Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

DOE PAGES

Snyder, Benjamin E. R.; Bottger, Lars H.; Bols, Max L.; ...

2018-04-02

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N 2O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. As a result, density functional theory calculations clarify howmore » the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.« less

Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

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

Snyder, Benjamin E. R.; Bottger, Lars H.; Bols, Max L.

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N 2O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. As a result, density functional theory calculations clarify howmore » the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.« less

Adrenocortical Underpinnings of Children's Psychological Reactivity to Interparental Conflict

PubMed Central

Davies, Patrick T.; Sturge-Apple, Melissa L.; Cicchetti, Dante; Cummings, E. Mark

2008-01-01

This study examined interrelationships among children's cortisol reactivity and their psychological reactivity to interparental conflict in a sample of 208 first-graders (mean age = 6.6 years). Assessments of children's psychological reactivity to conflict distinguished among their distress, hostile, and involvement responses across multiple methods (i.e., observation, questionnaire) and informants (i.e., observer, parent). Relative to other forms of conflict reactivity, children's distress responses to interparental conflict were consistent, unique predictors of their elevated cortisol reactivity to interparental conflict even after inclusion of demographic factors as moderators and covariates. Moderator analyses further revealed that associations between distress and elevated cortisol levels in response to interparental conflict were particularly pronounced when children exhibited high levels of involvement in conflicts. PMID:19037943

Affective and cognitive reactivity to mood induction in chronic depression.

PubMed

Guhn, Anne; Sterzer, Philipp; Haack, Friderike H; Köhler, Stephan

2018-03-15

Chronic depression (CD) is strongly associated with childhood maltreatment, which has been proposed to lead to inefficient coping styles that are characterized by abnormal affective responsiveness and dysfunctional cognitive attitudes. However, while this notion forms an important basis for psychotherapeutic strategies in the treatment of CD, there is still little direct empirical evidence for a role of altered affective and cognitive reactivity in CD. The present study therefore experimentally investigated affective and cognitive reactivity to two forms of negative mood induction in CD patients versus a healthy control sample (HC). For the general mood induction procedure, a combination of sad pictures and sad music was used, while for individualized mood induction, negative mood was induced by individualized scripts with autobiographical content. Both experiments included n = 15 CD patients versus n = 15 HC, respectively. Interactions between affective or cognitive reactivity and group were analyzed by repeated measurements ANOVAs. General mood induction neither revealed affective nor cognitive reactivity in the patient group while the control group reported the expected decrease of positive affect [interaction (IA) affective reactivity x group: p = .011, cognitive reactivity x group: n.s.]. In contrast, individualized mood induction specifically increased affective reactivity (IA: p = .037) as well as the amount of dysfunctional cognitions in patients versus controls (IA: p = .014). The experiments were not balanced in a crossover design, causal conclusions are thus limited. Additionally, the differences to non-chronic forms of depression are still outstanding. The results suggest that in patients with CD, specific emotional activation through autobiographical memories is a key factor in dysfunctional coping styles. Psychotherapeutic interventions aimed at modifying affective and cognitive reactivity are thus of high relevance in the treatment of CD. Copyright © 2018 Elsevier B.V. All rights reserved.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E [Ames, IA; Terpstra, Robert L [Ames, IA

2012-06-12

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E.; Terpstra, Robert L.

2010-04-20

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomized particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

A Preliminary Investigation of the E-Beam Induced Polymerization of Maleimide and Norbornene End-capped Polyimides

NASA Technical Reports Server (NTRS)

Palmese, Giuseppe R.; Meador, Michael A. (Technical Monitor)

2005-01-01

A research area of high activity in connection with aerospace engineering has been the development of polymer thermosetting resins that can resist temperature as high as 300 C while maintaining adequate toughness, and providing ease of processing to enable low temperature and low cost composite fabrication methods. In order to meet such requirements, sequential interpenetrating polymer networks (IPNs) based on bismaleimide (BMI) and cyanate ester (CE) monomers were investigated. In these systems, a polycyanurate network is first formed in the presence of BMI and appropriate reactive diluent monomers and in a second step, a network based on the BMI is created in the presence of a fully formed polycyanurate network. The materials developed can be processed at relatively low temperature (less than 150 C) and with the aid of electron beam (EB) curing. Of major importance to the success of this work was the identification of a reactive diluent that improves ease of processing and has tailored reactivity to allow for the controlled synthesis of CE-BMI sequential IPNs. Based on solubility and reactivity of a number of reactive diluents, N-acryloylmorpholine (AMP) was selected as a comonomer for BMI copolymerization. A donor-acceptoreaction mechanism was suggested to explain the relative reactivity of a variety of reactive diluents towards maleimide functionality. The optimum processing parameters for the formation of the first network were determined through the study of metal catalyzed cure and hydrolysis of cyanate esters, whereas the reaction behavior for second network formation in terms of the influence of EB dose rate and temperature was elucidated through an in-situ kinetics study of maleimide and AMP copolymerization. Structure-property relationships were developed which allowed for the design of improved resin systems. In particular, appropriate network coupler possessing cyanate ester and maleimide functionality was synthesized to link the polycyanurate first network to the BMI/AMP second network and thus form linked sequential IPNs (LIPNs). Consequently, Tg as high as 370 C was achieved and a fracture toughness of 120 Joules per square meters was obtained for resin systems that possess adequately low viscosity for processing using liquid molding techniques at low temperature.

Systems and methods for forming defects on graphitic materials and curing radiation-damaged graphitic materials

DOEpatents

Ryu, Sunmin; Brus, Louis E.; Steigerwald, Michael L.; Liu, Haitao

2012-09-25

Systems and methods are disclosed herein for forming defects on graphitic materials. The methods for forming defects include applying a radiation reactive material on a graphitic material, irradiating the applied radiation reactive material to produce a reactive species, and permitting the reactive species to react with the graphitic material to form defects. Additionally, disclosed are methods for removing defects on graphitic materials.

Myeloperoxidase-generated reactive nitrogen species convert LDL into an atherogenic form in vitro

PubMed Central

Podrez, Eugene A.; Schmitt, David; Hoff, Henry F.; Hazen, Stanley L.

