córdova, Elizabeth; Valdivia, Gonzalo; Agustí, Àlvar; Silva O, Rafael

2018-01-18

Exposure to noxious gases and particles contained in both tobacco smoking (TS) and biomass smoke (BS) are well recognized environmental risk factors for chronic obstructive pulmonary disease (COPD). COPD is characterized by an abnormal inflammatory response, both in the pulmonary and systemic compartments. The differential effects of TS, BS or their combined exposure have not been well characterized yet. This study sought to compare the lung function characteristics and systemic inflammatory response in COPD patients exposed to TS, BS or their combination. Sociodemographic, clinical and lung functional parameters were compared across 49 COPD patients with a history of smoking and no BS exposure (TS COPD), 31 never-smoker COPD patients with BS exposure (BS COPD), 46 COPD patients with a combined exposure (TS + BS COPD) and 52 healthy controls (HC) who have never been exposed neither to TS or BS. Blood cell counts, C-reactive protein (CRP), fibrinogen and immunoglobulin E (IgE) levels were quantified in all four groups. TS + BS COPD patients exhibited significantly lower oxygen saturation than the rest of groups (p < 0.01). Spirometry and diffusing capacity were significantly higher in BS than in TS or TS + BS patients. CRP levels were significantly higher in TS COPD patients than in BS COPD group (p < 0.05), whereas fibrinogen was raised in COPD patients with a history of smoking (TS and TS + BS) when compared to control subjects (p < 0.01). Finally, COPD patients with BS exposure (BS and BS + TS groups) showed higher IgE levels than TS and HC (p < 0.05). There are significant physiological and inflammatory differences between COPD patients with TS, BS and TS + BS exposures. The latter had worse blood oxygenation, whereas the raised levels of IgE in BS exposed patients suggests a differential Th2 systemic inflammatory pattern triggered by this pollutant.

Electrode influence on the number of oxygen vacancies at the gate/high-κ dielectric interface in nanoscale MIM capacitors

NASA Astrophysics Data System (ADS)

Stojanovska-Georgievska, Lihnida

2015-02-01

In this paper, a particular attention has been paid in determining the impact of the type of top electrode (the gate), on the overall characteristics of the examined metal-insulator-metal structures, that contain doped Ta2O5:Hf high-κ dielectric as an insulator. For that purpose MIM capacitors with different metal gates (conventional Al and also W, Au, Pt, Mo, TiN, Ta) were formed. The results obtained, consider both the influence of metal work function and oxygen affinity, as possible reasons for increasing of number of oxygen vacancies at the gate/dielectric interface. Here we use capacitance-voltage alteration (C-V measurements) under constant current stress (CCS) conditions as characterization technique. The measurements show grater creation of positive oxygen vacancies in the case of metal electrodes with high work function, like Au and Pt, for almost one order of magnitude. It is also indicative that these metals have also the lowest values of heat of oxygen formation, which also favors the creation of oxygen vacancies. All results are discussed taking into consideration the nanoscale thickness of the dielectric layer (of the order of 8 nm), implicating the stronger effect of interface properties on the overall behavior rather than the one originating from the bulk of material.

Hypoxic Regulation of Functional Extracellular Matrix Elaboration by Nucleus Pulposus Cells in Long-Term Agarose Culture

PubMed Central

Gorth, Deborah J; Lothstein, Katherine E; Chiaro, Joseph A; Farrell, Megan J; Dodge, George R; Elliott, Dawn M; Malhotra, Neil R; Mauck, Robert L; Smith, Lachlan J

2015-01-01

Degeneration of the intervertebral discs is strongly implicated as a cause of low back pain. Since current treatments for discogenic low back pain show poor long-term efficacy, a number of new, biological strategies are being pursued. For such therapies to succeed, it is critical that they be validated in conditions that mimic the unique biochemical microenvironment of the nucleus pulposus (NP), which include low oxygen tension. Therefore, the objective of this study was to investigate the effects of oxygen tension on NP cell functional extracellular matrix elaboration in 3D culture. Bovine NP cells were encapsulated in agarose constructs and cultured for 14 or 42 days in either 20% or 2% oxygen in defined media containing transforming growth factor beta-3. At each time point, extracellular matrix composition, biomechanics and mRNA expression of key phenotypic markers were evaluated. Results showed that while bulk mechanics and composition were largely independent of oxygen level, low oxygen promoted improved restoration of the NP phenotype, higher mRNA expression of extracellular matrix and NP specific markers, and more uniform matrix elaboration. These findings indicate that culture under physiological oxygen levels is an important consideration for successful development of cell and growth factor-based regenerative strategies for the disc. PMID:25640328

International comparison CCQM-K101: oxygen in nitrogen—a track B comparison and that the matrix contains argon

NASA Astrophysics Data System (ADS)

Zhou, Z.; Han, Q.; Wang, D.; Macé, T.; Kipphardt, H.; Maiwald, M.; Tuma, D.; Uehara, S.; Akima, D.; Shimosaka, T.; Jung, J.; Oh, S.-H.; van der Veen, A.; van Wijk, J. I. T.; Ziel, P. R.; Konopelko, L.; Valkova, M.; Mogale, David M.; Botha, A.; Brewer, P.; Murugan, A.; Doval Minnaro, M.; Miller, M.; Guenther, F.; Kelly, M. E.

2016-01-01

This key comparison aims to assess the capabilities of the participants to determine the amount-of-substance fraction oxygen in nitrogen. The GAWG has classified this as a track B comparison, due to the unexpected 50 μmol/mol argon mole fraction content of the transfer standards, which effects the achievable performance of some measurement techniques such a GC-TCD. The separation of oxygen and argon is challenging, and not all systems in use are equally well designed for it. As this analytical challenge due to a substantial fraction of argon in the transfer standards became a reality, the Gas Analysis Working Group (GAWG) decided to qualify this key comparison as a regular key comparison and not as a core comparison, which may be used to support calibration and measurement capabilities (CMCs) for oxygen in nitrogen, or for oxygen in nitrogen mixtures containing argon only (see also the section on support to CMCs). Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

The Evolution of Sterol Biosynthesis in Bacteria: In Situ Fluorescence Localization of Sterols in the Nucleoid Bacterium Gemmata obscuriglobus

NASA Astrophysics Data System (ADS)

Budin, M.; Jorgenson, T. L.; Pearson, A.

2004-12-01

The biosynthesis of sterols is generally regarded as a eukaryotic process. The first enzymatic step in the production of sterols requires molecular oxygen. Therefore, both the origin of eukaryotes and the evolution of sterol biosynthesis were thought to postdate the rise of oxygen in earth's atmosphere, until Brocks et al. discovered steranes in rocks aged 2.7 Ga (1). Many prokaryotes produce hopanoids, sterol-like compounds that are synthesized from the common precursor squalene without the use of molecular oxygen. However, a few bacterial taxa are also known to produce sterols, suggesting this pathway could precede the rise of oxygen (2, 3). Recently, we discovered the shortest sterol-producing biosynthetic pathway known to date in the bacterium Gemmata obscuriglobus (4). Using genomic searches, we found that Gemmata has the enzymes necessary for synthesis of sterols, and lipid analyses showed that the sterols produced are lanosterol and its isomer parkeol. Gemmata is a member of the Planctomycetes, an unusual group of bacteria, all of the known species of which contain intracellular compartmentalization. Among the Planctomycetes, Gemmata uniquely is the only prokaryote known to contain a double-membrane-bounded nuclear body (5). Since sterols usually are found in eukaryotes, and Gemmata has a eukaryote-like nuclear organelle, we investigated the location of the sterols within Gemmata to postulate whether they play a role in stabilization of the nuclear membrane and control of genomic organization. We used the sterol-specific fluorescent dye Filipin III in conjunction with fluorescent dyes for internal and external cellular membranes in order to determine whether the sterols are located in the nuclear body membrane, external membrane, or both. We found that sterols in Gemmata are concentrated in the internal membrane, implying that they function in maintaining this unusual cellular component. It is notable that Gemmata also produce hopanoids, suggesting that they acquired the ability to produce sterols for a specialized function related to their nuclear membrane. 1. Brocks, J.J., et al., Science 285:1033-36 (1999). 2. Bird, C.W., et al., Nature 230:473-74 (1971). 3. Bode, H.B., et al., Mol. Microbiol. 47:471-81 (2003). 4. Pearson, A., et al., Proc. Natl. Acad. Sci. USA 100:15352-57 (2003). 5. Fuerst, J.A. and R.I. Webb, Proc. Natl. Acad. Sci. USA 88:8184-88 (1991).

Tuning electronic properties in graphene quantum dots by chemical functionalization: Density functional theory calculations

NASA Astrophysics Data System (ADS)

Abdelsalam, Hazem; Elhaes, Hanan; Ibrahim, Medhat A.

2018-03-01

The energy gap and dipole moment of chemically functionalized graphene quantum dots are investigated by density functional theory. The energy gap can be tuned through edge passivation by different elements or groups. Edge passivation by oxygen considerably decreases the energy gap in hexagonal nanodots. Edge states in triangular quantum dots can also be manipulated by passivation with fluorine. The dipole moment depends on: (a) shape and edge termination of the quantum dot, (b) attached group, and (c) position to which the groups are attached. Depending on the position of attached groups, the total dipole can be increased, decreased, or eliminated.

Divergent Effects of Hypertonic Fluid Resuscitation on Renal Pathophysiological and Structural Parameters in Rat Model of Lower Body Ischemia/Reperfusion-Induced Sterile Inflammation.

PubMed

Ergin, Bulent; Zuurbier, Coert J; Kapucu, Aysegul; Ince, Can

2017-12-27

The pathogenesis of acute kidney injury (AKI) is characterized by the deterioration of tissue perfusion and oxygenation and enhanced inflammation. The purpose of this study was to investigate whether or not the hemodynamic and inflammatory effects of hypertonic saline (HS) protect the kidney by promoting renal microcirculatory oxygenation and possible deleterious effects of HS due to its high sodium content on renal functional and structural injury following ischemia/reperfusion. Mechanically ventilated and anesthetized rats were randomly divided into four groups (n = 6 per group): a sham-operated control group; a group subjected to renal ischemia for 45 min by supra-aortic occlusion followed by 2 h of reperfusion (I/R); and I/R group treated with a continuous i.v. infusion (5 mL/kg/h) of either % 0.9 NaCl (IR+NS) or %10 NaCl (I/R+HS) after releasing the clamp. Systemic and renal hemodynamic, renal cortical (CμPO2), and medullar microcirculatory pO2 (MμPO2) are measured by the oxygen-dependent quenching of the phosphorescence lifetime technique. Renal functional, inflammatory, and tissues damage parameters were also assessed. HS, but not NS, treatment restored I/R-induced reduced mean arterial pressure, CμPO2, renal oxygen deliver (DO2ren), and consumption (VO2ren). HS caused a decrease in tubular sodium reabsorption (TNa) that correlated with an elevation of fractional sodium excretion (EFNa) and urine output. HS had an anti-inflammatory effect by reducing the levels TNF-α, IL-6, and hyaluronic acid in the renal tissue samples as compared with the I/R and I/R+NS groups (P < 0.05). HS treatment was also associated with mild acidosis and an increased renal tubular damage. Despite HS resuscitation improving the systemic hemodynamics, microcirculatory oxygenation, and renal oxygen consumption as well as inflammation, it should be limited or strictly controlled for long-term use because of provoking widespread renal structural damage.

Effect of LEO Exposure on Aromatic Polymers Containing Phenylphosphine Oxide Groups

NASA Technical Reports Server (NTRS)

Lillehei, P. T.; Smith, J. G., Jr.; Connell, J. W.

2008-01-01

As part of the Materials on The International Space Station Experiment (MISSE), aromatic polymers containing phenylphosphine oxide groups were exposed to low Earth orbit for approx.4 years. All of the aromatic polymers containing phenylphosphine oxide groups survived the exposure despite the high fluence of atomic oxygen that completely eroded other polymer films such as Kapton(TradeMark) and Mylar(Trademark) of comparable or greater thickness. The samples were characterized for changes in physical properties, thermal/optical properties surface chemistry, and surface topography. The data from the polymer samples on MISSE were compared to samples from the same batch of material stored under ambient conditions on Earth. In addition, comparisons were made between the MISSE samples and those subjected to shorter term space flight exposures. The results of these analyses will be presented.

Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1992-01-01

Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with one or more nitro groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

Cyano- and polycyanometalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1992-01-01

Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been substituted with one or more cyano groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

Oxygenated Interface on Biomass Burn Tar Balls Determined bySingle Particle Scanning Transmission X-ray Microscopy

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

Tivanski, A.V.; Hopkins, R.J.; Tyliszczak, T.

2007-06-21

Carbonaceous particles originating from biomass burning canaccount for a large fraction of organic aerosols in a local environment.Presently, their composition, physical and chemical properties, as wellas their environmental effects are largely unknown. Tar balls, a distincttype of highly spherical carbonaceous biomass burn particles, have beenobserved in a number of field campaigns. The Yosemite AerosolCharacterization Study that took place in summer 2002 occurred during anactive fire season in the western United States; tar balls collectedduring this field campaign are described in this article. Scanningtransmission X-ray microscopy and near-edge X-ray absorption finestructure spectroscopy are used to determine the shape, structure, andsize-dependent chemicalmore » composition of ~;150 individual sphericalparticles ranging in size from 0.15 to 1.2mu m.The elemental compositionof tar balls is ~;55 percent atomic carbon and ~;45 percent atomicoxygen. Oxygen is present primarily as carboxylic carbonyls andoxygen-substituted alkyl (O-alkyl-C) functional groups, followed bymoderate amounts of ketonic carbonyls. The observed chemical composition,density, and carbon functional groups are distinctly different from sootor black carbon and more closely resemble high molecular weight polymerichumic-like substances, which could account for their reported opticalproperties. A detailed examination of the carboxylic carbonyl andO-alkyl-C functional groups as a function of particle size reveals a thinoxygenated interface layer. The high oxygen content, as well as thepresence of water-soluble carboxylic carbonyl groups, could account forthe reported hygroscopic properties of tar balls. The presence of theoxygenated layer is attributed to atmospheric processing of biomass burnparticles.« less

Effects of an immuno-enhanced diet containing antioxidants in esophageal cancer surgery following neoadjuvant therapy.

PubMed

Aiko, S; Kumano, I; Yamanaka, N; Tsujimoto, H; Takahata, R; Maehara, T

2012-02-01

Neoadjuvant therapy-induced immunological deterioration may be a key factor in postoperative morbidity in patients with esophageal cancer. This study aimed to determine the effects of perioperative feeding with an immuno-enhanced diet on immune competence in patients treated with neoadjuvant therapy followed by surgery. Because an immuno-enhanced diet that contained several antioxidants was used, perioperative oxidative stress and the effects of the immuno-enhanced diet on this stress were also investigated. Of 39 patients with esophageal cancer who underwent similar surgical procedures, 26 patients who received chemotherapy or chemoradiation therapy before surgery were randomly divided into two groups: group 1 (n= 14) was given an immuno-enhanced diet for 5 days before surgery, and group 2 (n= 12) received no enteral feeding products before surgery. Group 3 (n= 13) consisted of patients that did not receive neoadjuvant therapy and received no enteral feeding products before surgery. Several markers for coagulation and fibrinolysis were determined and immunological assessments were performed for each patient. To measure reactive oxygen metabolites and the total antioxidant capacity, diacron-reactive oxygen metabolites (d-ROMs) and OXY-adsorbent tests were performed using a free radical elective evaluator. Significant depression in lymphocyte numbers was observed in groups 1 and 2 before and early after surgery as compared to group 3. Numbers of B cells, CD4/CD8 ratio, and phytohemagglutinin-induced lymphocyte transformation tests were also significantly decreased in groups 1 and 2 on postoperative day 1. Fibrin and fibrinogen degradation products were significantly elevated in group 2 compared to group 1. d-ROMs and OXY-adsorbent test values were elevated before surgery and were decreased transiently early after surgery. Compared to groups 2 and 3, d-ROMs values were significantly lower in group 1 patients throughout the postoperative period, while OXY-adsorbent test values were significantly higher in group 2 patients. Oxidative index was significantly suppressed in group 1 compared to group 3. No significant intergroup differences were observed with regard to morbidity after surgery. Although the baseline levels of immunological function might have been different because of less-advanced cancer stages in group 3, neoadjuvant therapy significantly affected several immunological parameters. Preoperative administration of an immuno-enhanced diet did not significantly prevent neoadjuvant therapy-induced immunological deterioration prior to esophageal cancer surgery. Patients with esophageal cancer had elevated levels of oxidant and antioxidant activities before surgery, which were transiently decreased early after surgery. Although the underlying mechanisms for these perioperative changes are unclear, this study showed that an immuno-enhanced diet containing several antioxidants may reduce oxidative stress following esophageal cancer surgery. After these mechanisms are studied further, oxidative stress control may become another tool for perioperative management to reduce morbidity after esophageal cancer surgery. © 2011 Copyright the Authors. Journal compilation © 2011, Wiley Periodicals, Inc. and the International Society for Diseases of the Esophagus.