1999-01-01

Oxidized LDL is implicated in atherosclerosis; however, the pathways that convert LDL into an atherogenic form in vivo are not established. Production of reactive nitrogen species may be one important pathway, since LDL recovered from human atherosclerotic aorta is enriched in nitrotyrosine. We now report that reactive nitrogen species generated by the MPO-H2O2-NO2– system of monocytes convert LDL into a form (NO2-LDL) that is avidly taken up and degraded by macrophages, leading to massive cholesterol deposition and foam cell formation, essential steps in lesion development. Incubation of LDL with isolated MPO, an H2O2-generating system, and nitrite (NO2–)— a major end-product of NO metabolism—resulted in nitration of apolipoprotein B 100 tyrosyl residues and initiation of LDL lipid peroxidation. The time course of LDL protein nitration and lipid peroxidation paralleled the acquisition of high-affinity, concentration-dependent, and saturable binding of NO2-LDL to human monocyte–derived macrophages and mouse peritoneal macrophages. LDL modification and conversion into a high-uptake form occurred in the absence of free metal ions, required NO2–, occurred at physiological levels of Cl–, and was inhibited by heme poisons, catalase, and BHT. Macrophage binding of NO2-LDL was specific and mediated by neither the LDL receptor nor the scavenger receptor class A type I. Exposure of macrophages to NO2-LDL promoted cholesteryl ester synthesis, intracellular cholesterol and cholesteryl ester accumulation, and foam cell formation. Collectively, these results identify MPO-generated reactive nitrogen species as a physiologically plausible pathway for converting LDL into an atherogenic form. PMID:10359564

Liquid Crystalline Thermosets from Ester, Ester-Imide, and Ester-Amide Oligomers

NASA Technical Reports Server (NTRS)

Dingemans, Theodornus J. (Inventor); Weiser, Erik S. (Inventor); SaintClair, Terry L. (Inventor)

2005-01-01

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,OOO grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end- capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers

NASA Technical Reports Server (NTRS)

Dingemans, Theodorous J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

2005-01-01

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end-capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Apple polyphenols, phloretin and phloridzin: new trapping agents of reactive dicarbonyl species.

PubMed

Shao, Xi; Bai, Naisheng; He, Kan; Ho, Chi-Tang; Yang, Chung S; Sang, Shengmin

2008-10-01

Reactive dicarbonyl species, such as methylglyoxal (MGO) and glyoxal (GO), have received extensive attention recently due to their high reactivity and ability to form advanced glycation end products (AGEs) with biological substances such as proteins, phospholipids, and DNA. In the present study, we found that both phloretin and its glucoside, phloridzin, the major bioactive apple polyphenols, could efficiently trap reactive MGO or GO to form mono- and di-MGO or GO adducts under physiological conditions (pH 7.4, 37 degrees C). More than 80% MGO was trapped within 10 min, and 68% GO was trapped within 24 h by phloretin. Phloridzin also had strong trapping efficiency by quenching more than 70% MGO and 60% GO within 24 h. The glucosylation of the hydroxyl group at position 2 could significantly slow down the trapping rate and the formation of MGO or GO adducts. The products formed from phloretin (or phloridzin) and MGO (or GO), combined at different ratios, were analyzed using LC/MS. We successfully purified the major mono-MGO adduct of phloridzin and found that it was a mixture of tautomers based on the one- and two-dimensional NMR spectra. Our LC/MS and NMR data showed that positions 3 and 5 of the phloretin or phloridzin A ring were the major active sites for trapping reactive dicarbonyl species. We also found that phloretin was more reactive than lysine and arginine in terms of trapping reactive dicarbonyl species, MGO or GO. Our results suggest that dietary flavonoids that have the same A ring structure as phloretin may have the potential to trap reactive dicarbonyl species and therefore inhibit the formation of AGEs.

Bond formations by intermolecular and intramolecular trappings of acylketenes and their applications in natural product synthesis†

PubMed Central

Reber, Keith P.; Tilley, S. David

2011-01-01

The reactive intermediates known as acylketenes exhibit a rich chemistry and have been extensively utilized for many types of inter- and intramolecular bond-forming reactions within the field of organic synthesis. Characteristic reactions of acylketenes include cycloadditions, carbon–carbon bond-forming reactions, and nucleophilic capture with alcohols or amines to give β-keto acid derivatives. In particular, the intramolecular capture of acylketene intermediates with pendant nucleophiles represents a powerful method for forming both medium-sized rings and macrocycles, often in high yield. This tutorial review examines the history, generation, and reactivity of acylketenes with a special focus on their applications in the synthesis of natural products. PMID:19847338

Characterization of Impact Initiation of Aluminum-Based Intermetallic-Forming Reactive Materials

DTIC Science & Technology

2011-12-01

compressed intermetallic-forming aluminum-based reactive materials upon impact initiation, consisting of equi-volumetric tantalum-aluminum, tungsten-aluminum...18 2.3.4 Dynamic Energy Release Characterization using Pig Test . . . . . . 21 2.3.5 Shock Compression of Reactive Powder Mixtures...is to evaluate the reaction initiation characteristics of quasi-statically compressed intermetallic-forming aluminum-based reactive materials upon

Reactive chromophores for sensitive and selective detection of chemical warfare agents and toxic industrial chemicals

NASA Astrophysics Data System (ADS)

Frye-Mason, Greg; Leuschen, Martin; Wald, Lara; Paul, Kateri; Hancock, Lawrence F.

2005-05-01

A reactive chromophore developed at MIT exhibits sensitive and selective detection of surrogates for G-class nerve agents. This reporter acts by reacting with the agent to form an intermediate that goes through an internal cyclization reaction. The reaction locks the molecule into a form that provides a strong fluorescent signal. Using a fluorescent sensor platform, Nomadics has demonstrated rapid and sensitive detection of reactive simulants such as diethyl chloro-phosphate (simulant for sarin, soman, and related agents) and diethyl cyanophosphate (simulant for tabun). Since the unreacted chromophore does not fluoresce at the excitation wavelength used for the cyclized reporter, the onset of fluo-rescence can be easily detected. This fluorescence-based detection method provides very high sensitivity and could enable rapid detection at permissible exposure levels. Tests with potential interferents show that the reporter is very selective, with responses from only a few highly toxic, electrophilic chemicals such as phosgene, thionyl chloride, and strong acids such as HF, HCl, and nitric acid. Dimethyl methyl phosphonate (DMMP), a common and inactive simu-lant for other CW detectors, is not reactive enough to generate a signal. The unique selectivity to chemical reactivity means that a highly toxic and hazardous chemical is present when the reporter responds and illustrates that this sensor can provide very low false alarm rates. Current efforts focus on demonstrating the sensitivity and range of agents and toxic industrial chemicals detected with this reporter as well as developing additional fluorescent reporters for a range of chemical reactivity classes. The goal is to produce a hand-held sensor that can sensitively detect a broad range of chemical warfare agent and toxic industrial chemical threats.

Rhenium and technetium tricarbonyl, {M(CO)3} (+) (M = Tc, Re), binding to mammalian metallothioneins: new insights into chemical and radiopharmaceutical implications.

PubMed

Lecina, Joan; Palacios, Òscar; Atrian, Sílvia; Capdevila, Mercè; Suades, Joan

2015-04-01

This paper deals with the binding of the four mammalian metallothioneins (MTs) to the organometallic metal fragment {fac-M(CO)3}(+) (M = (99)Tc, Re), which is highly promising for the preparation of second-generation radiopharmaceuticals. The study of the transmetallation reaction between zinc and rhenium in Zn7-MT1 by means of UV-vis and CD spectroscopy demonstrated the incorporation of the {fac-Re(CO)3}(+) fragment to the MTs. This reaction should be performed at 70 °C to accelerate the reaction rate, a result that is consistent with the reported reactivity of the rhenium fragment. ESI-TOF MS demonstrated the formation of mixed-metal species as Zn6,{Re(CO)3}-MT, Zn6,{Re(CO)3}2-MT, and Zn5,{Re(CO)3}3-MT, as well as the different reactivity of the four MT isoforms. Hence, Zn-MT3 showed the highest reactivity, in agreement with its high Cu-thionein character, whereas Zn-MT2 exhibited the lowest reactivity, in line with its high Zn-thionein character. The reactivity of the Zn-loaded forms of MT1 and MT4 is intermediate between those of MT3 and MT2. The study of the binding of the {fac-(99)Tc(CO)3}(+) fragment to MTs showed a significant and very interesting different reactivity in relation to rhenium. The transmetallation reaction is much more effective with technetium than with rhenium and significant amounts of mixed Zn x ,{(99)Tc(CO)3} y -MT species were formed with the four MT isoforms whereas only MT3 rendered similar amounts of rhenium derivatives. The results obtained in this study support the possible use of technetium for labelling mammalian metallothioneins and also for possible radiopharmaceutical applications.

Reaction Mechanism of Covalent Modification of Phosphatidylethanolamine Lipids by Reactive Aldehydes 4-Hydroxy-2-nonenal and 4-Oxo-2-nonenal.

PubMed

Vazdar, Katarina; Vojta, Danijela; Margetić, Davor; Vazdar, Mario

2017-03-20

4-Hydroxy-2-nonenal (HNE) and 4-oxo-2-nonenal (ONE) are biologically important reactive aldehydes formed during oxidative stress in phospholipid bilayers. They are highly reactive species due to presence of several reaction centers and can react with amino acids in peptides and proteins, as well as phosphoethanolamine (PE) lipids, thus modifying their biological activity. The aim of this work is to study in a molecular detail the reactivity of HNE and ONE toward PE lipids in a simplified system containing only lipids and reactive aldehydes in dichloromethane as an inert solvent. We use a combination of quantum chemical calculations, 1 H NMR measurements, FT-IR spectroscopy, and mass spectrometry experiments and show that for both reactive aldehydes two types of chemical reactions are possible: formation of Michael adducts and Schiff bases. In the case of HNE, an initially formed Michael adduct can also undergo an additional cyclization step to a hemiacetal derivative, whereas no cyclization occurs in the case of ONE and a Michael adduct is identified. A Schiff base product initially formed when HNE is added to PE lipid can also further cyclize to a pyrrole derivative in contrast to ONE, where only a Schiff base product is isolated. The suggested reaction mechanism by quantum-chemical calculations is in a qualitative agreement with experimental yields of isolated products and is also additionally investigated by 1 H NMR measurements, FT-IR spectroscopy, and mass spectrometry experiments.

Dispersoid reinforced alloy powder and method of making

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

Anderson, Iver E.; Terpstra, Robert L.

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomizedmore » particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.« less

Dispersoid reinforced alloy powder and method of making

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

Anderson, Iver E.; Terpstra, Robert L.

2017-10-10

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with a reactive species acquired from an atomizing gas than does the alloying element. The melted alloy is atomized with the atomizing gas including the reactive species to form atomized particles so that the reactive species is (a) dissolved in solid solution to a depth below the surface of atomized particles and/or (b) reacted with the dispersoid-forming element to form dispersoids in the atomizedmore » particles to a depth below the surface of said atomized particles. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.« less

Hairy and Slippery Polyoxazoline-Based Copolymers on Model and Cartilage Surfaces.

PubMed

Morgese, Giulia; Ramakrishna, Shivaprakash N; Simic, Rok; Zenobi-Wong, Marcy; Benetti, Edmondo M

2018-02-12

Comb-like polymers presenting a hydroxybenzaldehyde (HBA)-functionalized poly(glutamic acid) (PGA) backbone and poly(2-methyl-2-oxazoline) (PMOXA) side chains chemisorb on aminolized substrates, including cartilage surfaces, forming layers that reduce protein contamination and provide lubrication. The structure, physicochemical, biopassive, and tribological properties of PGA-PMOXA-HBA films are finely determined by the copolymer architecture, its reactivity toward the surface, i.e. PMOXA side-chain crowding and HBA density, and by the copolymer solution concentration during assembly. Highly reactive species with low PMOXA content form inhomogeneous layers due to the limited possibility of surface rearrangements by strongly anchored copolymers, just partially protecting the functionalized surface from protein contamination and providing a relatively weak lubrication on cartilage. Biopassivity and lubrication can be improved by increasing copolymer concentration during assembly, leading to a progressive saturation of surface defects across the films. In a different way, less reactive copolymers presenting high PMOXA side-chain densities form uniform, biopassive, and lubricious films, both on model aminolized silicon oxide surfaces, as well as on cartilage substrates. When assembled at low concentrations these copolymers adopt a "lying down" conformation, i.e. adhering via their backbones onto the substrates, while at high concentrations they undergo a conformational transition, assuming a more densely packed, "standing up" structure, where they stretch perpendicularly from the substrate. This specific arrangement reduces protein contamination and improves lubrication both on model as well as on cartilage surfaces.

Diastereoselective Synthesis of Seven-Membered Ring trans-Alkenes from Dienes and Aldehydes by Silylene Transfer

PubMed Central

Greene, Margaret A.; Prévost, Michel; Tolopilo, Joshua; Woerpel, K. A.

2012-01-01

Silver-catalyzed silylene transfer to alkenes formed vinylsilacyclopropanes regioselectively. These allylic silanes underwent additions to aldehydes to form seven-membered ring trans-alkenes with high diastereoselectivity. The high reactivity of the trans alkenes is evidenced by their formal [1,3]-sigmatropic rearrangement reactions and their rapid additions of oxygen–hydrogen bonds across the carbon–carbon double bonds. PMID:22780578

Revealing Nanoscale Passivation and Corrosion Mechanisms of Reactive Battery Materials in Gas Environments.

PubMed

Li, Yuzhang; Li, Yanbin; Sun, Yongming; Butz, Benjamin; Yan, Kai; Koh, Ai Leen; Zhao, Jie; Pei, Allen; Cui, Yi

2017-08-09

Lithium (Li) metal is a high-capacity anode material (3860 mAh g -1 ) that can enable high-energy batteries for electric vehicles and grid-storage applications. However, Li metal is highly reactive and repeatedly consumed when exposed to liquid electrolyte (during battery operation) or the ambient environment (throughout battery manufacturing). Studying these corrosion reactions on the nanoscale is especially difficult due to the high chemical reactivity of both Li metal and its surface corrosion films. Here, we directly generate pure Li metal inside an environmental transmission electron microscope (TEM), revealing the nanoscale passivation and corrosion process of Li metal in oxygen (O 2 ), nitrogen (N 2 ), and water vapor (H 2 O). We find that while dry O 2 and N 2 (99.9999 vol %) form uniform passivation layers on Li, trace water vapor (∼1 mol %) disrupts this passivation and forms a porous film on Li metal that allows gas to penetrate and continuously react with Li. To exploit the self-passivating behavior of Li in dry conditions, we introduce a simple dry-N 2 pretreatment of Li metal to form a protective layer of Li nitride prior to battery assembly. The fast ionic conductivity and stable interface of Li nitride results in improved battery performance with dendrite-free cycling and low voltage hysteresis. Our work reveals the detailed process of Li metal passivation/corrosion and demonstrates how this mechanistic insight can guide engineering solutions for Li metal batteries.