Purinergic effects of a hydroalcoholic Agaricus brasiliensis (A. blazei) extract on liver functions.

PubMed

de Oliveira, Andrea L; Eler, G Jacklin; Bracht, Adelar; Peralta, Rosane M

2010-06-23

The effects of a hydroalcoholic extract of Agaricus brasiliensis (A. blazei) on functional parameters in the perfused rat liver were examined with emphasis on its content of nucleotides and nucleosides. Several nucleosides and nucleotides were identified in the A. brasiliensis extract, which was active on several liver functions. A significant part of the effects is the result of the purinergic action of nucleosides and nucleotides: pressure increment, glycogenolysis stimulation, transient inhibition of oxygen consumption, and redox state changes. Other phenomena such as the stimulation of gluconeogenesis, ureogenesis, and oxygen consumption are more likely consequences of the metabolic transformation of substrates contained within the extract, especially amino acids. It seems apparent that consumption of A. brasiliensis represents not only the ingestion of metabolic precursors but also the ingestion of substances that, even at low concentrations, can exert important signaling functions in the liver as well as in the organism as a whole.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A.; Simonetti, Dante A.; Kunkes, Edward L.

2015-12-08

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A [Verona, WI; Simonetti, Dante A [Middleton, WI; Kunkes, Edward L [Madison, WI

2011-12-13

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Surface chemical structure of poly(ethylene naphthalate) films during degradation in low-pressure high-frequency plasma treatments

NASA Astrophysics Data System (ADS)

Kamata, Noritsugu; Yuji, Toshifumi; Thungsuk, Nuttee; Arunrungrusmi, Somchai; Chansri, Pakpoom; Kinoshita, Hiroyuki; Mungkung, Narong

2018-06-01

The surface chemical structure of poly(ethylene naphthalate) (PEN) films treated with a low-pressure, high-frequency plasma was investigated by storing in a box at room temperature to protect the PEN film surface from dust. The functional groups on the PEN film surface changed over time. The functional groups of –C=O, –COH, and –COOH were abundant in the Ar + O2 mixture gas plasma-treated PEN samples as compared with those in untreated PEN samples. The changes occurred rapidly after 2 d following the plasma treatment, reaching steady states 8 d after the treatment. Hydrophobicity had an inverse relationship with the concentration of these functional groups on the surface. Thus, the effect of the low-pressure high-frequency plasma treatment on PEN varies as a function of storage time. This means that radical oxygen and oxygen molecules are clearly generated in the plasma, and this is one index to confirm that radical reaction has definitely occurred between the gas and the PEN film surface with a low-pressure high-frequency plasma.

Characterising non-covalent interactions with the Cambridge Structural Database.

PubMed

Lommerse, J P; Taylor, R

1997-02-01

This review describes how the CSD can be used to study non-covalent interactions. Several different types of information may be obtained. First, the relative frequencies of various interactions can be studied; for example, we have shown that the terminal oxygen atoms of phosphate groups accept hydrogen bonds far more often than the linkage oxygens. Secondly, information can be obtained about the geometries of nonbonded contacts; for example, hydrogen bonds to P-O groups rarely form along the extension of the P-O bond, whereas short contacts between oxygen and carbon-bound iodine show a strong preference for linear C-I ... O angles. Thirdly, the CSD can be searched for novel interactions which may be exploited in inhibitor design; for example, the I ... O contacts just mentioned, and N-H ... pi hydrogen bonds. Finally, the CSD can suggest synthetic targets for medicinal chemistry; for example, molecules containing delocalised electron deficient groups such as trimethylammonium, pyridinium, thaizolium and dinitrophenyl have a good chance of binding to an active-site tryptophan. Although the CSD contains small-molecule crystal structures, not protein-ligand complexes, there is considerable evidence that the contacts seen in the two types of structures are similar. We have illustrated this a number of times in the present review and additional evidence has been given previously by Klebe. The major advantages of the CSD are its size, diversity and experimental accuracy. For these reasons, it is a useful tool for modellers engaged in rational inhibitor design.

Preliminary Crystallographic Study of Hemoglobin from Buffalo (Bubalus bubalis): A Low Oxygen Affinity Species.

PubMed

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

2009-01-01

Hemoglobin is a tetrameric, iron-containing metalloprotein, which plays a vital role in the transportation of oxygen from lungs to tissues and carbon dioxide back to lungs. Though good amount of work has already been done on hemoglobins, the scarcity of data on three dimensional structures pertaining to low oxygen affinity hemoglobins from mammalian species, motivated our group to work on this problem specifically. Herein, we report the preliminary crystallographic analysis of buffalo hemoglobin, which belongs to low oxygen affinity species. The buffalo blood was collected, purified by anion exchange chromatography and crystallized with PEG 3350 using 50mM phosphate buffer at pH 6.7 as a precipitant by hanging drop vapor diffusion method. Data collection was carried out using mar345dtb image plate detector system. Buffalo hemoglobin crystallizes in orthorhombic space group P2(1)2(1)2(1) with one whole biological molecule (alpha2beta2) in the asymmetric unit with cell dimensions a=63.064A, b=74.677A, c=110.224A.

Vacuum-based surface modification of organic and metallic substrates

NASA Astrophysics Data System (ADS)

Torres, Jessica

Surface physico-chemical properties play an important role in the development and performance of materials in different applications. Consequently, understanding the chemical and physical processes involved during surface modification strategies is of great scientific and technological importance. This dissertation presents results from the surface modification of polymers, organic films and metallic substrates with reactive species, with the intent of simulating important modification processes and elucidating surface property changes of materials under different environments. The reactions of thermally evaporated copper and titanium with halogenated polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are used to contrast the interaction of metals with polymers. Results indicate that reactive metallization is thermodynamically favored when the metal-halogen bond strength is greater than the carbon-halogen bond strength. X-ray post-metallization treatment results in an increase in metal-halide bond formation due to the production of volatile halogen species in the polymer that react with the metallic overlayer. The reactions of atomic oxygen (AO) and atomic chlorine with polyethylene (PE) and self-assembled monolayers (SAMs) films were followed to ascertain the role of radical species during plasma-induced polymer surface modification. The reactions of AO with X-ray modified SAMs are initially the dominated by the incorporation of new oxygen containing functionality at the vacuum/film interface, leading to the production of volatile carbon containing species such as CO2 that erodes the hydrocarbon film. The reaction of atomic chlorine species with hydrocarbon SAMs, reveals that chlorination introduces C-Cl and C-Cl2 functionalities without erosion. A comparison of the reactions of AO and atomic chlorine with PE reveal a maximum incorporation of the corresponding C-O and C-Cl functionalities at the polymer surface. A novel method to prepare phosphorous-containing polymer surfaces through ion implantation of trimethyl phosphine onto PE is presented. Air exposure of the resulting P-implanted PE leads to the surface selective oxidation of phosphorous moieties. P-containing hydrocarbon films are used to model the surface chemical changes of P-containing polymers exposed to AO. Results indicate that oxidized phosphorous species protect the film from AO-induced erosion. The low temperature (<150 K) oxidation of nitrided iron surfaces exposed to oxygen reveal the formation of iron oxynitride (FexNyO z, nitrosonium ions (NO+) as well as nitrite/nitrito and nitrate type species. The production of nitrite/nitrito and nitrate species is taken as evidence for the existence of oxygen insertion chemistry into the iron nitride lattice under these low temperature oxidation conditions. Upon annealing the oxidized iron nitride surface, nitrogen desorbs exclusively as nitric oxide (NO).

DELAYING BLOOD TRANSFUSION IN EXPERIMENTAL ACUTE ANEMIA WITH A PERFLUOROCARBON EMULSION

PubMed Central

Cabrales, Pedro; Briceño, Juan Carlos

2011-01-01

Background To avoid unnecessary blood transfusions, physiologic transfusion triggers, rather than exclusively hemoglobin-based transfusion triggers have been suggested. The objective of this study was to determine systemic and microvascular effects of using a perfluorocarbon-based oxygen carrier (PFCOC) to maintaining perfusion and oxygenation during extreme anemia. Methods The hamster (weight 55-65 g) window chamber model was used. Two isovolemic hemodilution steps were performed using 10% hydroxyethyl starch at normoxic conditions to hematocrit of 19% (5.5 gHb/dl), point where the transfusion trigger was reached. Two additional hemodilution exchanges using the PFCOC (Oxycyte™, Synthetic Blood International, Inc. Costa Mesa, CA) and increasing fraction of inspired oxygen to 1.0 were performed to reduce hematocrit to 11% (3.8 gHb/dl) and 6% (2.0 gHb/dl), respectively. No control group was used in the study, as this level of hemodilution is lethal with conventional plasma expanders. Systemic parameters, microvascular perfusion, functional capillary density and oxygen tensions across the microvascular network were measured. Results At 6% hematocrit, the PFCOC maintained mean arterial pressure, cardiac output, systemic oxygen delivery and consumption. As hematocrit was lowered from 11% to 6%, functional capillary density, calculated microvascular oxygen delivery and consumption decreased, and oxygen extraction ratio was close to 100%. Peripheral tissue oxygenation was not predicted by systemic oxygenation. Conclusions PFCOC in conjunction with hyperoxia was able to sustain organ function, and partially provide systemic oxygenation during extreme anemia over the observation period. The PFCOC can work as a bridge until red blood cells are available for transfusion, or where additional oxygen is required, notwithstanding possible limitations in peripheral tissue oxygenation. PMID:21326091

The importance of physiological oxygen concentrations in the sandwich cultures of rat hepatocytes on gas-permeable membranes.

PubMed

Xiao, Wenjin; Shinohara, Marie; Komori, Kikuo; Sakai, Yasuyuki; Matsui, Hitoshi; Osada, Tomoharu

2014-01-01

Oxygen supply is a critical issue in the optimization of in vitro hepatocyte microenvironments. Although several strategies have been developed to balance complex oxygen requirements, these techniques are not able to accurately meet the cellular oxygen demand. Indeed, neither the actual oxygen concentration encountered by cells nor the cellular oxygen consumption rates (OCR) was assessed. The aim of this study is to define appropriate oxygen conditions at the cell level that could accurately match the OCR and allow hepatocytes to maintain liver specific functions in a normoxic environment. Matrigel overlaid rat hepatocytes were cultured on the polydimethylsiloxane (PDMS) membranes under either atmospheric oxygen concentration [20%-O2 (+)] or physiological oxygen concentrations [10%-O2 (+), 5%-O2 (+)], respectively, to investigate the effects of various oxygen concentrations on the efficient functioning of hepatocytes. In parallel, the gas-impermeable cultures (polystyrene) with PDMS membrane inserts were used as the control groups [PS-O2 (-)]. The results indicated that the hepatocytes under 10%-O2 (+) exhibited improved survival and maintenance of metabolic activities and functional polarization. The dramatic elevation of cellular OCR up to the in vivo liver rate proposed a normoxic environment for hepatocytes, especially when comparing with PS-O2 (-) cultures, in which the cells generally tolerated hypoxia. Additionally, the expression levels of 84 drug-metabolism genes were the closest to physiological levels. In conclusion, this study clearly shows the benefit of long-term culture of hepatocytes at physiological oxygen concentration, and indicates on an oxygen-permeable membrane system to provide a simple method for in vitro studies. © 2014 American Institute of Chemical Engineers.

Purification, crystallization and preliminary crystallographic studies of haemoglobin from mongoose (Helogale parvula) in two different crystal forms induced by pH variation.

PubMed

Mohamed Abubakkar, M; Saraboji, K; Ponnuswamy, M N

2013-02-01

Haemoglobin (Hb) is a respiratory pigment; it is a tetrameric protein that ferries oxygen from the lungs to tissues and transports carbon dioxide on the return journey. The oxygen affinity of haemoglobin is regulated by the concentration of oxygen surrounding it and several efforts have revealed the shapes of Hb in different states and with different functions. However, study of the molecular basis of Hbs from low-oxygen-affinity species is critically needed in order to increase the understanding of the mechanism behind oxygen adaptation. The present study reports the preliminary crystallographic study of low-oxygen-affinity haemoglobin from mongoose, a burrowing mammal. Haemoglobin from mongoose was purified by anion-exchange chromatography, crystallized using the hanging-drop vapour-diffusion method and diffraction data sets were collected from monoclinic (2.3 Å resolution) and orthorhombic (2.9 Å resolution) crystal forms obtained by pH variation. The monoclinic and orthorhombic asymmetric units contained half and a whole biological molecule, respectively.

Dyspnea on exertion in obese women: association with an increased oxygen cost of breathing.

PubMed

Babb, Tony G; Ranasinghe, Kamalini G; Comeau, Laurie A; Semon, Trisha L; Schwartz, Belinda

2008-07-15

Although exertional dyspnea in obesity is an important and prolific clinical concern, the underlying mechanism remains unclear. To investigate whether dyspnea on exertion in otherwise healthy obese women was associated with an increase in the oxygen cost of breathing or cardiovascular deconditioning. Obese women with and without dyspnea on exertion participated in two independent experiments (n = 16 and n = 14). All participants underwent pulmonary function testing, hydrostatic weighing, ratings of perceived breathlessness during cycling at 60 W, and determination of the oxygen cost of breathing during eucapnic voluntary hyperpnea at 40 and 60 L/min. Cardiovascular exercise capacity, fat distribution, and respiratory mechanics were determined in 14 women in experiment 2. Data were analyzed between groups by independent t test, and the relationship between the variables was determined by regression analysis. In both experiments, breathlessness during 60 W cycling was markedly increased in over 37% of the obese women (P < 0.01). Age, height, weight, lung function, and %body fat were not different between the groups in either experiment. In contrast, the oxygen cost of breathing was significantly (P < 0.01) and markedly (38-70%) greater in the obese women with dyspnea on exertion. The oxygen cost of breathing was significantly (P < 0.001) correlated with the rating of perceived breathlessness obtained during the 60 W exercise in experiment 1 (r(2) = 0.57) and experiment 2 (r(2) = 0.72). Peak cardiovascular exercise capacity, fat distribution, and respiratory mechanics were not different between groups in experiment 2. Dyspnea on exertion is prevalent in otherwise healthy obese women, which seems to be strongly associated with an increased oxygen cost of breathing. Exercise capacity is not reduced in obese women with dyspnea on exertion.

Resolving phase stability in the Ti-O binary with first-principles statistical mechanics methods

NASA Astrophysics Data System (ADS)

Gunda, N. S. Harsha; Puchala, Brian; Van der Ven, Anton

2018-03-01

The Ti-O system consists of a multitude of stable and metastable oxides that are used in wide ranging applications. In this work we investigate phase stability in the Ti-O binary from first principles. We perform a systematic search for ground state structures as a function of oxygen concentration by considering oxygen-vacancy and/or titanium-vacancy orderings over four parent crystal structures: (i) hcp Ti, (ii) ω -Ti, (iii) rocksalt, and (iv) hcp oxygen containing interstitial titanium. We explore phase stability at finite temperature using cluster expansion Hamiltonians and Monte Carlo simulations. The calculations predict a high oxygen solubility in hcp Ti and the stability of suboxide phases that undergo order-disorder transitions upon heating. Vacancy ordered rocksalt phases are also predicted at low temperature that disorder to form an extended solid solution at high temperatures. Predicted stable and metastable phase diagrams are qualitatively consistent with experimental observations, however, important discrepancies are revealed between first-principles density functional theory predictions of phase stability and the current understanding of phase stability in this system.

Solubility of copper in silicate melts as function of oxygen and sulfur fugacities, temperature, and silicate composition

NASA Astrophysics Data System (ADS)

Holzheid, A.; Lodders, K.