2'-Deoxyguanosine as a surrogate trapping agent for DNA reactive drug metabolites.

PubMed

Häkkinen, Merja R; Laine, Jaana E; Juvonen, Risto O; Auriola, Seppo; Häyrinen, Jukka; Pasanen, Markku

2011-11-10

Drug metabolism can result in the production of highly reactive metabolites that may form adducts with cellular macromolecules, and thus initiate adverse drug reactions, cause toxicity, and even require the withdrawal of drug from the market. In this study, a 2'-deoxyguanosine (dG)-based chemical trapping test system was developed for use as a fast screening tool for DNA adducting metabolites of new drug candidates. Reactive metabolites were generated from parent compounds in in vitro incubations with phenobarbital-induced mouse liver microsomes, human liver microsomes and different recombinant human CYP enzymes in the presence of dG. The formed dG-adducts were separated, characterized and their stability was studied by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method was evaluated with six test compounds, aflatoxin B1, estrone, clozapine, tolcapone, ticlopidine and imipramine. Estrone and aflatoxin B1 formed dG adducts with phenobarbital-induced mouse liver microsomes, human liver microsomes and human recombinant CYP enzymes. Adduct formation was also observed with tolcapone when phenobarbital-induced mouse liver microsomes were used as the enzyme source. The stability of each formed adduct was independent of the different enzyme sources. No dG-adducts were identified with ticlopidine, clozapine and imipramine. Compared to other classical DNA reactivity tests, e.g. Ames test, the present surrogate endpoint, the dG adduct, is faster, enables the characterization of the formed compounds, and also permits the investigation of more unstable adducts. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Study of thermite mixtures consolidated by cold gas dynamic spray process

NASA Astrophysics Data System (ADS)

Bacciochini, Antoine; Maines, Geoffrey; Poupart, Christian; Radulescu, Matei; Jodoin, Bertrand; Lee, Julian

2013-06-01

The present study focused on the cold gas dynamic spray process for manufacturing finely structured energetic materials with high reactivity, vanishing porosity, as well as structural integrity and arbitrary shape. The experiments have focused the reaction between the aluminum and metal oxides, such as Al-CuO and Al-MoO3 systems. To increase the reactivity, an initial mechanical activation was achieved through interrupted ball milling. The consolidation of the materials used the supersonic cold gas spray technique, where the particles are accelerated to high speeds and consolidated via plastic deformation upon impact, forming activated nano-composites in arbitrary shapes with close to zero porosity. This technique permits to retain the feedstock powder micro-structure and prevents any reactions during the consolidation phase. Reactivity of mixtures has been investigated through flame propagation analysis on cold sprayed samples and compacted powder mixture. Deflagration tests showed the influence of porosity on the reactivity.

Development and manufacture of reactive-transfer-printed CIGS photovoltaic modules

NASA Astrophysics Data System (ADS)

Eldada, Louay; Sang, Baosheng; Lu, Dingyuan; Stanbery, Billy J.

2010-09-01

In recent years, thin-film photovoltaic (PV) companies started realizing their low manufacturing cost potential, and grabbing an increasingly larger market share from multicrystalline silicon companies. Copper Indium Gallium Selenide (CIGS) is the most promising thin-film PV material, having demonstrated the highest energy conversion efficiency in both cells and modules. However, most CIGS manufacturers still face the challenge of delivering a reliable and rapid manufacturing process that can scale effectively and deliver on the promise of this material system. HelioVolt has developed a reactive transfer process for CIGS absorber formation that has the benefits of good compositional control, high-quality CIGS grains, and a fast reaction. The reactive transfer process is a two stage CIGS fabrication method. Precursor films are deposited onto substrates and reusable print plates in the first stage, while in the second stage, the CIGS layer is formed by rapid heating with Se confinement. High quality CIGS films with large grains were produced on a full-scale manufacturing line, and resulted in high-efficiency large-form-factor modules. With 14% cell efficiency and 12% module efficiency, HelioVolt started to commercialize the process on its first production line with 20 MW nameplate capacity.

Fluidizable zinc titanate materials with high chemical reactivity and attrition resistance

DOEpatents

Gupta, Raghubir P.; Gangwal, Santosh K.; Jain, Suresh C.

1993-01-01

Highly durable and chemically reactive zinc titanate materials are prepared in a particle size range of 50 to 400 .mu.m suitable for a fluidized-bed reactor for removing reduced sulfur species in a gaseous form by granulating a mixture of fine zinc oxide and titanium oxide with inorganic and organic binders and by optional additions of small amounts of activators such as CoO and MoO.sub.3 ; and then indurating it at 800.degree. to 900.degree. C. for a time sufficient to produce attrition-resistant granules.

Fluidizable zinc titanate materials with high chemical reactivity and attrition resistance

DOEpatents

Gupta, R.P.; Gangwal, S.K.; Jain, S.C.

1993-10-19

Highly durable and chemically reactive zinc titanate materials are prepared in a particle size range of 50 to 400 [mu]m suitable for a fluidized-bed reactor for removing reduced sulfur species in a gaseous form by granulating a mixture of fine zinc oxide and titanium oxide with inorganic and organic binders and by optional additions of small amounts of activators such as CoO and MoO[sub 3]; and then indurating it at 800 to 900 C for a time sufficient to produce attrition-resistant granules.

Sorbents for the oxidation and removal of mercury

DOEpatents

Olson, Edwin S; Holmes, Michael J; Pavlish, John Henry

2013-08-20

A promoted activated carbon sorbent is described that is highly effective for the removal of mercury from flue gas streams. The sorbent comprises a new modified carbon form containing reactive forms of halogen and halides. Optional components may be added to increase reactivity and mercury capacity. These may be added directly with the sorbent, or to the flue gas to enhance sorbent performance and/or mercury capture. Mercury removal efficiencies obtained exceed conventional methods. The sorbent can be regenerated and reused. Sorbent treatment and preparation methods are also described. New methods for in-flight preparation, introduction, and control of the active sorbent into the mercury contaminated gas stream are described.

Sorbents for the oxidation and removal of mercury

DOEpatents

Olson, Edwin S [Grand Forks, ND; Holmes, Michael J [Thompson, ND; Pavlish, John H [East Grand Forks, MN

2008-10-14

A promoted activated carbon sorbent is described that is highly effective for the removal of mercury from flue gas streams. The sorbent comprises a new modified carbon form containing reactive forms of halogen and halides. Optional components may be added to increase reactivity and mercury capacity. These may be added directly with the sorbent, or to the flue gas to enhance sorbent performance and/or mercury capture. Mercury removal efficiencies obtained exceed conventional methods. The sorbent can be regenerated and reused. Sorbent treatment and preparation methods are also described. New methods for in-flight preparation, introduction, and control of the active sorbent into the mercury contaminated gas stream are described.