2001-06-01

The solubility of Cu in silicate melts coexisting with liquid Cu(Fe) metal and liquid Cu(Fe) sulfide was determined experimentally at oxygen fugacities ranging from 10 -9.1 to 10 -13.6 bar and sulfur fugacities ranging from 10 -2.5 to 10 -6.3 bar at 1300°C. An iron oxide-free silicate of anorthite-diopside eutectic composition and a synthetic MgO-rich basaltic silicate (FeO-bearing) were used in the partitioning experiments. In S-containing systems, some of the metal reacted to metal sulfide. The silicates in the four systems investigated (Fe-free and S-free; Fe-containing and S-free; Fe-free and S-containing; Fe-containing and S-containing) had different colors depending on the dissolved Cu species and the presence of iron and/or sulfur. Irrespective of the presence of sulfur, the solubility of Cu in the silicate increases with increasing oxygen fugacity and metal/silicate partition coefficients for Cu decrease. Increasing the temperature from 1300°C to 1514°C increases the Cu solubility (decreases the metal/silicate partition coefficient) at an oxygen fugacity 0.5 log units below the iron-wüstite (IW) equilibrium in the Fe-free, S-free and Fe-containing, S-free systems. We infer the presence of monovalent Cu + ("CuO 0.5") in the silicate melt on the basis of the solubility of Cu as function of oxygen fugacity. Experiments containing iron yield a formal valence of ˜0.5 for Cu at very low oxygen fugacities, which is not observed in Fe-free systems. The low formal valence is explained by redox reactions between iron and copper in the silicate melts. There is no evidence for sulfidic dissolution of Cu in the silicates but sulfur has indirect effects on Cu partitioning. Iron metal/silicate partition coefficients depend on oxygen fugacity and on sulfur fugacity. Sulfidic dissolution of iron and oxide-sulfide exchange reactions with Cu cause a small increase in Cu metal/silicate partition coefficients. We derive an activity coefficient (γ CuO 0.5) of 10 ± 1 for liquid CuO 0.5 at 1300°C for the silicate melts used here. A comparison with literature data shows that log γ CuO 0.5 increases in proportion to the mass percentages [CaO +(Al 2O 3)/2] in silicate melts. We recommend the following equations for Cu metal/silicate and sulfide/silicate partitioning for geochemical and cosmochemical modeling if silicate composition and the activity of Cu in the metal or sulfide is known: log D met/sil = -0.48 - 0.25 · log fO 2 - log γ Cu metal + 0.02 · [CaO + (Al 2O 3)/2; wt%] silicate logD sul/sil=+0.76-0.25 · logfO 2+0.25logfS 2-logγ CS 0.5,sulfide +0.02 · [CaO+Al 2O 3/2;wt%] silicate. The derived Cu metal/silicate and metal/sulfide partition coefficients are applied to core formation in the Earth and Mars. The observed Cu abundances in the Earth cannot be easily explained by simple core-mantle equilibrium, but the observed Cu abundances for Mars are consistent with core-mantle equilibrium at low pressure and temperatures.

(1)H, (13)C, (15)N backbone and side-chain resonance assignment of Nostoc sp. C139A variant of the heme-nitric oxide/oxygen binding (H-NOX) domain.

PubMed

Alexandropoulos, Ioannis I; Argyriou, Aikaterini I; Marousis, Kostas D; Topouzis, Stavros; Papapetropoulos, Andreas; Spyroulias, Georgios A

2016-10-01

The H-NOX (Heme-nitric oxide/oxygen binding) domain is conserved across eukaryotes and bacteria. In human soluble guanylyl cyclase (sGC) the H-NOX domain functions as a sensor for the gaseous signaling agent nitric oxide (NO). sGC contains the heme-binding H-NOX domain at its N-terminus, which regulates the catalytic site contained within the C-terminal end of the enzyme catalyzing the conversion of GTP (guanosine 5'-triphosphate) to GMP (guanylyl monophosphate). Here, we present the backbone and side-chain assignments of the (1)H, (13)C and (15)N resonances of the 183-residue H-NOX domain from Nostoc sp. through solution NMR.

Efficacy of Mirror Therapy Containing Functional Tasks in Poststroke Patients

PubMed Central

2016-01-01

Objective To investigate the effect of mirror therapy containing functional tasks on upper extremity function and activities of daily living in patients with subacute stroke. Methods The subjects were randomly divided into two groups: the mirror therapy group (30 patients) and the sham therapy group (30 patients). The mirror therapy group underwent a mirror therapy program together with conventional therapy for 20 minutes per day on 5 days per week for 4 weeks. The control group received a sham conventional therapy program under the same schedule as the mirror therapy group. The Fugl-Meyer Motor Function Assessment (FMA), Brunnstrom motor recovery stage, and Modified Barthel Index (MBI) were evaluated 4 weeks after the treatment. Results The upper extremity function on the affected side and ability to perform daily life activities after the intervention were significantly improved in both groups. After 4 weeks of intervention, improvements in the FMA (p=0.027) and MBI (p=0.041) were significantly greater in the mirror therapy group than the sham therapy group. Conclusion In this study, we found that the mirror therapy containing functional task was effective in terms of improving the upper extremity functions and activities of daily living in patients with subacute stroke. PMID:27606269

Efficacy of Mirror Therapy Containing Functional Tasks in Poststroke Patients.

PubMed

Lim, Kil-Byung; Lee, Hong-Jae; Yoo, Jeehyun; Yun, Hyun-Ju; Hwang, Hye-Jung

2016-08-01

To investigate the effect of mirror therapy containing functional tasks on upper extremity function and activities of daily living in patients with subacute stroke. The subjects were randomly divided into two groups: the mirror therapy group (30 patients) and the sham therapy group (30 patients). The mirror therapy group underwent a mirror therapy program together with conventional therapy for 20 minutes per day on 5 days per week for 4 weeks. The control group received a sham conventional therapy program under the same schedule as the mirror therapy group. The Fugl-Meyer Motor Function Assessment (FMA), Brunnstrom motor recovery stage, and Modified Barthel Index (MBI) were evaluated 4 weeks after the treatment. The upper extremity function on the affected side and ability to perform daily life activities after the intervention were significantly improved in both groups. After 4 weeks of intervention, improvements in the FMA (p=0.027) and MBI (p=0.041) were significantly greater in the mirror therapy group than the sham therapy group. In this study, we found that the mirror therapy containing functional task was effective in terms of improving the upper extremity functions and activities of daily living in patients with subacute stroke.

Interface Analyses Between a Case-Hardened Ingot Casting Steel and Carbon-Containing and Carbon-Free Refractories

NASA Astrophysics Data System (ADS)

Fruhstorfer, Jens; Dudczig, Steffen; Rudolph, Martin; Schmidt, Gert; Brachhold, Nora; Schöttler, Leandro; Rafaja, David; Aneziris, Christos G.

2018-06-01

Corrosion tests of carbon-free and carbon-containing refractories were performed. The carbon-free crucibles corroded, whereas the carbon-containing crucibles were negligibly attacked. On them, inclusions were attached. This study investigates melt oxygen contents, interface properties, and steel compositions with their non-metallic inclusions in order to explore the inclusion formation and deposition mechanisms. The carbon-free crucibles were based on alumina, mullite, and zirconia- and titania-doped alumina (AZT). The carbon-containing (-C) ones were alumina-C and AZT-C. Furthermore, nanoscaled carbon and alumina additives (-n) were applied in an AZT-C-n material. In the crucibles, the case-hardened steel 17CrNiMo7-6 was remelted at 1580 °C. It was observed that the melt and steel oxygen contents were higher for the tests in the carbon-free crucibles. Into these crucibles, the deoxidizing alloying elements Mn and Si diffused. Reducing contents of deoxidizing elements resulted in higher steel oxygen levels and less inclusions, mainly of the inclusion group SiO2-core-MnS-shell (2.5 to 8 μ m). These developed from smaller SiO2 nuclei. The inclusion amount in the steel was highest after remelting in AZT-C-n for 30 minutes but decreased strongly with increasing remelting time (60 minutes) due to inclusions' deposition on the refractory surface. The Ti from the AZT and the nanoadditives supported inclusion growth and deposition. Other inclusion groups were alumina and calcium aluminate inclusions. Their contents were high after remelting in carbon- or AZT-containing crucibles but generally decreased during remelting. On the AZT-C-n crucible, a dense layer formed from vitreous compositions including Al, Ca, Mg, Si, and Ti. To summarize, for reducing forming inclusion amounts, mullite is recommended as refractory material. For capturing formed inclusions, AZT-C-n showed a high potential.

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

Andrews, M.A.; Cheng, C.W.; Kelley, K.P.

Process for converting alkenes to form epoxides utilizes transition metal nitro complexes of the formula: M(RCN)/sub 2/XNO/sub 2/ wherein M is palladium or platinum, R is an alkyl or aryl group containing up to 12 carbon atoms, and X is a monoanionic, monodentate ligand such as chlorine, optionally in the presence of molecular oxygen.

Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

DOEpatents

Nicholas, Christpher P; Boldingh, Edwin P

2013-12-17

A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and show to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hyrdocarbons into hydrocarbons removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

DOEpatents

Nicholas, Christopher P; Boldingh, Edwin P

2014-10-07

A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub.1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Key Elements of the Chemistry of Cytochrome P-450: The Oxygen Rebound Mechanism.

ERIC Educational Resources Information Center

Groves, John T.

1985-01-01

Discusses the structure and function of the liver protein cytochrome P-450, an important catalyst for a variety of detoxification reactions. Diagnostic substracts for this heme-containing monooxygenase, synthetic modes of the active site, and oxidations with synthetic metalloporphyrins are the major topic areas considered. (JN)

Improving the electrocatalytic performance of carbon nanotubes for VO2+/VO2+ redox reaction by KOH activation

NASA Astrophysics Data System (ADS)

Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

2017-04-01

In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO2+/VO2+ redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO2+/VO2+ redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO2+/VO2+ redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO2+/VO2+ redox reaction for VRFB system.

New Boron Analogues of Pyrophosphates and Deoxynucleoside Boranophosphates

PubMed Central

Vyakaranam, Kamesh; Rana, Geeta; Spielvogel, Bernard F.

2001-01-01

Tetraethyldicyanoborane pyrophosphate (2) and 3'-(diethylphosphite-cyanoborano)-5'-dimethoxytrityl.N4-benzoyl-deoxycytidine (3) have been synthesized in 70% and 76% yields, respectively. The compatibility of the substituted boranophosphates with common protecting groups is hereby demonstrated. Boron containing biologically active compounds, such as nucleosides and nucleotides 1-6 and amino acids 7-9 are important due to their potential therapeutic activity, research and diagnostic applications. Many boron containing compounds have shown promising activity as anticancer, 10. 11. 12 antiinflammatory,13 and antiosteoporotic 13agents. Oligonucleotdes in which a non-bridging oxygen atom is replaced by a borane(BH3) group are a very important class of modified nucleic acids. 1. 3. 14-16 The BH3 group is isoelectronic with oxygen in natural oligonucleotides and isoelectronic and isostructural with the oligonucleotide methyl phosphonates, which are nuclease resistant. On the other hand, the α-borano triphosphates are good substrates for DNA polymerases and incorporation of boranophosphates into DNA causes an increase in the resistance to exo- and endonucleases 2. 17a as compared to non-modified DNA. There are also notable applications of the α-borano triphosphates in PCR sequencing 17a and nucleic acid detection 17b. PMID:18475988

Ozone Therapy on Rats Submitted to Subtotal Nephrectomy: Role of Antioxidant System

PubMed Central

Calunga, José Luis; Zamora, Zullyt B.; Borrego, Aluet; del Río, Sarahí; Barber, Ernesto; Menéndez, Silvia; Hernández, Frank; Montero, Teresita; Taboada, Dunia

2005-01-01

Chronic renal failure (CRF) represents a world health problem. Ozone increases the endogenous antioxidant defense system, preserving the cell redox state. The aim of this study is to evaluate the effect of ozone/oxygen mixture in the renal function, morphology, and biochemical parameters, in an experimental model of CRF (subtotal nephrectomy). Ozone/oxygen mixture was applied daily, by rectal insufflation (0.5 mg/kg) for 15 sessions after the nephrectomy. Renal function was evaluated, as well as different biochemical parameters, at the beginning and at the end of the study (10 weeks). Renal plasmatic flow (RPF), glomerular filtration rate (GFR), the urine excretion index, and the sodium and potassium excretions (as a measurement of tubular function) in the ozone group were similar to those in Sham group. Nevertheless, nephrectomized rats without ozone (positive control group) showed the lowest RPF, GFR, and urine excretion figures, as well as tubular function. Animals treated with ozone showed systolic arterial pressure (SAP) figures lower than those in the positive control group, but higher values compared to Sham group. Serum creatinine values and protein excretion in 24 hours in the ozone group were decreased compared with nephrectomized rats, but were still higher than normal values. Histological study demonstrated that animals treated with ozone showed less number of lesions in comparison with nephrectomized rats. Thiobarbituric acid reactive substances were significantly increased in nephrectomized and ozone-treated nephrectomized rats in comparison with Sham group. In the positive control group, superoxide dismutase (SOD) and catalase (CAT) showed the lowest figures in comparison with the other groups. However, ozone/oxygen mixture induced a significant stimulation in the enzymatic activity of CAT, SOD, and glutathione peroxidase, as well as reduced glutathione in relation with Sham and positive control groups. In this animal model of CRF, ozone rectal administrations produced a delay in the advance of the disease, protecting the kidneys against vascular, hemorheological, and oxidative mechanisms. This behavior suggests ozone therapy has a protective effect on renal tissue by downregulation of the oxidative stress shown in CRF. PMID:16192672

Dietary glutamine supplementation partly reverses impaired macrophage function resulting from overload training in rats.

PubMed

Xiao, Weihua; Chen, Peijie; Dong, Jingmei; Wang, Ru; Luo, Beibei

2015-04-01

The aim of this study was to evaluate the effect of overload training on the function of peritoneal macrophages in rats, and to test the hypothesis that glutamine in vivo supplementation would partly reverse the eventual functional alterations induced by overload training in these cells. Forty male Wistar rats were randomly divided into 5 groups: control group (C), overload training group (E1), overload training and restore one week group (E2), glutamine-supplementation group (EG1), and glutamine-supplementation and restore 1-week group (EG2). All rats, except those placed on sedentary control were subjected to 11 weeks of overload training protocol. Blood hemoglobin, serum testosterone, and corticosterone of rats were measured. Moreover, the functions (chemotaxis, phagocytosis, cytokines synthesis, reactive oxygen species generation) of peritoneal macrophages were determined. Data showed that blood hemoglobin, serum testosterone, corticosterone and body weight in the overload training group decreased significantly as compared with the control group. Meanwhile, the chemotaxis capacity (decreased by 31%, p = .003), the phagocytosis capacity (decreased by 27%, p = .005), the reactive oxygen species (ROS) generation (decreased by 35%, p = .003) and the cytokines response capability of macrophages were inhibited by overload training. However, the hindering of phagocytosis and the cytokines response capability of macrophages induced by overload training could be ameliorated and reversed respectively, by dietary glutamine supplementation. These results suggest that overload training impairs the function of peritoneal macrophages, which is essential for the microbicidal actions of macrophages. This may represent a novel mechanism of immunodepression induced by overload training. Nonetheless, dietary glutamine supplementation could partly reverse the impaired macrophage function resulting from overload training.

Importance of oxygen in the metal-free catalytic growth of single-walled carbon nanotubes from SiO(x) by a vapor-solid-solid mechanism.

PubMed

Liu, Bilu; Tang, Dai-Ming; Sun, Chenghua; Liu, Chang; Ren, Wencai; Li, Feng; Yu, Wan-Jing; Yin, Li-Chang; Zhang, Lili; Jiang, Chuanbin; Cheng, Hui-Ming

2011-01-19

To understand in-depth the nature of the catalyst and the growth mechanism of single-walled carbon nanotubes (SWCNTs) on a newly developed silica catalyst, we performed this combined experimental and theoretical study. In situ transmission electron microscopy (TEM) observations revealed that the active catalyst for the SWCNT growth is solid and amorphous SiO(x) nanoparticles (NPs), suggesting a vapor-solid-solid growth mechanism. From in situ TEM and chemical vapor deposition growth experiments, we found that oxygen plays a crucial role in SWCNT growth in addition to the well-known catalyst size effect. Density functional theory calculations showed that oxygen atoms can enhance the capture of -CH(x) and consequently facilitate the growth of SWCNTs on oxygen-containing SiO(x) NPs.

Deoxygenation alters bacterial diversity and community composition in the ocean's largest oxygen minimum zone.

PubMed

Beman, J Michael; Carolan, Molly T

2013-01-01

Oceanic oxygen minimum zones (OMZs) have a central role in biogeochemical cycles and are expanding as a consequence of climate change, yet how deoxygenation will affect the microbial communities that control these cycles is unclear. Here we sample across dissolved oxygen gradients in the oceans' largest OMZ and show that bacterial richness displays a unimodal pattern with decreasing dissolved oxygen, reaching maximum values on the edge of the OMZ and decreasing within it. Rare groups on the OMZ margin are abundant at lower dissolved oxygen concentrations, including sulphur-cycling Chromatiales, for which 16S rRNA was amplified from extracted RNA. Microbial species distribution models accurately replicate community patterns based on multivariate environmental data, demonstrate likely changes in distributions and diversity in the eastern tropical North Pacific Ocean, and highlight the sensitivity of key bacterial groups to deoxygenation. Through these mechanisms, OMZ expansion may alter microbial composition, competition, diversity and function, all of which have implications for biogeochemical cycling in OMZs.

Deoxygenation alters bacterial diversity and community composition in the ocean’s largest oxygen minimum zone

NASA Astrophysics Data System (ADS)

Beman, J. Michael; Carolan, Molly T.

2013-10-01

Oceanic oxygen minimum zones (OMZs) have a central role in biogeochemical cycles and are expanding as a consequence of climate change, yet how deoxygenation will affect the microbial communities that control these cycles is unclear. Here we sample across dissolved oxygen gradients in the oceans’ largest OMZ and show that bacterial richness displays a unimodal pattern with decreasing dissolved oxygen, reaching maximum values on the edge of the OMZ and decreasing within it. Rare groups on the OMZ margin are abundant at lower dissolved oxygen concentrations, including sulphur-cycling Chromatiales, for which 16S rRNA was amplified from extracted RNA. Microbial species distribution models accurately replicate community patterns based on multivariate environmental data, demonstrate likely changes in distributions and diversity in the eastern tropical North Pacific Ocean, and highlight the sensitivity of key bacterial groups to deoxygenation. Through these mechanisms, OMZ expansion may alter microbial composition, competition, diversity and function, all of which have implications for biogeochemical cycling in OMZs.

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

NASA Technical Reports Server (NTRS)

Pawley, Alison R.; Holloway, John R.; Mcmillan, Paul F.

1992-01-01

The solubility of CO2-CO fluids in a midocean ridge basalt have been measured at 1200 C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. In agreement with results of previous studies, the results reported here imply that, at least at low pressures, CO2 dissolves in basaltic melt only in the form of carbonate groups. The dissolution reaction is heterogeneous, with CO2 molecules in the fluid reacting directly with reactive oxygens in the melt to produce CO3(2-). CO, on the other hand, is insoluble, dissolving neither as carbon, molecular CO, nor CO3(2-). It is shown that, for a given pressure and temperature, the concentration of dissolved carbon-bearing species in basaltic melt in equilibrium with a carbon-oxygen fluid is proportional to the mole fraction of CO2 in the fluid, which is a function of fO2. At low pressures CO2 solubility is a linear function of CO2 fugacity at constant temperatures.

Comparison of the bulk geochemical features and thermal reactivity of kerogens from Mol (Boom Clay), Bure (Callovo-Oxfordian argillite) and Tournemire (Toarcian shales) underground research laboratories.

PubMed

Deniau, I; Devol-Brown, I; Derenne, S; Behar, F; Largeau, C

2008-01-25

Deep argillaceous formations are potential repositories for the long-term disposal of nuclear waste because of their low permeability and high sorption capacity with respect to radioelements and heavy metals. Such sedimentary rocks contain organic matter, mostly macromolecular and insoluble (kerogen). Upon temperature elevation related to high-level long-lived radioactive waste disposal, the kerogen may release significant quantities of gaseous and liquid effluents, especially oxygen-containing ones, which may influence the ability of the clay to retain radionuclides. The aim of the present study is to assess the global geochemical features and the thermal reactivity of the kerogens isolated from samples collected in the Bure and Tournemire sites, France (Callovo-Oxfordian Clay and Toarcian Shales, respectively) and to draw comparisons with data previously obtained for the Mol site, Belgium (Boom Clay). The study is based on a combination of elemental, spectroscopic (FTIR, solid state (13)C NMR) and pyrolytic (Rock-Eval pyrolysis, Curie point pyrolysis-gas chromatography/mass spectrometry) analyses. Different levels of maturity and resulting differences in the relative abundance of oxygen-containing groups were thus observed for the three kerogens. This is linked with differences in their ability to generate CO(2) and various oxygen-containing, low molecular weight, water-soluble compounds under thermal stress, decreasing from Mol to Bure and to Tournemire.

Acquired deficiency of tafazzin in the adult heart: Impact on mitochondrial function and response to cardiac injury.

PubMed

Szczepanek, Karol; Allegood, Jeremy; Aluri, Hema; Hu, Ying; Chen, Qun; Lesnefsky, Edward J

2016-04-01

The content and composition of cardiolipin (CL) is critical for preservation of mitochondrial oxidative phosphorylation (OXPHOS) and inner membrane integrity. Tafazzin (Taz) is an enzyme responsible for remodeling of immature CL containing mixed acyl groups into the mature tetralinoleyl form (C18:2)4-CL. We hypothesized that acquired defects in Taz in the mature heart would impact remodeling of CL and augment cardiac injury. The role of acquired Taz deficiency was studied using the inducible Taz knockdown (TazKD) mouse. Taz-specific shRNA is induced by doxycycline (DOX). One day of DOX intake decreased Taz mRNA in the heart to 20% vs. DOX-treated WT. Knockdown was initiated at an adult age and was stable during long term feeding. CL phenotype was assessed by (C18:2)4-CL content and was reduced 40% vs. WT at two months of DOX. TazKD showed increased production of reactive oxygen species and increased susceptibility to permeability transition pore opening at baseline. However, OXPHOS measured using the rate of oxygen consumption was unchanged in the setting of acquired Taz deficiency. Infarct size, measured in isolated buffer-perfused Langendorff hearts following 25min. Stop flow ischemia and 60min. Reperfusion was not altered in TazKD hearts. Thus, impaired Taz-function with onset at adult age does not enhance susceptibility to ischemia-reperfusion injury. Published by Elsevier B.V.

Preparation, quantitative surface analysis, intercalation characteristics and industrial implications of low temperature expandable graphite

NASA Astrophysics Data System (ADS)

Peng, Tiefeng; Liu, Bin; Gao, Xuechao; Luo, Liqun; Sun, Hongjuan

2018-06-01

Expandable graphite is widely used as a new functional carbon material, especially as fire-retardant; however, its practical application is limited due to the high expansion temperature. In this work, preparation process of low temperature and highly expandable graphite was studied, using natural flake graphite as raw material and KMnO4/HClO4/NH4NO3 as oxidative intercalations. The structure, morphology, functional groups and thermal properties were characterized during expanding process by Fourier transform infrared spectroscopy (FTIR), Raman spectra, thermo-gravimetry differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), and scanning electron microscope (SEM). The analysis showed that by oxidation intercalation, some oxygen-containing groups were grafted on the edge and within the graphite layer. The intercalation reagent entered the graphite layer to increase the interlayer spacing. After expansion, the original flaky expandable graphite was completely transformed into worm-like expanded graphite. The order of graphite intercalation compounds (GICs) was proposed and determined to be 3 for the prepared expandable graphite, based on quantitative XRD peak analysis. Meanwhile, the detailed intercalation mechanisms were also proposed. The comprehensive investigation paved a benchmark for the industrial application of such sulfur-free expanded graphite.

Hydrophilic property of 316L stainless steel after treatment by atmospheric pressure corona streamer plasma using surface-sensitive analyses

NASA Astrophysics Data System (ADS)

Al-Hamarneh, Ibrahim; Pedrow, Patrick; Eskhan, Asma; Abu-Lail, Nehal

2012-10-01

Surgical-grade 316L stainless steel (SS 316L) had its surface hydrophilic property enhanced by processing in a corona streamer plasma reactor using O2 gas mixed with Ar at atmospheric pressure. Reactor excitation was 60 Hz ac high-voltage (0-10 kVRMS) applied to a multi-needle-to-grounded screen electrode configuration. The treated surface was characterized with a contact angle tester. Surface free energy (SFE) for the treated stainless steel increased measurably compared to the untreated surface. The Ar-O2 plasma was more effective in enhancing the SFE than Ar-only plasma. Optimum conditions for the plasma treatment system used in this study were obtained. X-ray photoelectron spectroscopy (XPS) characterization of the chemical composition of the treated surfaces confirms the existence of new oxygen-containing functional groups contributing to the change in the hydrophilic nature of the surface. These new functional groups were generated by surface reactions caused by reactive oxidation of substrate species. Atomic force microscopy (AFM) images were generated to investigate morphological and roughness changes on the plasma treated surfaces. The aging effect in air after treatment was also studied.

Pyrolysis of polyethylene terephthalate containing real waste plastics using Ni loaded zeolite catalysts

NASA Astrophysics Data System (ADS)

Al-asadi, M.; Miskolczi, N.

2018-05-01

In this work the pyrolysis of polyethylene terephthalate (PET) containing real waste plastic was investigated using different Ni loaded catalysts: Ni/ZSM-5, Ni/y-zeolite, Ni/β-zeolite and Ni/natural zeolite (clinoptilolite). Raw materials were pyrolyzed in a horizontal tubular reactor between 600 and 900°C using 10% of catalysts. It was found, that both temperature increasing and catalysts presence can increase the gas yields, however owing to gasification reactions, the pyrolysis oil yield decreased with increasing temperature. Ni/y-zeolite catalyst had the most benefit in gas yield increasing at low temperature; however Ni/ZSM-5 showed advanced property in gas yield increasing at high temperature. Gases contained hydrogen, carbon oxides and hydrocarbons, which composition was significantly affected by catalysts. Ni loaded zeolites favoured to the formation of hydrogen and branched hydrocarbons; furthermore the concentrations of both CO and CO2 were also increased as function of elevated temperature. That phenomenon was attributed to the further decomposition of PET, especially to the side chain scission reactions. Owing to the Boudouard reaction, the ratio of CO2/CO can increased with temperature. Pyrolysis oils were the mixtures of n-saturated, n-unsaturated, branched, oxygen free aromatics and oxygenated hydrocarbons. Temperature increasing has a significant effect to the aromatization and isomerization reactions, while the catalysts can efficiently decreased the concentration of oxygen containing compounds.

77 FR 49386 - Airworthiness Directives; Airbus Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-16

... prompted by reports of silicon particles inside the oxygen generator manifolds, which had chafed from the... the part number and serial number of each passenger oxygen container, replacing the oxygen generator manifold of the affected oxygen container with a serviceable manifold, and performing an operational check...

Reactive oxygen species inactivate neuronal nicotinic acetylcholine receptors through a highly conserved cysteine near the intracellular mouth of the channel: implications for diseases that involve oxidative stress

PubMed Central

Krishnaswamy, Arjun; Cooper, Ellis

2012-01-01

Abstract An intriguing feature of several nicotinic acetylcholine receptors (nAChRs) on neurons is that their subunits contain a highly conserved cysteine residue located near the intracellular mouth of the receptor pore. The work summarized in this review indicates that α3β4-containing and α4β2-containing neuronal nAChRs, and possibly other subtypes, are inactivated by elevations in intracellular reactive oxygen species (ROS). This review discusses a model for the molecular mechanisms that underlie this inactivation. In addition, we explore the implications of this mechanism in the context of complications that arise from diabetes. We review the evidence that diabetes elevates cytosolic ROS in sympathetic neurons and inactivates postsynaptic α3β4-containing nAChRs shortly after the onset of diabetes, leading to a depression of synaptic transmission in sympathetic ganglia, an impairment of sympathetic reflexes. These effects of ROS on nAChR function are due to the highly conserved Cys residues in the receptors: replacing the cysteine residues in α3 allow ganglionic transmission and sympathetic reflexes to function normally in diabetes. This example from diabetes suggests that other diseases involving oxidative stress, such as Parkinson's disease, could lead to the inactivation of nAChRs on neurons and disrupt cholinergic nicotinic signalling. PMID:21969449

Effect of physical training in cool and hot environments on +Gz acceleration tolerance in women

NASA Technical Reports Server (NTRS)

Brock, P. J.; Sciaraffa, D.; Greenleaf, J. E.

1982-01-01

Acceleration tolerance, plasma volume, and maximal oxygen uptake were measured in 15 healthy women before and after submaximal isotonic exercise training periods in cool and hot environments. The women were divided on the basis of age, maximal oxygen uptake, and +Gz tolerance into three groups: a group that exercised in heat (40.6 C), a group that exercised at a lower temperature (18.7 C), and a sedentary control group that functioned in the cool environment. There was no significant change in the +Gz tolerance in any group after training, and terminal heart rates were similar within each group. It is concluded that induction of moderate acclimation responses without increases in sweat rate or resting plasma volume has no influence on +Gz acceleration tolerance in women.

Heterocyclic energetic materials: Synthesis, characterization and computational design

NASA Astrophysics Data System (ADS)

Tsyshevsky, Roman; Pagoria, Philip; Smirnov, Aleksander; Kuklja, Maija

2017-06-01

Achievement of the tailored properties (high performance, low sensitivity, etc.) in targeted new energetic materials (EM) remains a great challenge. Recently, attention of researchers has shifted from conventional nitroester-, nitramine-, and nitroaromatic-based explosives to new heterocyclic EM with oxygen- and nitrogenrich molecular structures. They have increased densities and formation enthalpies complemented by attractive performance and high stability to external stimuli. We will demonstrate that oxadiazol-containing heterocycles offer a convenient playground to probe specific chemical functional groups as building blocks for design of EM. We discuss a joint experimental and computational approach for design, characterization, synthesis, and modeling of novel heterocyclic EM. Combinatorically, we comprehensively analyzed how overall stability and performance of each material in the family (BNFF, LLM-172, LLM-175, LLM-191, LLM-192, LLM-200) depends upon their chemical composition and details of the molecular structure (such as a substitution of a nitro group by an amino group and 1,2,5-oxadiazole fragment by 1,2,3- or 1,2,4-oxadiazol ring). We will also discuss proposed new EM with predicted superior chemical and physical properties. P. Pagoria, R. Tsyshevsky, A. Smirnov.

Crown oxygen-doping graphene with embedded main-group metal atoms

NASA Astrophysics Data System (ADS)

Wu, Liyuan; Wang, Qian; Yang, Chuanghua; Quhe, Ruge; Guan, Pengfei; Lu, Pengfei

2018-02-01

Different main-group metal atoms embedded in crown oxygen-doping graphene (metal@OG) systems are studied by the density functional theory. The binding energies and electronic structures are calculated by using first-principles calculations. The binding energy of metal@OG system mainly depends on the electronegativity of the metal atom. The lower the value of the electronegativity, the larger the binding energy, indicating the more stable the system. The electronic structure of metal@OG arouses the emergence of bandgap and shift of Dirac point. It is shown that interaction between metal atom and crown oxygen-doping graphene leads to the graphene's stable n-doping, and the metal@OG systems are stable semiconducting materials, which can be used in technological applications.

Assessment of cognitive impairment in long-term oxygen therapy-dependent COPD patients.

PubMed

Karamanli, Harun; Ilik, Faik; Kayhan, Fatih; Pazarli, Ahmet Cemal

2015-01-01

A number of studies have shown that COPD, particularly in its later and more severe stages, is associated with various cognitive deficits. Thus, the primary goal of the present study was to elucidate the extent of cognitive impairment in patients with long-term oxygen therapy-dependent (LTOTD) COPD. In addition, this study aimed to determine the effectiveness of two cognitive screening tests, the Mini-Mental State Examination (MMSE) and the Montreal Cognitive Assessment (MoCA), for COPD patients and the ability of oxygen therapy to mitigate COPD-related deficits in cognitive function. The present study enrolled 45 subjects: 24 nonuser and 21 regular-user LTOTD-COPD patients. All subjects had a similar grade of education, and there were no significant differences regarding age or sex. The MoCA (cutoff: <26 points) and MMSE (cutoff: ≤24 points) scores were compared between these two groups. The nonuser LTOTD-COPD group had a significantly lower MoCA score than that of the regular-user LTOTD-COPD group (19.38±2.99 vs 21.68±2.14, respectively) as well as a significantly lower MMSE score. Moreover, the absence of supplemental oxygen therapy increased the risk of cognitive impairment (MoCA, P=0.007 and MMSE, P=0.014), and the MoCA and MMSE scores significantly correlated with the number of emergency admissions and the number of hospitalizations in the last year. In the present study, the nonuser LTOTD-COPD group exhibited a significant decrease in cognitive status compared with the regular-user LTOTD-COPD group. This suggests that the assessment of cognitive function in nonuser LTOTD-COPD patients and the use of protective strategies, such as continuous supplemental oxygen treatment, should be considered during the management of COPD in this population. In addition, the MoCA score was superior to the MMSE score for the determination of cognitive impairment in the nonuser LTOTD-COPD patients.

Modeling oxygen transport in human placental terminal villi.