Sorbents for the oxidation and removal of mercury

DOEpatents

Olson, Edwin S [Grand Forks, ND; Holmes, Michael J [Thompson, ND; Pavlish, John H [East Grand Forks, MN

2012-05-01

A promoted activated carbon sorbent is described that is highly effective for the removal of mercury from flue gas streams. The sorbent comprises a new modified carbon form containing reactive forms of halogen and halides. Optional components may be added to increase reactivity and mercury capacity. These may be added directly with the sorbent, or to the flue gas to enhance sorbent performance and/or mercury capture. Mercury removal efficiencies obtained exceed conventional methods. The sorbent can be regenerated and reused. Sorbent treatment and preparation methods are also described. New methods for in-flight preparation, introduction, and control of the active sorbent into the mercury contaminated gas stream are described.

Sorbents for the oxidation and removal of mercury

DOEpatents

Olson, Edwin S.; Holmes, Michael J.; Pavlish, John Henry

2014-09-02

A promoted activated carbon sorbent is described that is highly effective for the removal of mercury from flue gas streams. The sorbent comprises a new modified carbon form containing reactive forms of halogen and halides. Optional components may be added to increase reactivity and mercury capacity. These may be added directly with the sorbent, or to the flue gas to enhance sorbent performance and/or mercury capture. Mercury removal efficiencies obtained exceed conventional methods. The sorbent can be regenerated and reused. Sorbent treatment and preparation methods are also described. New methods for in-flight preparation, introduction, and control of the active sorbent into the mercury contaminated gas stream are described.

Children's aggressive responses to neutral peer behavior: a form of unprovoked reactive aggression.

PubMed

Kempes, Maaike; Matthys, Walter; de Vries, Han; van Engeland, Herman

2010-04-30

Previous studies that operationalized reactive aggression using behavioral observations in general populations have not taken into account the type of stimulus that elicits reactive aggression. In the present study we define a specific form of reactive aggression, i.e., reactive aggression in response to neutral behavior of a peer, which we will call unprovoked reactive aggression. We were specifically interested in children with severe aggressive behavior problems, since they may respond with reactive aggression even though the opponent did not clearly provoke them, but instead showed neutral behavior. Children with a disruptive behavior disorder (DBD) and normal control (NC) children participated in separate play sessions in which they played with a normal peer (NP). Children with DBD showed more unprovoked reactive aggression than NC children, during a cooperative game. Moreover, for children with DBD, unprovoked reactive aggressive behavior in this game correlated with parent-rated reactive aggression. Results of this study suggest that an unprovoked reactive form of aggression can be identified in children with DBD. Copyright (c) 2008. Published by Elsevier Ireland Ltd.

Iron-catalyzed oxidative biaryl cross-couplings via mixed diaryl titanates: significant influence of the order of combining aryl Grignard reagents with titanate.

PubMed

Liu, Kun Ming; Wei, Juan; Duan, Xin Fang

2015-03-18

The mixed diaryl titanates were used for the first time to modify the reactivity of two aryl Grignard reagents. Two titanate intermediates, Ar[Ar'Ti(OR)3]MgX and Ar'[ArTi(OR)3]MgX, formed via alternating the sequence of combining Grignard reagents with ClTi(OR)3 showed a significant reactivity difference. Taking advantage of such different reactivity, two highly structurally similar aryl groups could be facilely assembled through iron-catalyzed oxidative cross-couplings using oxygen as the oxidant.

Self-organised synthesis of Rh nanostructures with tunable chemical reactivity

PubMed Central

2007-01-01

Nonequilibrium periodic nanostructures such as nanoscale ripples, mounds and rhomboidal pyramids formed on Rh(110) are particularly interesting as candidate model systems with enhanced catalytic reactivity, since they are endowed with steep facets running along nonequilibrium low-symmetry directions, exposing a high density of undercoordinated atoms. In this review we report on the formation of these novel nanostructured surfaces, a kinetic process which can be controlled by changing parameters such as temperature, sputtering ion flux and energy. The role of surface morphology with respect to chemical reactivity is investigated by analysing the carbon monoxide dissociation probability on the different nanostructured surfaces.

Reactive sintering process of ferromagnetic MnBi under high magnetic fields

NASA Astrophysics Data System (ADS)

Mitsui, Yoshifuru; Umetsu, Rie Y.; Takahashi, Kohki; Koyama, Keiichi

2018-05-01

The magnetic field effect on the reactive sintering process of MnBi was investigated. Magnetic-field-induced enhancement of the reaction was found to be exhibited at the initial stages. The coercivity field decreased with an increase in the in-field annealing time. The kinetics of the reaction were in good agreement with the diffusion-controlled reaction model. It is suggested that the decrease in activation energy at the initial stages of reaction increased the amount of formed MnBi phases, resulting in enhancement of the reaction Mn + Bi to MnBi phase by in-field reactive sintering.

Anisotropic Etching Using Reactive Cluster Beams

NASA Astrophysics Data System (ADS)

Koike, Kunihiko; Yoshino, Yu; Senoo, Takehiko; Seki, Toshio; Ninomiya, Satoshi; Aoki, Takaaki; Matsuo, Jiro

2010-12-01

The characteristics of Si etching using nonionic cluster beams with highly reactive chlorine-trifluoride (ClF3) gas were examined. An etching rate of 40 µm/min or higher was obtained even at room temperature when a ClF3 molecular cluster was formed and irradiated on a single-crystal Si substrate in high vacuum. The etching selectivity of Si with respect to a photoresist and SiO2 was at least 1:1000. We also succeeded in highly anisotropic etching with an aspect ratio of 10 or higher. Moreover, this etching method has a great advantage of low damage, compared with the conventional plasma process.

Decreased photosynthetic rate under high temperature in wheat is due to lipid desaturation, oxidation, acylation, and damage of organelles.

PubMed

Djanaguiraman, M; Boyle, D L; Welti, R; Jagadish, S V K; Prasad, P V V

2018-04-05

High temperature is a major abiotic stress that limits wheat (Triticum aestivum L.) productivity. Variation in levels of a wide range of lipids, including stress-related molecular species, oxidative damage, cellular organization and ultrastructural changes were analyzed to provide an integrated view of the factors that underlie decreased photosynthetic rate under high temperature stress. Wheat plants of cultivar Chinese Spring were grown at optimum temperatures (25/15 °C, maximum/minimum) until the onset of the booting stage. Thereafter, plants were exposed to high temperature (35/25 °C) for 16 d. Compared with optimum temperature, a lower photosynthetic rate was observed at high temperature which is an interplay between thylakoid membrane damage, thylakoid membrane lipid composition, oxidative damage of cell organelle, and stomatal and non-stomatal limitations. Triacylglycerol levels were higher under high temperature stress. Polar lipid fatty acyl unsaturation was lower at high temperature, while triacylglycerol unsaturation was the same at high temperature and optimum temperature. The changes in lipid species indicates increases in activities of desaturating, oxidizing, glycosylating and acylating enzymes under high temperature stress. Cumulative effect of high temperature stress led to generation of reactive oxygen species, cell organelle and membrane damage, and reduced antioxidant enzyme activity, and imbalance between reactive oxygen species and antioxidant defense system. Taken together with recent findings demonstrating that reactive oxygen species are formed from and are removed by thylakoid lipids, the data suggest that reactive oxygen species production, reactive oxygen species removal, and changes in lipid metabolism contribute to decreased photosynthetic rate under high temperature stress.

Float processing of high-temperature complex silicate glasses and float baths used for same

NASA Technical Reports Server (NTRS)

Cooper, Reid Franklin (Inventor); Cook, Glen Bennett (Inventor)

2000-01-01

A float glass process for production of high melting temperature glasses utilizes a binary metal alloy bath having the combined properties of a low melting point, low reactivity with oxygen, low vapor pressure, and minimal reactivity with the silicate glasses being formed. The metal alloy of the float medium is exothermic with a solvent metal that does not readily form an oxide. The vapor pressure of both components in the alloy is low enough to prevent deleterious vapor deposition, and there is minimal chemical and interdiffusive interaction of either component with silicate glasses under the float processing conditions. Alloys having the desired combination of properties include compositions in which gold, silver or copper is the solvent metal and silicon, germanium or tin is the solute, preferably in eutectic or near-eutectic compositions.

Highly Manufacturable Deep (Sub-Millimeter) Etching Enabled High Aspect Ratio Complex Geometry Lego-Like Silicon Electronics.

PubMed

Ghoneim, Mohamed Tarek; Hussain, Muhammad Mustafa

2017-04-01

A highly manufacturable deep reactive ion etching based process involving a hybrid soft/hard mask process technology shows high aspect ratio complex geometry Lego-like silicon electronics formation enabling free-form (physically flexible, stretchable, and reconfigurable) electronic systems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Estimation of incremental reactivities for multiple day scenarios: an application to ethane and dimethyoxymethane

NASA Astrophysics Data System (ADS)

Stockwell, William R.; Geiger, Harald; Becker, Karl H.

Single-day scenarios are used to calculate incremental reactivities by definition (Carter, J. Air Waste Management Assoc. 44 (1994) 881-899.) but even unreactive organic compounds may have a non-negligible effect on ozone concentrations if multiple-day scenarios are considered. The concentration of unreactive compounds and their products may build up over a multiple-day period and the oxidation products may be highly reactive or highly unreactive affecting the overall incremental reactivity of the organic compound. We have developed a method for calculating incremental reactivities for multiple days based on a standard scenario for polluted European conditions. This method was used to estimate maximum incremental reactivities (MIR) and maximum ozone incremental reactivities (MOIR) for ethane and dimethyoxymethane for scenarios ranging from 1 to 6 days. It was found that the incremental reactivities increased as the length of the simulation period increased. The MIR of ethane increased faster than the value for dimethyoxymethane as the scenarios became longer. The MOIRs of ethane and dimethyoxymethane increased but the change was more modest for scenarios longer than 3 days. MOIRs of both volatile organic compounds were equal within the uncertainties of their chemical mechanisms by the 5 day scenario. These results show that dimethyoxymethane has an ozone forming potential on a per mass basis that is only somewhat greater than ethane if multiple-day scenarios are considered.

Water-free synthesis of polyurethane foams using highly reactive diisocyanates derived from 5-hydroxymethylfurfural.

PubMed

Neumann, Christopher N D; Bulach, Winfried D; Rehahn, Matthias; Klein, Roland

2011-09-01

This paper reports on the synthesis of a new highly reactive diisocyanate monomer based on hydroxymethylfurfural. It further describes its catalyst-free conversion to linear-chain thermoplastic polyurethanes as well as to cross-linked polyurethane foams. In addition, a novel strategy for the synthesis of polyurethane foams without the necessity of using water is developed. Nitrogen is utilized herein as blowing agent which is formed during Curtius rearrangement of a new furan based carboxylic azide into its corresponding diisocyanate. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, Gary L.

1988-08-16

A method for preparing highly hydrogen-reactive surfaces on metals which normally require substantial heating, high pressures, or an extended induction period, which involves pretreatment of said surfaces with either a non-oxidizing acid or hydrogen gas to form a hydrogen-bearing coating on said surfaces, and subsequently heating said coated metal in the absence of moisture and oxygen for a period sufficient to decompose said coating and cooling said metal to room temperature. Surfaces so treated will react almost instantaneously with hydrogen gas at room temperature and low pressure. The method is particularly applicable to uranium, thorium, and lanthanide metals.

Reactive processing and mechanical properties of polymer derived silicon nitride matrix composites and their use in coating and joining ceramics and ceramic matrix composites

NASA Astrophysics Data System (ADS)

Stackpoole, Margaret Mary

Use of preceramic polymers offers many advantages over conventional ceramic processing routes. Advantages include being able to plastically form the part, form a pyrolized ceramic material at lower temperatures and form high purity microstructures which are tailorable depending on property requirements. To date preceramic polymers are mostly utilized in the production of low dimensional products such as fibers since loss of volatiles during pyrolysis leads to porosity and large shrinkage (in excess of 30%). These problems have been partially solved by use of active fillers (e.g. Ti, Cr, B). The reactive filler converts to a ceramic material with a volume expansion and this increases the density and reduces shrinkage and porosity. The expansion of the reactive filler thus compensates for the polymer shrinkage if the appropriate volume fraction of filler is present in a reactive atmosphere (e.g. N2 or NH3). This approach has resulted in structural composites with limited success. The present research investigates the possibility of using filled preceramic polymers to form net shaped ceramic composite materials and to investigate the use of these unique composite materials to join and coat ceramics and ceramic composites. The initial research focused on phase and microstructural development of bulk composites from the filled polymer/ceramic systems. A processing technique was developed to insure consistency between different samples and the most promising filler/polymer choices for this application have been determined. The processing temperatures and atmospheres have also been optimized. The work covers processing and characterization of bulk composites, joints and coatings. With careful control of processing near net shape bulk composites were fabricated. Both ambient and high temperature strength and fracture toughness was obtained for these composite systems. The potential of using reactively filled preceramic polymers to process joints and coatings was also investigated. A critical thickness below which crack free joints/coatings could be processed was determined. Finally, mechanical properties of the joints and coatings at ambient and elevated temperatures (including oxidation studies) have been evaluated. The interfacial fracture behavior of the joints and coatings was also evaluated.