PubMed

Gill, J S; Salafia, C M; Grebenkov, D; Vvedensky, D D

2011-12-21

Oxygen transport from maternal blood to fetal blood is a primary function of the placenta. Quantifying the effectiveness of this exchange remains key in identifying healthy placentas because of the great variability in capillary number, caliber and position within the villus-even in placentas deemed clinically "normal". By considering villous membrane to capillary membrane transport, stationary oxygen diffusion can be numerically solved in terminal villi represented by digital photomicrographs. We aim to provide a method to determine whether and if so to what extent diffusional screening may operate in placental villi. Segmented digital photomicrographs of terminal villi from the Pregnancy, Infection and Nutrition study in North Carolina 2002 are used as a geometric basis for solving the stationary diffusion equation. Constant maternal villous oxygen concentration and perfect fetal capillary membrane absorption are assumed. System efficiency is defined as the ratio of oxygen flux into a villus and the sum of the capillary areas contained within. Diffusion screening is quantified by comparing numerical and theoretical maximum oxygen fluxes. A strong link between various measures of villous oxygen transport efficiency and the number of capillaries within a villus is established. The strength of diffusional screening is also related to the number of capillaries within a villus. Our measures of diffusional efficiency are shown to decrease as a function of the number of capillaries per villus. This low efficiency, high capillary number relationship supports our hypothesis that diffusional screening is present in this system. Oxygen transport per capillary is reduced when multiple capillaries compete for diffusing oxygen. A complete picture of oxygen fluxes, capillary and villus areas is obtainable and presents an opportunity for future work. Copyright © 2011 Elsevier Ltd. All rights reserved.

Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2013-03-14

We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, inducedmore » by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Biodegradation improvement of poly(3-hydroxy-butyrate) films by entomopathogenic fungi and UV-assisted surface functionalization.

PubMed

Kessler, Felipe; Marconatto, Leticia; Rodrigues, Roberta da Silva Bussamara; Lando, Gabriela Albara; Schrank, Augusto; Vainstein, Marilene Henning; Weibel, Daniel Eduardo

2014-01-05

Ultraviolet (UV)-assisted surface modification in the presence of oxygen was used as initial step to achieve controlled degradation of poly(3-hydroxy-butyrate), PHB, films by entomopathogenic fungi. Treated surfaces were investigated by surface analysis techniques (water contact angle, Fourier Transformed Infrared Spectroscopy in Attenuated Total Reflectance mode, X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure, Gel Permeation Chromatography, Optical Microscopy, Scanning Electron Microscopy, and weight loss). After the UV-assisted treatments, new carbonyl groups in new chemical environments were detected by XPS and NEXAFS spectroscopy. The oxidizing atmosphere did not allow the formation of CC bonds, indicating that Norrish Type II mechanism is suppressed during or by the treatments. The higher hydrophilicity and concentration of oxygenated functional groups at the surface of the treated films possibly improved the biodegradation of the films. It was observed a clear increase in the growth of this fungus when oxygenated groups were grafted on the polymers surfaces. This simple methodology can be used to improve and control the degradation rate of PHB films in applications that require a controllable degradation rate. Copyright © 2013 Elsevier B.V. All rights reserved.

78 FR 40074 - Airworthiness Directives; Airbus Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2013-07-03

... certain batch of passenger emergency oxygen container assemblies might become detached by extreme pulling of the mask tube at the end of oxygen supply causing a high temperature oxygen generator and mask to fall down. This proposed AD would require modifying the passenger emergency oxygen container assembly...

Highly sensitive humidity sensing properties of carbon quantum dots films

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

Zhang, Xing; Ming, Hai; Liu, Ruihua

2013-02-15

Graphical abstract: Display Omitted Highlights: ► A humidity sensing device was fabricated based on carbon quantum dots (CQDs) films. ► The conductivity of the CQDs films shows a linear and rapid response to atmosphere humidity. ► The humidity sensing property was due to the hydrogen bonds between the functional groups on CQDs. -- Abstract: We reported the fabrication of a humidity sensing device based on carbon quantum dots (CQDs) film. The conductivity of the CQDs film has a linear and rapid response to relative humidity, providing the opportunity for the fabrication of humidity sensing devices. The mechanism of our humiditymore » sensor was proposed to be the formation of hydrogen bonds between carbon quantum dots and water molecules in the humidity environment, which significantly promote the electrons migration. In a control experiment, this hypothesis was confirmed by comparing the humidity sensitivity of candle soot (i.e. carbon nanoparticles) with and without oxygen containing groups on the surfaces.« less

Modification of carbon fabrics by radio-frequency capacitive discharge at low pressure to regulate mechanical properties of carbon fiber reinforced plastics based on it

NASA Astrophysics Data System (ADS)

Garifullin, A. R.; Krasina, I. V.; Skidchenko, E. A.; Shaekhov, M. F.; Tikhonova, N. V.

2017-01-01

To increase the values of mechanical properties of carbon fiber (CF) composite materials used in sports equipment production the method of radio-frequency capacitive (RFC) low-pressure plasma treatment in air was proposed. Previously it was found that this type of modification allows to effectively regulate the surface properties of fibers of different nature. This treatment method differs from the traditional ones by efficiency and environmental friendliness as it does not require the use of aggressive, environmentally hazardous chemicals. In this paper it was established that RFC low-pressure air plasma treatment of carbon fabrics enhances the interlaminar shear strength (ILSS) of carbon fiber reinforced plastic (CFRP). As a result of experimental studies of CF by Fourier Transform Infrared (FTIR) spectroscopy method it was proved that after radio-frequency capacitive plasma treatment at low pressure in air the oxygen-containing functional groups is grafted on the surface. These groups improve adhesion at the interface “matrix-fiber”.

In situ biodegradation of naphthenic acids in oil sands tailings pond water using indigenous algae-bacteria consortium.

PubMed

Mahdavi, Hamed; Prasad, Vinay; Liu, Yang; Ulrich, Ania C

2015-01-01

In this study, the biodegradation of total acid-extractable organics (TAOs), commonly called naphthenic acids (NAs), was investigated. An indigenous microbial culture containing algae and bacteria was taken from the surface of a tailings pond and incubated over the course of 120days. The influence of light, oxygen and the presence of indigenous algae and bacteria, and a diatom (Navicula pelliculosa) on the TAO removal rate were elucidated. The highest biodegradation rate was observed with bacteria growth only (without light exposure) with a half-life (t(1/2)) of 203days. The algae-bacteria consortium enhanced the detoxification process, however, bacterial biomass played the main role in toxicity reduction. Principal component analysis (PCA) conducted on FT-IR spectra, identified functional groups and bonds (representing potential markers for biotransformation of TAOs) as follows: hydroxyl, carboxyl and amide groups along with CH, arylH, arylOH and NH bonds. Copyright © 2015 Elsevier Ltd. All rights reserved.

Quantitative evaluation of noncovalent interactions between polyphosphate and dissolved humic acids in aqueous conditions.

PubMed

Fang, Wei; Sheng, Guo-Ping; Wang, Long-Fei; Ye, Xiao-Dong; Yu, Han-Qing

2015-12-01

As one kind of phosphorus species, polyphosphate (poly-P) is ubiquitous in natural environments, and the potential interactions between poly-P and humic substances in the sediments or natural waters would influence the fate of poly-P in the environments. However, the mechanism of the interactions has not yet been understood clearly. In this work, the characteristics and mechanisms of the interactions between humic acids (HA) and two model poly-P compounds with various chain lengths have been investigated. Results show that a stable polyphosphate-HA complex would be formed through the noncovalent interactions, and hydrogen bond might be the main driving force for the binding process, which might be formed between the proton-accepting groups of poly-P (e.g., PO and P-O(-)) and the oxygen containing functional groups in HA. Our findings implied that the presence of humic substances in natural waters, soils and sediments would influence the potential transport and/or mobility of environmental poly-P. Copyright © 2015 Elsevier Ltd. All rights reserved.

Discovering herbal functional groups of traditional Chinese medicine.

PubMed

He, Ping; Deng, Ke; Liu, Zhihai; Liu, Delin; Liu, Jun S; Geng, Zhi

2012-03-30

For the traditional Chinese medicine (TCM), a prescription for a patient often contains several herbs. Some herbs are often used together in prescriptions, and these herbs can be considered as a functional group. In this paper, we propose an approach for discovering herbal functional groups from a large set of prescriptions recorded in TCM books. These functional groups are allowed to overlap with each other. Our approach is validated with a simulation study and applied to a data set containing thousands of TCM prescriptions. Copyright © 2011 John Wiley & Sons, Ltd.

Porous carbon derived from disposable shaddock peel as an excellent catalyst toward VO2+/VO2+ couple for vanadium redox battery

NASA Astrophysics Data System (ADS)

Liu, J.; Wang, Z. A.; Wu, X. W.; Yuan, X. H.; Hu, J. P.; Zhou, Q. M.; Liu, Z. H.; Wu, Y. P.

2015-12-01

Functional porous carbon (PC) derived from bio-friendly shaddock peel has been firstly explored as catalyst for vanadium redox flow battery (VRB). The prepared PC is micro-mesoporous with high BET surface area of 882.7 m2 g-1, has some surface oxygen-containing functional groups, and is doped with N and P heteroatoms. These three factors greatly favor the electrochemical reactions of VO2+/VO2+ on the PC modified glass carbon (PC-GC). Compared with the naked GC and graphite modified GC, the PC-GC presents a lower peak separation (66 mV), higher anodic current density (17.1 mA cm-2) and cathodic current density (15.0 mA cm-2). The VRB using PC modified graphite felt (GF) as positive electrode demonstrates an enhanced voltage efficiency of 82.7% at the current density of 60 mA cm-2, and a better rate performance than that from the virginal GF.

Function of the iron-binding chelator produced by Coriolus versicolor in lignin biodegradation.

PubMed

Wang, Lu; Yan, WenChao; Chen, JiaChuan; Huang, Feng; Gao, PeiJi

2008-03-01

An ultrafiltered low-molecular-weight preparation of chelating compounds was isolated from a wood-containing culture of the white-rot basidiomycete Coriolus versicolor. This preparation could chelate Fe3+ and reduce Fe3+ to Fe2+, demonstrating that the substance may serve as a ferric chelator, oxygen-reducing agent, and redox-cycling molecule, which would include functioning as the electron transport carrier in Fenton reaction. Lignin was treated with the iron-binding chelator and the changes in structure were investigated by 1H-NMR, 13C-NMR, difference spectrum caused by ionization under alkaline conditions and nitrobenzene oxidation. The results indicated that the iron-binding chelator could destroy the beta-O-4 bonds in etherified lignin units and insert phenolic hydroxyl groups. The low-molecular-weight chelator secreted by C. versicolor resulted in new phenolic substructures in the lignin polymer, making it susceptible to attack by laccase or manganese peroxidase. Thus, the synergic action of the iron-binding chelator and the lignocellulolytic enzymes made the substrate more accessible to degradation.

Effects of Oxygen Supply During Training on Subjects With COPD Who Are Normoxemic at Rest and During Exercise: A Blinded Randomized Controlled Trial.

PubMed

Spielmanns, Marc; Fuchs-Bergsma, Chantal; Winkler, Aurelia; Fox, Gabriele; Krüger, Stefan; Baum, Klaus

2015-04-01

It is well established that physical training enhances functionality and quality of life in patients with COPD. However, little data exist concerning the effects of the usefulness of oxygen supply during exercise training for > 3 months in patients with COPD who are normoxemic at rest and during exercise. We hypothesized that oxygen supply during training sessions enables higher training intensity and thus optimizes training results in patients with COPD. In this blinded randomized controlled study, we carried out a 24-week training program with progressively increasing loads involving large muscle groups. In addition, we compared the influences of oxygen supplementation. Thirty-six subjects with moderate-to-severe COPD who were not dependent on long-term oxygen therapy trained under supervision for 24 weeks (3 times/week at 30 min/session). Subjects were randomized into 2 groups: oxygen supply via nasal cannula at a flow of 4 L/min and compressed air at the same flow throughout the training program. Lung function tests at rest (inspiratory vital capacity, FEV1, Tiffeneau index), cycle spiroergometry (peak ventilation, peak oxygen uptake, peak respiratory exchange rate, submaximal and peak lactic acid concentrations), 6-min walk tests, and quality-of-life assessments (Medical Outcomes Study 36-Item Short Form questionnaire) were conducted before and after 12 and 24 weeks. Independent of oxygen supplementation, statistically significant improvements occurred in quality of life, maximal tolerated load during cycling, peak oxygen uptake, and 6-min walk test after 12 weeks of training. Notably, there were no further improvements from 12 to 24 weeks despite progressively increased training loads. Endurance training 3 times/week resulted in significant improvements in quality of life and exercise capacity in subjects with moderate-to-severe COPD within the initial 12 weeks, followed by a stable period over the following 12 weeks with no further benefits of supplemental oxygen. Copyright © 2015 by Daedalus Enterprises.

Myocardial perfusion and oxidative stress after 21% vs. 100% oxygen ventilation and uninterrupted chest compressions in severely asphyxiated piglets.

PubMed

Solevåg, Anne Lee; Schmölzer, Georg M; O'Reilly, Megan; Lu, Min; Lee, Tze-Fun; Hornberger, Lisa K; Nakstad, Britt; Cheung, Po-Yin

2016-09-01

Despite the minimal evidence, neonatal resuscitation guidelines recommend using 100% oxygen when chest compressions (CC) are needed. Uninterrupted CC in adult cardiopulmonary resuscitation (CPR) may improve CPR hemodynamics. We aimed to examine 21% oxygen (air) vs. 100% oxygen in 3:1 CC:ventilation (C:V) CPR or continuous CC with asynchronous ventilation (CCaV) in asphyxiated newborn piglets following cardiac arrest. Piglets (1-3 days old) were progressively asphyxiated until cardiac arrest and randomized to 4 experimental groups (n=8 each): air and 3:1 C:V CPR, 100% oxygen and 3:1 C:V CPR, air and CCaV, or 100% oxygen and CCaV. Time to return of spontaneous circulation (ROSC), mortality, and clinical and biochemical parameters were compared between groups. We used echocardiography to measure left ventricular (LV) stroke volume at baseline, at 30min and 4h after ROSC. Left common carotid artery blood pressure was measured continuously. Time to ROSC (heart rate ≥100min(-1)) ranged from 75 to 592s and mortality 50-75%, with no differences between groups. Resuscitation with air was associated with higher LV stroke volume after ROSC and less myocardial oxidative stress compared to 100% oxygen groups. CCaV was associated with lower mean arterial blood pressure after ROSC and higher myocardial lactate than those of 3:1 C:V CPR. In neonatal asphyxia-induced cardiac arrest, using air during CC may reduce myocardial oxidative stress and improve cardiac function compared to 100% oxygen. Although overall recovery may be similar, CCaV may impair tissue perfusion compared to 3:1 C:V CPR. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Refining of fossil resin flotation concentrates from Western coal. Final fifth quarterly report, January 1, 1994--March 31, 1994

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

Jensen, G.F.; Miller, J.D.

1994-05-07

Fossil resins occurring in the Wasatch Plateau coal field are composed mainly of aliphatic components, partially aromatized multi-cyclic terpenoids and a few oxygen functional groups (such as {minus}OH and {minus}COOH). The solvent extracted resins show the presence of a relatively large number of methyl groups when compared to the methylene groups, and this indicates the presence of extensive tertiary carbon and/or highly branching chains. In contrast coal consists primarily of aromatic ring structures, various oxygen functional groups ({minus}OH, >C=O, {minus}C{minus}O) and few aliphatic chains. The color difference observed among the four resin types is explained by the presence of chromophoresmore » (aromatized polyterpenoid) and also by the presence of finely dispersed coal particle inclusions in the resin matrix. The hexane soluble resin fraction has few aromatic compounds when compared to the hexane insoluble but toluene soluble resin fraction.« less

Digital image analysis of fingernail colour in cadavers comparing carbon monoxide poisoning to controls.

PubMed

Langlois, Neil E I

2010-03-01

Carbon monoxide is a component of motor vehicle exhaust fumes, provided a functional catalytic converter is not present. This gas binds avidly to the hemoglobin molecule in red blood cells preventing its oxygen transport function, effectively poisoning the body by starving it of oxygen. In binding to hemoglobin, carbon monoxide forms carboxyhemoglobin, which has a characteristic bright pink color. It has been remarked that the fingernails of victims of carbon monoxide tend to exhibit pink color, otherwise fingernails of deceased bodies tend towards a dark red to blue color. This study sought to objectively determine by using digital image analysis if a color difference occurred between the fingernails of a group of cadavers with carbon monoxide poisoning compared to a group of controls. The fingernails of the carbon monoxide group did tend to be more red than the controls, but due to overlap between the two groups assessment of the fingernails cannot be recommended as a rapid screening test.