Sorbents for the oxidation and removal of mercur

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

Olson, Edwin S.; Holmes, Michael J.; Pavlish, John Henry

A promoted activated carbon sorbent is described that is highly effective for the removal of mercury from flue gas streams. The sorbent comprises a new modified carbon form containing reactive forms of halogen and halides. Optional components may be added to increase reactivity and mercury capacity. These may be added directly with the sorbent, or to the flue gas to enhance sorbent performance and/or mercury capture. Mercury removal efficiencies obtained exceed conventional methods. The sorbent can be regenerated and reused. Sorbent treatment and preparation methods are also described. New methods for in-flight preparation, introduction, and control of the active sorbentmore » into the mercury contaminated gas stream are described.« less

Fabrication of submicron structures in nanoparticle/polymer composite by holographic lithography and reactive ion etching

NASA Astrophysics Data System (ADS)

Zhang, A. Ping; He, Sailing; Kim, Kyoung Tae; Yoon, Yong-Kyu; Burzynski, Ryszard; Samoc, Marek; Prasad, Paras N.

2008-11-01

We report on the fabrication of nanoparticle/polymer submicron structures by combining holographic lithography and reactive ion etching. Silica nanoparticles are uniformly dispersed in a (SU8) polymer matrix at a high concentration, and in situ polymerization (cross-linking) is used to form a nanoparticle/polymer composite. Another photosensitive SU8 layer cast upon the nanoparticle/SU8 composite layer is structured through holographic lithography, whose pattern is finally transferred to the nanoparticle/SU8 layer by the reactive ion etching process. Honeycomb structures in a submicron scale are experimentally realized in the nanoparticle/SU8 composite.

Bonding reactivity descriptor from conceptual density functional theory and its applications to elucidate bonding formation

NASA Astrophysics Data System (ADS)

Zhou, Pan-Pan; Liu, Shubin; Ayers, Paul W.; Zhang, Rui-Qin

2017-10-01

Condensed-to-atom Fukui functions which reflect the atomic reactivity like the tendency susceptible to either nucleophilic or electrophilic attack demonstrate the bonding trend of an atom in a molecule. Accordingly, Fukui functions based concepts, that is, bonding reactivity descriptors which reveal the bonding properties of molecules in the reaction were put forward and then applied to pericyclic and cluster reactions to confirm their effectiveness and reliability. In terms of the results from the bonding descriptors, a covalent bond can readily be predicted between two atoms with large Fukui functions (i.e., one governs nucleophilic attack while the other one governs electrophilic attack, or both of them govern radical attacks) for pericyclic reactions. For SinOm clusters' reactions, the clusters with a low O atom ratio readily form a bond between two Si atoms with big values of their Fukui functions in which they respectively govern nucleophilic and electrophilic attacks or both govern radical attacks. Also, our results from bonding descriptors show that Si—Si bonds can be formed via the radical mechanism between two Si atoms, and formations of Si—O and O—O bonds are possible when the O content is high. These results conform with experimental findings and can help experimentalists design appropriate clusters to synthesize Si nanowires with high yields. The approach established in this work could be generalized and applied to study reactivity properties for other systems.

Experimental demonstration of radicaloid character in a RuV=O intermediate in catalytic water oxidation

PubMed Central

Moonshiram, Dooshaye; Alperovich, Igor; Concepcion, Javier J.; Meyer, Thomas J.; Pushkar, Yulia

2013-01-01

Water oxidation is the key half reaction in artificial photosynthesis. An absence of detailed mechanistic insight impedes design of new catalysts that are more reactive and more robust. A proposed paradigm leading to enhanced reactivity is the existence of oxyl radical intermediates capable of rapid water activation, but there is a dearth of experimental validation. Here, we show the radicaloid nature of an intermediate reactive toward formation of the O-O bond by assessing the spin density on the oxyl group by Electron Paramagnetic Resonance (EPR). In the study, an 17O-labeled form of a highly oxidized, short-lived intermediate in the catalytic cycle of the water oxidation catalyst cis,cis-[(2,2-bipyridine)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+ was investigated. It contains Ru centers in oxidation states [4,5], has at least one RuV = O unit, and shows |Axx| = 60G 17O hyperfine splittings (hfs) consistent with the high spin density of a radicaloid. Destabilization of π-bonding in the d3 RuV = O fragment is responsible for the high spin density on the oxygen and its high reactivity. PMID:23417296

Cytotoxic and Antitumor Activity of Sulforaphane: The Role of Reactive Oxygen Species

PubMed Central

Sestili, Piero

2015-01-01

According to recent estimates, cancer continues to remain the second leading cause of death and is becoming the leading one in old age. Failure and high systemic toxicity of conventional cancer therapies have accelerated the identification and development of innovative preventive as well as therapeutic strategies to contrast cancer-associated morbidity and mortality. In recent years, increasing body of in vitro and in vivo studies has underscored the cancer preventive and therapeutic efficacy of the isothiocyanate sulforaphane. In this review article, we highlight that sulforaphane cytotoxicity derives from complex, concurring, and multiple mechanisms, among which the generation of reactive oxygen species has been identified as playing a central role in promoting apoptosis and autophagy of target cells. We also discuss the site and the mechanism of reactive oxygen species' formation by sulforaphane, the toxicological relevance of sulforaphane-formed reactive oxygen species, and the death pathways triggered by sulforaphane-derived reactive oxygen species. PMID:26185755

Microheterogeneity of alpha 1-acid glycoprotein in healthy elderly subjects: patterns obtained by crossed affino-immunoelectrophoresis.

PubMed

Kawerk, N; Succari-Aderschlag, M; Foglietti, M J

1991-10-14

Total serum alpha 1-acid glycoprotein (AGP) concentration and concanavalin A-dependent microheterogeneity were studied in 31 healthy elderly subjects (18 men, 13 women, 71 to 76 yr old). Crossed affino-immunoelectrophoresis (CAIE) revealed three microheterogeneity variants of AGP: non-reactive, weakly reactive and strongly reactive with ConA. Two patterns were found in both elderly men and women, i.e. a normal pattern and one with an increase in the non-reactive form. Mean serum AGP levels in the elderly subjects with slightly higher than in a reference group of younger subjects. The Con A non-reactive form of AGP was increased in 42% of the elderly population. An increase in the non-reactive form of AGP in CAIE should be considered as general expression of chronic inflammation which is of no clinical relevance.

Antibody reactivity to the major fish allergen parvalbumin is determined by isoforms and impact of thermal processing.

PubMed

Saptarshi, Shruti R; Sharp, Michael F; Kamath, Sandip D; Lopata, Andreas L

2014-04-01

The EF-hand calcium binding protein, parvalbumin, is a major fish allergen. Detection of this allergen is often difficult due to its structural diversity among various fish species. The aim of this study was to evaluate the cross-reactivity of parvalbumin in a comprehensive range of bony and cartilaginous fish, from the Asia-Pacific region, and conduct a molecular analysis of this highly allergenic protein. Using the monoclonal anti-parvalbumin antibody PARV-19, we demonstrated the presence of monomeric and oligomeric parvalbumin in all fish analysed, except for gummy shark a cartilaginous fish. Heat processing of this allergen greatly affected its antibody reactivity. While heating caused a reduction in antibody reactivity to multimeric forms of parvalbumins for most bony fish, a complete loss of reactivity was observed for cartilaginous fish. Molecular analysis demonstrated that parvalbumin cross-reactivity, among fish species, is due to the molecular phylogenetic association of this major fish allergen. Copyright © 2013 Elsevier Ltd. All rights reserved.