The origins of marine bioluminescence: turning oxygen defence mechanisms into deep-sea communication tools.

PubMed

Rees, J F; de Wergifosse, B; Noiset, O; Dubuisson, M; Janssens, B; Thompson, E M

1998-04-01

Bioluminescence, the emission of ecologically functional light by living organisms, emerged independently on several occasions, yet the evolutionary origins of most bioluminescent systems remain obscure. We propose that the luminescent substrates of the luminous reactions (luciferins) are the evolutionary core of most systems, while luciferases, the enzymes catalysing the photogenic oxidation of the luciferin, serve to optimise the expression of the endogenous chemiluminescent properties of the luciferin. Coelenterazine, a luciferin occurring in many marine bioluminescent groups, has strong antioxidative properties as it is highly reactive with reactive oxygen species such as the superoxide anion or peroxides. We suggest that the primary function of coelenterazine was originally the detoxification of the deleterious oxygen derivatives. The functional shift from its antioxidative to its light-emitting function might have occurred when the strength of selection for antioxidative defence mechanisms decreased. This might have been made possible when marine organisms began colonising deeper layers of the oceans, where exposure to oxidative stress is considerably reduced because of reduced light irradiance and lower oxygen levels. A reduction in metabolic activity with increasing depth would also have decreased the endogenous production of reactive oxygen species. Therefore, in these organisms, mechanisms for harnessing the chemiluminescence of coelenterazine in specialised organs could have developed, while the beneficial antioxidative properties were maintained in other tissues. The full range of graded irradiance in the mesopelagic zone, where the majority of organisms are bioluminescent, would have provided a continuum for the selection and improvement of proto-bioluminescence. Although the requirement for oxygen or reactive oxygen species observed in bioluminescent systems reflects the high energy required to produce visible light, it may suggest that oxygen-detoxifying mechanisms provided excellent foundations for the emergence of many bioluminescent systems.

Cardiopulmonary function and oxygen delivery during total liquid ventilation.

PubMed

Tsagogiorgas, Charalambos; Alb, Markus; Herrmann, Peter; Quintel, Michael; Meinhardt, Juergen P

2011-10-01

Total liquid ventilation (TLV) with perfluorocarbons has shown to improve cardiopulmonary function in the injured and immature lung; however there remains controversy over the normal lung. Hemodynamic effects of TLV in the normal lung currently remain undetermined. This study compared changes in cardiopulmonary and circulatory function caused by either liquid or gas tidal volume ventilation. In a prospective, controlled study, 12 non-injured anesthetized, adult New Zealand rabbits were primarily conventionally gas-ventilated (CGV). After instrumentation for continuous recording of arterial (AP), central venous (CVP), left artrial (LAP), pulmonary arterial pressures (PAP), and cardiac output (CO) animals were randomized into (1) CGV group and (2) TLV group. In the TLV group partial liquid ventilation was initiated with instillation of perfluoroctylbromide (12 ml/kg). After 15 min, TLV was established for 3 hr applying a volume-controlled, pressure-limited, time-cycled ventilation mode using a double-piston configured TLV. Controls (CGV) remained gas-ventilated throughout the experiment. During TLV, heart rate, CO, PAP, MAP, CVP, and LAP as well as derived hemodynamic variables, arterial and mixed venous blood gases, oxygen delivery, PVR, and SVR did not differ significantly compared to CGV. Liquid tidal volumes suitable for long-term TLV in non-injured rabbits do not significantly impair CO, blood pressure, and oxygen dynamics when compared to CGV. Copyright © 2011 Wiley-Liss, Inc.

Milrinone, dobutamine or epinephrine use in asphyxiated newborn pigs resuscitated with 100% oxygen.

PubMed

Joynt, Chloë; Bigam, David L; Charrois, Gregory; Jewell, Laurence D; Korbutt, Gregory; Cheung, Po-Yin

2010-06-01

After resuscitation, asphyxiated neonates often develop poor cardiac function with hypotension, pulmonary hypertension and multiorgan ischemia. In a swine model of neonatal hypoxia-reoxygenation, effects of epinephrine, dobutamine and milrinone on systemic, pulmonary and regional hemodynamics and oxygen transport were compared. Controlled, block-randomized study. University research laboratory. Mixed breed piglets (1-3 days, 1.5-2.3 kg). In acutely instrumented piglets, normocapnic alveolar hypoxia (10-15% oxygen) was induced for 2 h followed by reoxygenation with 100% oxygen (1 h) then 21% oxygen (3 h). At 2 h of reoxygenation, after volume loading (Ringer's lactate 10 ml/kg), either saline (placebo), epinephrine (0.5 microg/kg/min), dobutamine (20 microg/kg/min) or milrinone (0.75 microg/kg/min) were infused for 2 h in a blinded, block-randomized fashion (n = 6/group). All medications similarly improved cardiac output, stroke volume and systemic oxygen delivery (vs. placebo-controls, p < 0.05). Epinephrine and dobutamine significantly increased, while milrinone maintained, mean arterial pressure over pretreatment values while placebo-treated piglets developed hypotension and shock. The mean arterial to pulmonary arterial pressures ratio was not different among groups. All medications significantly increased carotid and intestinal, but not renal, arterial blood flows and oxygen delivery, whereas milrinone caused lower renal vascular resistance than epinephrine and dobutamine-treated groups. Plasma troponin I, plasma and myocardial lactate levels, and histologic ischemic features were not different among groups. In newborn piglets with hypoxia-reoxygenation, epinephrine, dobutamine and milrinone are effective inotropes to improve cardiac output, carotid and intestinal perfusion, without aggravating pulmonary hypertension. Milrinone may also improve renal perfusion.

Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

PubMed

Sumaraj; Padhye, Lokesh P

2017-10-01

Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of oxygen supply on the size of implantable islet-containing encapsulation devices.

PubMed

Papas, Klearchos K; Avgoustiniatos, Efstathios S; Suszynski, Thomas M

2016-03-01

Beta-cell replacement therapy is a promising approach for the treatment of diabetes but is currently limited by the human islet availability and by the need for systemic immunosuppression. Tissue engineering approaches that will enable the utilization of islets or β-cells from alternative sources (such as porcine islets or human stem cell derived beta cells) and minimize or eliminate the need for immunosuppression have the potential to address these critical limitations. However, tissue engineering approaches are critically hindered by the device size (similar to the size of a large flat screen television) required for efficacy in humans. The primary factor dictating the device size is the oxygen availability to islets to support their viability and function (glucose-stimulated insulin secretion [GSIS]). GSIS is affected (inhibited) at a much higher oxygen partial pressure [pO2] than that of viability (e.g. 10 mmHg as opposed to 0.1 mmHg). Enhanced oxygen supply (higher pO2) than what is available in vivo at transplant sites can have a profound effect on the required device size (potentially reduce it to the size of a postage stamp). This paper summarizes key information on the effect of oxygen on islet viability and function within immunoisolation devices and describes the potential impact of enhanced oxygen supply to devices in vivo on device size reduction.

Solid state oxygen sensor

DOEpatents

Garzon, Fernando H.; Chung, Brandon W.; Raistrick, Ian D.; Brosha, Eric L.

1996-01-01

Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer.

78 FR 64162 - Airworthiness Directives; Airbus Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-28

... container assembly. We are issuing this AD to prevent a high temperature oxygen generator and mask from... oxygen generators installed on a certain batch of passenger emergency oxygen container assemblies might become detached by extreme pulling of the mask tube at the end of the oxygen supply causing a high...

Strong coupling diagram technique for the three-band Hubbard model

NASA Astrophysics Data System (ADS)

Sherman, A.

2016-03-01

Strong coupling diagram technique equations are derived for hole Green’s functions of the three-band Hubbard model, which describes Cu-O planes of high-Tc cuprates. The equations are self-consistently solved in the approximation, in which the series for the irreducible part in powers of the oxygen-copper hopping constant is truncated to two lowest-order terms. For parameters used for hole-doped cuprates, the calculated energy spectrum consists of lower and upper Hubbard subbands of predominantly copper nature, oxygen bands with a small admixture of copper states and the Zhang-Rice states of mixed nature, which are located between the lower Hubbard subband and oxygen bands. The spectrum contains also pseudogaps near transition frequencies of Hubbard atoms on copper sites.

Charge transfer and surface defect healing within ZnO nanoparticle decorated graphene hybrid materials

NASA Astrophysics Data System (ADS)

Pham, Chuyen V.; Repp, Sergej; Thomann, Ralf; Krueger, Michael; Weber, Stefan; Erdem, Emre

2016-05-01

To harness the unique properties of graphene and ZnO nanoparticles (NPs) for novel applications, the development of graphene-ZnO nanoparticle hybrid materials has attracted great attention and is the subject of ongoing research. For this contribution, graphene-oxide-ZnO (GO-ZnO) and thiol-functionalized reduced graphene oxide-ZnO (TrGO-ZnO) nanohybrid materials were prepared by novel self-assembly processes. Based on electron paramagnetic resonance (EPR) and photoluminescence (PL) investigations on bare ZnO NPs, GO-ZnO and TrGO-ZnO hybrid materials, we found that several physical phenomena were occurring when ZnO NPs were hybridized with GO and TrGO. The electrons trapped in Zn vacancy defects (VZn-) within the core of ZnO NPs vanished by transfer to GO and TrGO in the hybrid materials, thus leading to the disappearance of the core signals in the EPR spectra of ZnO NPs. The thiol groups of TrGO and sulfur can effectively ``heal'' the oxygen vacancy (VO+) related surface defects of ZnO NPs while oxygen-containing functionalities have low healing ability at a synthesis temperature of 100 °C. Photoexcited electron transfer from the conduction band of ZnO NPs to graphene leads to photoluminescence (PL) quenching of near band gap emission (NBE) of both GO-ZnO and TrGO-ZnO. Simultaneously, electron transfer from graphene to defect states of ZnO NPs is the origin of enhanced green defect emission from GO-ZnO. This observation is consistent with the energy level diagram model of hybrid materials.To harness the unique properties of graphene and ZnO nanoparticles (NPs) for novel applications, the development of graphene-ZnO nanoparticle hybrid materials has attracted great attention and is the subject of ongoing research. For this contribution, graphene-oxide-ZnO (GO-ZnO) and thiol-functionalized reduced graphene oxide-ZnO (TrGO-ZnO) nanohybrid materials were prepared by novel self-assembly processes. Based on electron paramagnetic resonance (EPR) and photoluminescence (PL) investigations on bare ZnO NPs, GO-ZnO and TrGO-ZnO hybrid materials, we found that several physical phenomena were occurring when ZnO NPs were hybridized with GO and TrGO. The electrons trapped in Zn vacancy defects (VZn-) within the core of ZnO NPs vanished by transfer to GO and TrGO in the hybrid materials, thus leading to the disappearance of the core signals in the EPR spectra of ZnO NPs. The thiol groups of TrGO and sulfur can effectively ``heal'' the oxygen vacancy (VO+) related surface defects of ZnO NPs while oxygen-containing functionalities have low healing ability at a synthesis temperature of 100 °C. Photoexcited electron transfer from the conduction band of ZnO NPs to graphene leads to photoluminescence (PL) quenching of near band gap emission (NBE) of both GO-ZnO and TrGO-ZnO. Simultaneously, electron transfer from graphene to defect states of ZnO NPs is the origin of enhanced green defect emission from GO-ZnO. This observation is consistent with the energy level diagram model of hybrid materials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00393a

Investigation of the factors that influence lead accumulation onto polyethylene: Implication for potable water plumbing pipes.

PubMed

Salehi, Maryam; Jafvert, Chad T; Howarter, John A; Whelton, Andrew J

2018-04-05

The influence of polymer aging, water pH, and aqueous Pb concentration on Pb deposition onto low density polyethylene (LDPE) was investigated. LDPE pellets were aged by ozonation at 85 °C. ATR-FTIR and X-ray photoelectron spectroscopy (XPS) analysis of aged LDPE surfaces showed that a variety of polar functional groups (>CO<, >CO, >COO) were formed during aging. These functional groups likely provided better nucleation sites for Pb(OH) 2 deposition compared to new LDPE, which did not have these oxygen-containing functional groups. The type and amount of Pb species present on these surfaces were evaluated through XPS. The influence of exposure duration on Pb deposition onto LDPE was modeled using the pseudo-first-order equation. Distribution ratios of 251.5 for aged LDPE and 69.3 for new LDPE showed that Pb precipitates had greater affinity for the surface of aged LDPE compared to new LDPE. Aged LDPE had less Pb surface loading at pH 11 compared to loading at pH 7.8. Pb surface loading for aged LDPE changed linearly with aging duration (from 0.5-7.5 h). Pb surface loading on both new and aged LDPE increased linearly with increasing Pb initial concentration. Greater Pb precipitation rates were found for aged LDPE compared to new LDPE at both tested pH values. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of a helium/oxygen mixture on individuals' lung function and metabolic cost during submaximal exercise for participants with obstructive lung diseases.

PubMed

Häussermann, Sabine; Schulze, Anja; Katz, Ira M; Martin, Andrew R; Herpich, Christiane; Hunger, Theresa; Texereau, Joëlle

2015-01-01

Helium/oxygen therapies have been studied as a means to reduce the symptoms of obstructive lung diseases with inconclusive results in clinical trials. To better understand this variability in results, an exploratory physiological study was performed comparing the effects of helium/oxygen mixture (78%/22%) to that of medical air. The gas mixtures were administered to healthy, asthmatic, and chronic obstructive pulmonary disease (COPD) participants, both moderate and severe (6 participants in each disease group, a total of 30); at rest and during submaximal cycling exercise with equivalent work rates. Measurements of ventilatory parameters, forced spirometry, and ergospirometry were obtained. There was no statistical difference in ventilatory and cardiac responses to breathing helium/oxygen during submaximal exercise. For asthmatics, but not for the COPD participants, there was a statistically significant benefit in reduced metabolic cost, determined through measurement of oxygen uptake, for the same exercise work rate. However, the individual data show that there were a mixture of responders and nonresponders to helium/oxygen in all of the groups. The inconsistent response to helium/oxygen between individuals is perhaps the key drawback to the more effective and widespread use of helium/oxygen to increase exercise capacity and for other therapeutic applications.

Stable Isotope Analyses of Phosphate Oxygen From Micro-samples of Biological Apatite: A new Routine Procedure for Silverphosphate Micro-precipitation and the Removal of Organic Contamination

NASA Astrophysics Data System (ADS)

Wiedemann-Bidlack, F. B.; Colman, A. S.; Fogel, M. L.

2003-12-01

Oxygen isotope analyses in bone and teeth of living and fossil animals are widely used for testing hypotheses about variability of diet and habitat. For the analysis of environmental or dietary changes in the past, tooth enamel has become the preferred study material, because its mineral content is higher than bone and dentine, and the relatively large size of the carbonato-apatite crystals of enamel make it more stable against post mortem diagenetic alteration than dentine or bone. Intra-tooth sampling of dental enamel is increasingly used for the investigation of seasonal climate variability, taking advantage of both the high correlation between an animal's drinking water and the δ 18O in its mineralized tissues and the incremental growth pattern of tooth enamel. The different oxygen-containing ions of bioapatite (phosphate, carbonate, and hydroxyl group) incorporate into the mineral lattice at different rates during enamel mineralization, and differ in their susceptibility against post mortem diagenetic alteration. In addition, it is difficult to account for the different reaction chemistries of phosphate, carbonate, and hydroxyl group using isotope analysis techniques that include all oxygen contained in the enamel (e.g., laser ablation). These problems can be addressed analyzing phosphate oxygen only. However, two major factors limit the potential of δ 18O analyses in dental enamel: A) the starting sample size for isotope analyzes often precludes the use of small teeth or the intra-tooth sampling of a given tooth; B) Small amounts of biogenic organic material in tooth enamel (less than 1% by wt) can reduce the precision and lead to anomalous analytical results in δ 18O measurements on Ag3PO4 produced from tooth enamel. A new procedure was developed for the pre-treatment and δ 18O analysis of phosphate from small samples (500 μ g) of tooth enamel containing organic matter. Ag3PO{4} was precipitated quantitatively for analysis of δ 18Ophosphate using a Thermoquest-Finnigan TC/EA coupled to Delta Plus XL. A sodium hypochlorite sample pre-treatment step was determined to remove organic matter quantitatively without altering the isotopic composition of the phosphate oxygen. The reproducibility of δ 18O values for pretreated samples (0.2-0.3 ‰ , 1σ ) is much better than for samples without pre-treatment (1.2 ‰ , 1σ ). Phosphate oxygen isotope standards processed using this technique gave measured values indistinguishable from the standard composition, demonstrating the accuracy of the new technique.

The Mn4Ca-cluster of the photosynthetic oxygen evolving centre: its structure, function and evolution.

PubMed

Barber, James

2016-10-05

Photosystem II is the chlorophyll containing enzyme in which the very first chemical energy storing reaction of photosynthesis occurs. It does so by splitting water into molecular oxygen and hydrogen equivalents at a catalytic centre composed of four Mn ions and one Ca2+. All the oxygen in the atmosphere is derived from this reaction and without it the biosphere, as we know it, would not exist. Indeed its appearance about 3 billion years ago gave rise to the "big bang of evolution". Thus understanding the structure and functioning of this metal cluster is a major topic in science and here I discuss it in terms of research over of the last twelve years dating back to when it was first proposed to be a Mn3CaO4 cubane with the fourth Mn attached to cubane by one of its oxo bridging bonds. In so doing a number of novel properties emerge for this metallo-protein with implications for its mechanism and evolutionary origin.

Are soluble factors relevant for polymorphonuclear leukocyte dysregulation in septicemia?

PubMed Central

Wenisch, C; Graninger, W

1995-01-01

Polymorphonuclear leukocytes (PMNs) of twelve patients with gram-negative septicemia exhibited a decreased capacity to phagocytize Escherichia coli and generate reactive oxygen products which normalized within 7 days of treatment. Ex vivo exchange of plasma from age-, sex-, and blood-group-identical normal controls resulted in an increase of both phagocytic capacity and reactive oxygen intermediate generation in PMNs of septicemic patients and transiently reduced phagocytosis and reactive oxygen intermediate production in PMNs of normal controls. These results suggest that extrinsic factors are crucial for PMN function. PMID:7697538

Impact of Plasma Surface Treatment on Bamboo Charcoal/silver Nanocomposite

NASA Astrophysics Data System (ADS)

Vignesh, K.; Vijayalakshmi, K. A.; Karthikeyan, N.

2016-10-01

Bamboo charcoal (BC) accompanied silver (Ag) nanocomposite is synthesized through sol-gel method. The produced BC/Ag nanocomposite was surface modified by air and oxygen plasma treatments. Silver ions (Ag+) will serve to improve the antibacterial activity as well as the surface area of BC. Plasma treatment has improved the surface functional groups, crystalline intensity and antibacterial activity of the prepared nanocomposite. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) studies show that Ag nanoparticles have good agreement with BC and the particle size has a mean diameter of 20-40nm. We observe the carboxyl functional groups in Fourier transform infrared spectroscopy (FTIR) after the oxygen plasma treatment. Moreover surface area and adsorption were analyzed by using the Brunauer, Emmett and Teller (BET) surface area (SBET) and UV-Vis spectroscopy.

Organic Liquids Containing Oxygen.

ERIC Educational Resources Information Center

McDonald, J.; And Others

This unit is one of a group of units written to fit the Certificate of Sixth Year Studies (CSYS) chemistry course, but it could be used with most Sixth Form courses. It includes: (1) background information for teachers with notes on five topics (antifreeze, ethanol production, solvent prices, iron extraction, and paint solvents); (2) a student…

40 CFR 79.56 - Fuel and fuel additive grouping system.

Code of Federal Regulations, 2010 CFR

2010-07-01

... further testing under the provisions of Tier 3 or to support regulatory decisions affecting that fuel or... elements or classes of compounds other than those permitted in the base fuel for the respective fuel family... all of the following criteria: (1) Contain no elements other than carbon, hydrogen, oxygen, nitrogen...

Long life lithium batteries with stabilized electrodes

DOEpatents

Amine, Khalil [Downers Grove, IL; Liu, Jun [Naperville, IL; Vissers, Donald R [Naperville, IL; Lu, Wenquan [Darien, IL

2009-03-24

The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In some embodiments the additives include a substituted or unsubstituted cyclic or spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group. When used in electrochemical devices with, e.g., lithium manganese oxide spinel electrodes or olivine or carbon-coated olivine electrodes, the new electrolytes provide batteries with improved calendar and cycle life.

Directional liquefaction of biomass for phenolic compounds and in situ hydrodeoxygenation upgrading of phenolics using bifunctional catalysts

Treesearch

Junfeng Feng; Chung-yun Hse; Kui Wang; Zhongzhi Yang; Jianchun Jiang; Junming Xu

2017-01-01

Phenolic compounds derived from biomass are important feedstocks for the sustainable production of hydrocarbon biofuels. Hydrodeoxygenation is an effective process to remove oxygen-containing functionalities in phenolic compounds. This paper reported a simple method for producing hydrocarbons by liquefying biomass and upgrading liquefied products. Three phenolic...

Nanoporous carbon materials with enhanced supercapacitance performance and non-aromatic chemical sensing with C1/C2 alcohol discrimination

NASA Astrophysics Data System (ADS)

Shrestha, Lok Kumar; Adhikari, Laxmi; Shrestha, Rekha Goswami; Adhikari, Mandira Pradhananga; Adhikari, Rina; Hill, Jonathan P.; Pradhananga, Raja Ram; Ariga, Katsuhiko

2016-01-01

We have investigated the textural properties, electrochemical supercapacitances and vapor sensing performances of bamboo-derived nanoporous carbon materials (NCM). Bamboo, an abundant natural biomaterial, was chemically activated with phosphoric acid at 400 °C and the effect of impregnation ratio of phosphoric acid on the textural properties and electrochemical performances was systematically investigated. Fourier transform-infrared (FTIR) spectroscopy confirmed the presence of various oxygen-containing surface functional groups (i.e. carboxyl, carboxylate, carbonyl and phenolic groups) in NCM. The prepared NCM are amorphous in nature and contain hierarchical micropores and mesopores. Surface areas and pore volumes were found in the range 218-1431 m2 g-1 and 0.26-1.26 cm3 g-1, respectively, and could be controlled by adjusting the impregnation ratio of phosphoric acid and bamboo cane powder. NCM exhibited electrical double-layer supercapacitor behavior giving a high specific capacitance of c.256 F g-1 at a scan rate of 5 mV s-1 together with high cyclic stability with capacitance retention of about 92.6% after 1000 cycles. Furthermore, NCM exhibited excellent vapor sensing performance with high sensitivity for non-aromatic chemicals such as acetic acid. The system would be useful to discriminate C1 and C2 alcohol (methanol and ethanol).

Rapid and efficient removal of Pb(II) from aqueous solutions using biomass-derived activated carbon with humic acid in-situ modification.

PubMed

Guo, Zizhang; Zhang, Jian; Kang, Yan; Liu, Hai

2017-11-01

This study developed an humic acid (HA) in-situ modified activated carbon adsorbent (AC-HA) for the rapid and efficient removal of Pb(II) from aqueous media, and adsorption mechanisms are discussed. The physicochemical characteristics of activated carbons (AC) were investigated via N 2 adsorption/desorption, scanning electron microscopy (SEM), Boehm's titration method and Fourier transform infrared spectroscopy (FTIR). AC-HA exhibited richer oxygen-containing functional groups than the original AC. In addition, the removal performance of AC-HA (250.0mg/g) toward Pb(II) was greatly improved compared with the original AC (166.7mg/g). The batch adsorption study results revealed that the Pb(II) adsorption data were best fit by the pseudo-second-order model of kinetics and Langmuir isotherm of isothermals, and therefore, the effect of the solution pH was studied. The superior performance of AC-HA was attributed to the HA modification, which contains numbers of groups and has a strong π-π interaction binding energy with AC and Pb(II) species. The adsorption mechanisms were confirmed via the XPS study. More importantly, the modified method is simple and has a low cost of production. Copyright © 2017 Elsevier Inc. All rights reserved.

Alcohol conversion

DOEpatents

Wachs, Israel E.; Cai, Yeping

2002-01-01

Preparing an aldehyde from an alcohol by contacting the alcohol in the presence of oxygen with a catalyst prepared by contacting an intimate mixture containing metal oxide support particles and particles of a catalytically active metal oxide from Groups VA, VIA, or VIIA, with a gaseous stream containing an alcohol to cause metal oxide from the discrete catalytically active metal oxide particles to migrate to the metal oxide support particles and to form a monolayer of catalytically active metal oxide on said metal oxide support particles.

Detonation nanodiamonds for doping Kevlar.

PubMed

Comet, Marc; Pichot, Vincent; Siegert, Benny; Britz, Fabienne; Spitzer, Denis

2010-07-01

This paper reports on the first attempt to enclose diamond nanoparticles--produced by detonation--into a Kevlar matrix. A nanocomposite material (40 wt% diamond) was prepared by precipitation from an acidic solution of Kevlar containing dispersed nanodiamonds. In this material, the diamond nanoparticles (Ø = 4 nm) are entirely wrapped in a Kevlar layer about 1 nm thick. In order to understand the interactions between the nanodiamond surface and the polymer, the oxygenated surface functional groups of nanodiamond were identified and titrated by Boehm's method which revealed the exclusive presence of carboxyl groups (0.85 sites per nm2). The hydrogen interactions between these groups and the amide groups of Kevlar destroy the "rod-like" structure and the classical three-dimensional organization of this polymer. The distortion of Kevlar macromolecules allows the wrapping of nanodiamonds and leads to submicrometric assemblies, giving a cauliflower structure reminding a fractal object. Due to this structure, the macroscopic hardness of Kevlar doped by nanodiamonds (1.03 GPa) is smaller than the one of pure Kevlar (2.31 GPa). To our knowledge, this result is the first illustration of the change of the mechanical properties induced by doping the Kevlar with nanoparticles.

Novel Functions of an Iron-Sulfur Flavoprotein from Trichomonas vaginalis Hydrogenosomes

PubMed Central

Smutná, Tamara; Pilarová, Katerina; Tarábek, Ján; Tachezy, Jan

2014-01-01

Iron-sulfur flavoproteins (Isf) are flavin mononucleotide (FMN)- and FeS cluster-containing proteins commonly encountered in anaerobic prokaryotes. However, with the exception of Isf from Methanosarcina thermophila, which participates in oxidative stress management by removing oxygen and hydrogen peroxide, none of these proteins has been characterized in terms of function. Trichomonas vaginalis, a sexually transmitted eukaryotic parasite of humans, was found to express several iron-sulfur flavoprotein (TvIsf) homologs in its hydrogenosomes. We show here that in addition to having oxygen-reducing activity, the recombinant TvIsf also functions as a detoxifying reductase of metronidazole and chloramphenicol, both of which are antibiotics effective against a variety of anaerobic microbes. TvIsf can utilize both NADH and reduced ferredoxin as electron donors. Given the prevalence of Isf in anaerobic prokaryotes, we propose that these proteins are central to a novel defense mechanism against xenobiotics. PMID:24663020

Catalytic routes and oxidation mechanisms in photoreforming of polyols

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

Sanwald, Kai E.; Berto, Tobias F.; Eisenreich, Wolfgang

2016-12-01

Photocatalytic reforming of biomass-derived oxygenates leads to H 2 generation and evolution of CO 2 via parallel formation of organic intermediates through anodic oxidations on a Rh/TiO 2 photocatalyst. The reaction pathways and kinetics in the photoreforming of C 3–C 6 polyols were explored. Polyols are converted via direct and indirect hole transfer pathways resulting in (i) oxidative rupture of C–C bonds, (ii) oxidation to a-oxygen functionalized aldoses and ketoses (carbonyl group formation) and (iii) light-driven dehydration. Direct hole transfer to chemisorbed oxygenates on terminal Ti(IV)-OH groups, generating alkoxy-radicals that undergo ß-C–C-cleavage, is proposed for the oxidative C–C rupture. Carbonylmore » group formation and dehydration are attributed to indirect hole transfer at surface lattice oxygen sites [Ti_ _ _O_ _ _Ti] followed by the generation of carbon-centered radicals. Polyol chain length impacts the contribution of the oxidation mechanisms favoring the C–C bond cleavage (internal preferred over terminal) as the dominant pathway with higher polyol carbon number.« less

Polymer composites with graphene nanofillers: electrical properties and applications.

PubMed

Tjong, Sie Chin

2014-02-01

Graphene with extraordinary high elastic modulus and excellent electrical conductivity has good prospects for use as the filler material for fabricating novel polymer composites designed for electrostatic discharge and EMI shielding protection, field emission, gas sensor, and fuel cell applications. Large amounts of graphene oxide (GO) can be obtained by wet chemical oxidation of graphite into a mixture of concentrated sulfuric acid, sodium nitrate and potassium permanganate. Accordingly, carbon atoms in the basal plane and edges of GO are decorated with oxygenated functional groups, forming an electrical insulator. To restore electrical conductivity, chemical reduction or thermal annealing is needed to eliminate oxygenated groups of GO. However, such treatments induce internal defects and remove oxygenated atoms of GO partially. The remnant-oxygenated groups affect electrical conductivity of graphene greatly. Nevertheless, reduced graphene oxide and thermally reduced graphene oxide are sufficiently conductive to form polymer nanocomposites at very low percolation threshold. This review provides the fundamentals and state-of-the-art developments in the fabrication methods and electrical property characterizations as well as the applications of novel graphene/polymer nanocomposites. Particular attention is paid to their processing-structural-electrical property relationships.

Dietary incorporation of feedstuffs naturally high in organic selenium for racing pigeons (Columba livia): effects on plasma antioxidant markers after a standardised simulation of a flying effort.

PubMed

Schoonheere, N; Dotreppe, O; Pincemail, J; Istasse, L; Hornick, J L

2009-06-01

Selenium is a trace element of importance for animal health. It is essential for adequate functioning of many enzymes such as, the antioxidant enzyme, glutathione peroxidase, which protects the cell against free radicals. A muscular effort induces a rise in reactive oxygen species production which, in turn, can generate an oxidative stress. Two groups of eight racing pigeons were fed respectively with a diet containing 30.3 (control group) and 195.3 (selenium group) microg selenium/kg diet. The pigeons were submitted to a standardised simulation of a flying effort during 2 h. Blood was taken before and after the effort to measure antioxidant markers and blood parameters related to muscle metabolism. Plasma selenium concentration and glutathione peroxidase activity were significantly higher in the selenium group. There were no significant differences for the other measured parameters. As a consequence of the effort, the pigeons of the selenium group showed a higher increase of glutathione peroxidase activity and a smaller increase of plasma lactate concentration. Variations because of the effort in the other markers were not significantly different between the two groups. It is concluded that the selenium status was improved with the feeding of feedstuffs high in Selenium.

Modification of polystyrene-based activated carbon spheres to improve adsorption of dibenzothiophene

NASA Astrophysics Data System (ADS)

Wang, Qin; Liang, Xiaoyi; Qiao, Wenming; Liu, Chaojun; Liu, Xiaojun; Zhang, Rui; Ling, Licheng

2009-01-01

Polystyrene-based activated carbon spheres (PACS) were modified with either air, HNO 3, (NH 4) 2S 2O 8, H 2O 2 or H 2 to improve their adsorption properties of dibenzothiophene (DBT). The texture and surface chemistry of PACS were characterized by N 2 adsorption, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), acid-base titration and elemental analysis. The results showed that HNO 3 and (NH 4) 2S 2O 8 treatments introduced large amount of acidic groups such as carboxylic, lactones and anhydride groups, while air and H 2O 2 had relatively mild effects and introduced a small quantity of phenol, carbonyl and ether groups. In the HNO 3 treatment, the acidic groups might be fixed on the internal and external surface of PACS, which may act as active sites of adsorption, resulting in increase of the adsorption amount by 45%. Whereas H 2O 2 and (NH 4) 2S 2O 8 treatments might fix more oxygen-containing groups on the external surface, which may hinder DBT molecule enter into micropores, leading to rather lower adsorption capacity with the extent of oxidation. So, the concentration, distribution and types of the acidic functional groups are responsible for the removal of DBT.

Asymmetric 3d Electronic Structure for Enhanced Oxygen Evolution Catalysis.

PubMed

Liu, Yang; Yin, Shibin; Shen, Pei Kang

2018-06-27

The oxygen evolution reaction (OER) is an essential process for renewable energy, and designing a bifunctional oxygen electrocatalyst with high catalytic performance plays a significant role. In this work, FeS, Ni 3 S 2 , Fe 5 Ni 4 S 8 , and N, O, S-doped meshy carbon base were successfully synthesized. The sample containing Fe 5 Ni 4 S 8 exhibited excellent OER performance. The density functional theory calculations indicate that the partial density of states for 3d electrons (3d-PDOS) of Fe and Ni atoms are changed from monometallic sulfide to bimetallic sulfide at the sulfur vacancy. The asymmetric 3d electronic structure optimizes the 3d-PDOS of Fe and Ni atoms, and leads to an enhanced OER activity. This work provides a new strategy to prepare a low-cost electrocatalyst for oxygen evolution with high-efficiency.

Basic analytical investigation of plasma-chemically modified carbon fibers1

NASA Astrophysics Data System (ADS)

Bubert, H.; Ai, X.; Haiber, S.; Heintze, M.; Brüser, V.; Pasch, E.; Brandl, W.; Marginean, G.

2002-10-01

The background of the present investigation is to enhance the overall adherence of vapor grown carbon fibers (VGCF) to the surrounding polymer matrix in different applications by forming polar groups at their surfaces and by modifying the surface morphology. This has been done by plasma treatments using a low-pressure plasma with different gases, flow rates, pressures and powers. Two different types of carbon fibers were investigated: carbon microfibers and carbon nanofibers. The characterization of fiber surfaces was achieved by photoelectron spectroscopy (XPS), contact angle measurements and titration. These investigations were accompanied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The oxygen plasma treatment of the fibers changes the surfaces by forming a layer with a thickness of the order of one nanometer mainly consisting of functional groups like hydroxyl, carbonyl and carboxyl. After functionalization of the complete surface, a further plasma treatment does not enhance the superficial oxygen content but changes slightly the portions of the functional groups. A comparison of the methods applied provides a largely consistent image of the effect of plasma treatment.

Functional recovery in rat spinal cord injury induced by hyperbaric oxygen preconditioning.

PubMed

Lu, Pei-Gang; Hu, Sheng-Li; Hu, Rong; Wu, Nan; Chen, Zhi; Meng, Hui; Lin, Jiang-Kai; Feng, Hua

2012-12-01

It is a common belief that neurosurgical interventions can cause inevitable damage resulting from the procedure itself in surgery especially for intramedullary spinal cord tumors. The present study was designed to examine if hyperbaric oxygen preconditioning (HBO-PC) was neuroprotective against surgical injuries using a rat model of spinal cord injury (SCI). Sprague-Dawley rats were randomly divided into three groups: HBO-PC group, hypobaric hypoxic preconditioning (HH-PC) control group, and normobaric control group. All groups were subjected to SCI by weight drop device. Rats from each group were examined for neurological behavior and electrophysiological function. Tissue sections were analyzed by using immunohistochemistry, TdT-mediated dUTP-biotin nick end labeling, and axonal tract tracing. Significant neurological deficits were observed after SCI and HBO-PC and HH-PC improved neurological deficits 1 week post-injury. The latencies of motor-evoked potential and somatosensory-evoked potential were significantly delayed after SCI, which was attenuated by HBO-PC and HH-PC. Compared with normobaric control group, pretreatment with HBO and hypobaric hypoxia significantly reduced the number of TdT-mediated dUTP-biotin nick end labeling-positive cells, and increased nestin-positive cells. HBO-PC and HH-PC enhanced axonal growth after SCI. In conclusion, preconditioning with HBO and hypobaric hypoxia can facilitate functional recovery and suppress cell apoptosis after SCI and may prove to be a useful preventive strategy to neurosurgical SCI.

Efficient epoxidation of a terminal alkene containing allylic hydrogen atoms: trans-methylstyrene on Cu{111}.

PubMed

Cropley, Rachael L; Williams, Federico J; Urquhart, Andrew J; Vaughan, Owain P H; Tikhov, Mintcho S; Lambert, Richard M

2005-04-27

The selective oxidation of trans-methylstyrene, a phenyl-substituted propene that contains labile allylic hydrogen atoms, has been studied on Cu{111}. Mass spectrometry and synchrotron fast XPS were used to detect, respectively, desorbing gaseous products and the evolution of surface species as a function of temperature and time. Efficient partial oxidation occurs yielding principally the epoxide, and the behavior of the system is sensitive to the order in which reactants are adsorbed. The latter is understandable in terms of differences in the spatial distribution of oxygen adatoms; isolated adatoms lead to epoxidation, while islands of "oxidic" oxygen do not. NEXAFS data taken over a range of coverages and in the presence and absence of coadsorbed oxygen indicate that the adsorbed alkene lies essentially flat with the allylic hydrogen atoms close to the surface. The photoemission results and comparison with the corresponding behavior of styrene on Cu{111} strongly suggest that allylic hydrogen abstraction is indeed a critical factor that limits epoxidation selectivity. An overall mechanism consistent with the structural and reactive properties is proposed.

Functional near infrared spectroscopy as a probe of brain function in people with prolonged disorders of consciousness.

PubMed

Kempny, Agnieszka M; James, Leon; Yelden, Kudret; Duport, Sophie; Farmer, Simon; Playford, E Diane; Leff, Alexander P

2016-01-01

Near infrared spectroscopy (NIRS) is a non-invasive technique which measures changes in brain tissue oxygenation. NIRS has been used for continuous monitoring of brain oxygenation during medical procedures carrying high risk of iatrogenic brain ischemia and also has been adopted by cognitive neuroscience for studies on executive and cognitive functions. Until now, NIRS has not been used to detect residual cognitive functions in patients with prolonged disorders of consciousness (pDOC). In this study we aimed to evaluate the brain function of patients with pDOC by using a motor imagery task while recording NIRS. We also collected data from a group of age and gender matched healthy controls while they carried out both real and imagined motor movements to command. We studied 16 pDOC patients in total, split into two groups: five had a diagnosis of Vegetative state/Unresponsive Wakefulness State, and eleven had a diagnosis of Minimally Conscious State. In the control subjects we found a greater oxy-haemoglobin (oxyHb) response during real movement compared with imagined movement. For the between group comparison, we found a main effect of hemisphere, with greater depression of oxyHb signal in the right > left hemisphere compared with rest period for all three groups. A post-hoc analysis including only the two pDOC patient groups was also significant suggesting that this effect was not just being driven by the control subjects. This study demonstrates for the first time the feasibility of using NIRS for the assessment of brain function in pDOC patients using a motor imagery task.

Solid state oxygen sensor

DOEpatents

Garzon, F.H.; Chung, B.W.; Raistrick, I.D.; Brosha, E.L.

1996-08-06

Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer. 4 figs.

[Effect of hypertonic-hyperoncotic solution infusion on tissue perfusion during surgical treatment of the abdominal aorta].

PubMed

Soskić, Ljiljana; Davidović, Lazar; Milicić, Biljana; Kocica, Mladen; Kovacević, Natasa; Simić, Tijana

2007-10-01

Decreasing of arterial flow below the critical level leads to capillary endothelium edema and to further worsening of tissue perfusion. Hypertonic solution infusion provides mild and short plasma osmolality increasing, while colloidal solutions intensify that effect. The aim of this study was to investigate the effect of hypertonic-hyperoncotic solution (HH) on the organs perfusion during reconstructive surgical procedure on the abdominal aorta (AA). The study included 40 patients submitted to AA reconstruction due to aneurysm or Leriche's syndrome. A clamp was put transversally to the aorta, under the outlets of the renal arterias. According to the solution received when a clamp was on the aorta, the patients were divided into two groups containing 20 patients each: the tested group (A) which received 4 ml/kg of the solution (7.2% NaCl/10% dextran), and the control group (B) which received 0.9% NaCl. The study excluded the patients with the preoperative creatinine level more than 139 micromol/l, and ejection heart fraction less than 40%. The mixed venous blood oxygen saturation increased from 73.3+/-7.33 to 74.95+/-6.19% in the group A, while it decreased from 65.35+/-10.39 to 62.65+/-10.42% in the group B (p = 0.001). The quantity of the provided oxygen in the group A increased significantly from 684.44+/-244.34 to 1362.45+/-2351.01 ml/min, while it decreased from 668.2+/-382.12 to 651.7+/-313.98 ml/min in the group B (p = 0.016). Alveolo-arterial difference in oxygen decreased from 23.12+/-14.74 to 21.1+/-10 mmHg in the group A, while it increased from 23.79+/-15.22 to 26.33+/-13.78 mmHg in the group B (p = 0.05). Satisfactory perfusion of organs during the AA surgery is obtained by using both HH and an isotonic solution. Due to maintaining the optimal values of the minute heart volume, saturation of vein blood blended with oxygen, and al-veolo-arterial difference in oxygen, it is recommended to use HH solution for reanimation of patients in declamping shock.

Changes in Ocular Surface Characteristics after Switching from Benzalkonium Chloride-Preserved Latanoprost to Preservative-Free Tafluprost or Benzalkonium Chloride-Preserved Tafluprost.

PubMed

Tokuda, Naoto; Kitaoka, Yasushi; Matsuzawa, Akiko; Tsukamoto, Ayaka; Sase, Kana; Sakae, Shinsuke; Takagi, Hitoshi

2017-01-01

The aim of the present study was to examine the effects of switching from Latanoprost ophthalmic solution containing a preservative to preservative-free Tafluprost ophthalmic solution or Tafluprost containing a preservative on ocular surfaces. Forty patients (40 eyes) with glaucoma (mean age: 62.0 ± 10.9 years) using Latanoprost with preservative for six months or longer were assigned either to a Tafluprost-containing-preservative group (20 eyes) or preservative-free-Tafluprost group (20 eyes). The intraocular pressure, corneal epithelial barrier function (fluorescein uptake concentration with fluorophotometer FL-500), superficial punctate keratopathy (AD classification), and tear film breakup time (TBUT) were assessed before switching and at 12 weeks after switching. No significant differences in intraocular pressure were noted after switching in either group. Corneal epithelial barrier function was improved significantly after switching in both the Tafluprost-containing-preservative and the preservative-free-Tafluprost groups. There were no significant differences in AD scores after switching in the Tafluprost-containing-preservative group, but significant improvements were noted in the preservative-free-Tafluprost group. No significant differences in TBUT were noted in the Tafluprost-containing-preservative or preservative-free-Tafluprost groups after switching. After switching from preservative Latanoprost to Tafluprost containing-preservative or preservative-free Tafluprost, corneal epithelial barrier function was improved while the intraocular pressure reduction was retained.

Purification, crystallization and preliminary crystallographic studies of haemoglobin from mongoose (Helogale parvula) in two different crystal forms induced by pH variation

PubMed Central

Mohamed Abubakkar, M.; Saraboji, K.; Ponnuswamy, M. N.

2013-01-01

Haemoglobin (Hb) is a respiratory pigment; it is a tetrameric protein that ferries oxygen from the lungs to tissues and transports carbon dioxide on the return journey. The oxygen affinity of haemoglobin is regulated by the concentration of oxygen surrounding it and several efforts have revealed the shapes of Hb in different states and with different functions. However, study of the molecular basis of Hbs from low-oxygen-affinity species is critically needed in order to increase the understanding of the mechanism behind oxygen adaptation. The present study reports the preliminary crystallographic study of low-oxygen-affinity haemoglobin from mongoose, a burrowing mammal. Haemoglobin from mongoose was purified by anion-exchange chromatography, crystallized using the hanging-drop vapour-diffusion method and diffraction data sets were collected from monoclinic (2.3 Å resolution) and orthorhombic (2.9 Å resolution) crystal forms obtained by pH variation. The monoclinic and orthorhombic asymmetric units contained half and a whole biological molecule, respectively. PMID:23385751

Off-pump versus on-pump coronary artery revascularization: effects on pulmonary function.

PubMed

e Silva, Ana M R P; Saad, Roberto; Stirbulov, Roberto; Rivetti, Luiz A

2010-07-01

Many studies have shown important changes in lung function tests after coronary artery surgeries. It is controversial if off-pump surgery can give a better and shorter recovery than the on-pump. A prospective study was conducted on 42 patients submitted to coronary artery surgery and divided into two groups: 21 off-pump using intraluminal shunt (G (I)) and 21 on-pump (G (II)), matched by the anatomical location of the coronary arteries lesions. All patients had spirometric evaluation, blood gas measurements and alveolo-arterial oxygen gradient (A-aDO(2)), at the fourth and 10th postoperative days (PO(4) and PO(10)). Preoperatively, G(I) and G(II) had similar results (P>0.372). Spirometry showed decreases at PO(4) and remained decreased until PO(10) for both groups, with significant differences between the groups. The blood gas measurements showed reduction in arterial oxygen pressure (PaO(2)) and carbon dioxide pressure (PaCO(2)), while there was an increase in A-aDO(2) at PO(4) and PO(10) in both groups. The results suggest that different changes occur in pulmonary function when the surgery is performed with or without cardiopulmonary bypass. The off-pump patients showed significantly greater improvement than the on-pump group.

Validation of oxygen extraction fraction measurement by qBOLD technique.

PubMed

He, Xiang; Zhu, Mingming; Yablonskiy, Dmitriy A

2008-10-01

Measurement of brain tissue oxygen extraction fraction (OEF) in both baseline and functionally activated states can provide important information on brain functioning in health and disease. The recently proposed quantitative BOLD (qBOLD) technique is MRI-based and provides a regional in vivo OEF measurement (He and Yablonskiy, MRM 2007, 57:115-126). It is based on a previously developed analytical BOLD model and incorporates prior knowledge about the brain tissue composition including the contributions from grey matter, white matter, cerebrospinal fluid, interstitial fluid and intravascular blood. The qBOLD model also allows for the separation of contributions to the BOLD signal from OEF and the deoxyhemoglobin containing blood volume (DBV). The objective of this study is to validate OEF measurements provided by the qBOLD approach. To this end we use a rat model and compare qBOLD OEF measurements against direct measurements of the blood oxygenation level obtained from venous blood drawn directly from the superior sagittal sinus. The cerebral venous oxygenation level of the rat was manipulated by utilizing different anestheisa methods. The study demonstrates a very good agreement between qBOLD approach and direct measurements. (c) 2008 Wiley-Liss, Inc.

High efficiency of CO2-activated graphite felt as electrode for vanadium redox flow battery application

NASA Astrophysics Data System (ADS)

Chang, Yu-Chung; Chen, Jian-Yu; Kabtamu, Daniel Manaye; Lin, Guan-Yi; Hsu, Ning-Yih; Chou, Yi-Sin; Wei, Hwa-Jou; Wang, Chen-Hao

2017-10-01

A simple method for preparing CO2-activated graphite felt as an electrode in a vanadium redox flow battery (VRFB) was employed by the direct treatment in a CO2 atmosphere at a high temperature for a short period. The CO2-activated graphite felt demonstrates excellent electrochemical activity and reversibility. The VRFB using the CO2-activated graphite felts in the electrodes has coulombic, voltage, and energy efficiencies of 94.52%, 88.97%, and 84.15%, respectively, which is much higher than VRFBs using the electrodes of untreated graphite felt and N2-activated graphite felt. The efficiency enhancement was attributed to the higher number of oxygen-containing functional groups on the graphite felt that are formed during the CO2-activation, leading to improving the electrochemical behaviour of the resultant VRFB.

Oxygen transport membrane system and method for transferring heat to catalytic/process reactors

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

Kelly, Sean M.; Kromer, Brian R.; Litwin, Michael M.

A method and apparatus for producing heat used in a synthesis gas production process is provided. The disclosed method and apparatus include a plurality of tubular oxygen transport membrane elements adapted to separate oxygen from an oxygen containing stream contacting the retentate side of the membrane elements. The permeated oxygen is combusted with a hydrogen containing synthesis gas stream contacting the permeate side of the tubular oxygen transport membrane elements thereby generating a reaction product stream and radiant heat. The present method and apparatus also includes at least one catalytic reactor containing a catalyst to promote the steam reforming reactionmore » wherein the catalytic reactor is surrounded by the plurality of tubular oxygen transport membrane elements. The view factor between the catalytic reactor and the plurality of tubular oxygen transport membrane elements radiating heat to the catalytic reactor is greater than or equal to 0.5« less

Oxygen transport membrane system and method for transferring heat to catalytic/process reactors

DOEpatents

Kelly, Sean M; Kromer, Brian R; Litwin, Michael M; Rosen, Lee J; Christie, Gervase Maxwell; Wilson, Jamie R; Kosowski, Lawrence W; Robinson, Charles

2014-01-07

A method and apparatus for producing heat used in a synthesis gas production is provided. The disclosed method and apparatus include a plurality of tubular oxygen transport membrane elements adapted to separate oxygen from an oxygen containing stream contacting the retentate side of the membrane elements. The permeated oxygen is combusted with a hydrogen containing synthesis gas stream contacting the permeate side of the tubular oxygen transport membrane elements thereby generating a reaction product stream and radiant heat. The present method and apparatus also includes at least one catalytic reactor containing a catalyst to promote the stream reforming reaction wherein the catalytic reactor is surrounded by the plurality of tubular oxygen transport membrane elements. The view factor between the catalytic reactor and the plurality of tubular oxygen transport membrane elements radiating heat to the catalytic reactor is greater than or equal to 0.5.