Impact of layer thickness and well orientation on caprock integrity for geologic carbon storage

DOE PAGES

Newell, P.; Martinez, M. J.; Eichhubl, P.

2016-07-29

Economic feasibility of geologic carbon storage demands sustaining large storage rates without damaging caprock seals. Reactivation of pre-existing or newly formed fractures may provide a leakage pathway across caprock layers. In this paper, we apply an equivalent continuum approach within a finite element framework to model the fluid-pressure-induced reactivation of pre-existing fractures within the caprock, during high-rate injection of super-critical CO 2 into a brine-saturated reservoir in a hypothetical system, using realistic geomechanical and fluid properties. We investigate the impact of reservoir to caprock layer thickness, wellbore orientation, and injection rate on overall performance of the system with respect tomore » caprock failure and leakage. We find that vertical wells result in locally higher reservoir pressures relative to horizontal injection wells for the same injection rate, with high pressure inducing caprock leakage along reactivated opening-mode fractures in the caprock. After prolonged injection, leakage along reactivated fractures in the caprock is always higher for vertical than horizontal injection wells. Furthermore, we find that low ratios of reservoir to caprock thickness favor high excess pressure and thus fracture reactivation in the caprock. Finally, injection into thick reservoir units thus lowers the risk associated with CO 2 leakage.« less

Method for bonding thin film thermocouples to ceramics

DOEpatents

Kreider, Kenneth G.

1993-01-01

A method is provided for adhering a thin film metal thermocouple to a ceramic substrate used in an environment up to 700 degrees Centigrade, such as at a cylinder of an internal combustion engine. The method includes the steps of: depositing a thin layer of a reactive metal on a clean ceramic substrate; and depositing thin layers of platinum and a platinum-10% rhodium alloy forming the respective legs of the thermocouple on the reactive metal layer. The reactive metal layer serves as a bond coat between the thin noble metal thermocouple layers and the ceramic substrate. The thin layers of noble metal are in the range of 1-4 micrometers thick. Preferably, the ceramic substrate is selected from the group consisting of alumina and partially stabilized zirconia. Preferably, the thin layer of reactive metal is in the range of 0.015-0.030 micrometers (15-30 nanometers) thick. The preferred reactive metal is chromium. Other reactive metals may be titanium or zirconium. The thin layer of reactive metal may be deposited by sputtering in ultra high purity argon in a vacuum of approximately 2 milliTorr (0.3 Pascals).

Reactive intermediates revealed in secondary organic aerosol formation from isoprene

PubMed Central

Surratt, Jason D.; Chan, Arthur W. H.; Eddingsaas, Nathan C.; Chan, ManNin; Loza, Christine L.; Kwan, Alan J.; Hersey, Scott P.; Flagan, Richard C.; Wennberg, Paul O.; Seinfeld, John H.

2010-01-01

Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NOx conditions, respectively. Isoprene low-NOx SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NOx conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NOx SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO2 and NO2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models. PMID:20080572

Fluorine-Based DRIE of Fused Silica

NASA Technical Reports Server (NTRS)

Yee, Karl; Shcheglov, Kirill; Li, Jian; Choi, Daniel

2007-01-01

A process of deep reactive-ion etching (DRIE) using a fluorine-based gas mixture enhanced by induction-coupled plasma (ICP) has been demonstrated to be effective in forming high-aspect-ratio three-dimensional patterns in fused silica. The patterns are defined in part by an etch mask in the form of a thick, high-quality aluminum film. The process was developed to satisfy a need to fabricate high-aspect-ratio fused-silica resonators for vibratory microgyroscopes, and could be used to satisfy similar requirements for fabricating other fused-silica components.

Large unexplained suite of chemically reactive compounds present in ambient air due to biomass fires.

PubMed

Kumar, V; Chandra, B P; Sinha, V

2018-01-12

Biomass fires impact global atmospheric chemistry. The reactive compounds emitted and formed due to biomass fires drive ozone and organic aerosol formation, affecting both air quality and climate. Direct hydroxyl (OH) Reactivity measurements quantify total gaseous reactive pollutant loadings and comparison with measured compounds yields the fraction of unmeasured compounds. Here, we quantified the magnitude and composition of total OH reactivity in the north-west Indo-Gangetic Plain. More than 120% increase occurred in total OH reactivity (28 s -1 to 64 s -1 ) and from no missing OH reactivity in the normal summertime air, the missing OH reactivity fraction increased to ~40 % in the post-harvest summertime period influenced by large scale biomass fires highlighting presence of unmeasured compounds. Increased missing OH reactivity between the two summertime periods was associated with increased concentrations of compounds with strong photochemical source such as acetaldehyde, acetone, hydroxyacetone, nitromethane, amides, isocyanic acid and primary emissions of acetonitrile and aromatic compounds. Currently even the most detailed state-of-the art atmospheric chemistry models exclude formamide, acetamide, nitromethane and isocyanic acid and their highly reactive precursor alkylamines (e.g. methylamine, ethylamine, dimethylamine, trimethylamine). For improved understanding of atmospheric chemistry-air quality-climate feedbacks in biomass-fire impacted atmospheric environments, future studies should include these compounds.

Reactive and proactive aggression as meaningful distinctions at the variable and person level in primary school-aged children.

PubMed

Carroll, Annemaree; McCarthy, Molly; Houghton, Stephen; Sanders O'Connor, Emma; Zadow, Corinne

2018-04-24

Reactive and proactive aggression is a dichotomous classification of aggression in adults and children. This distinction has been supported by a number of variable-based and factor analytic studies. Due to high inter-correlations, however, the reactive-proactive aggression distinction may not be entirely useful for understanding how group or individual aggressive behavior varies in children and adolescents. Drawing on a sample of primary school-aged children (N = 242) aged 7-12 years, this study sought to determine whether reactive and proactive aggression could be distinguished at the variable-level and the person-level in children. Exploratory Factor Analysis of data from an aggression instrument measuring both functions and forms of aggression, found a two-factor construct of aggression constituted by a reactive and proactive aggression factor. A person-based analysis was then conducted after classifying children according to the presence of reactive and/or proactive aggression. Discriminant function analysis was used to discern whether classifications on the basis of aggression function produced meaningful distinctions in terms of antisocial traits and emotional valence and intensity measures. Two functions were identified which distinguished children with different combinations of reactive and proactive aggression. Reactive-only aggressive children were defined primarily by high levels of impulsivity, while proactive-only children were defined primarily by higher levels of antisocial traits. Children high in both types of aggression exhibited both the presence of antisocial traits and impulsivity. Contrary to recent findings, this suggests that differences in aggression functions remain meaningful at the person level in children. Implications for interventions are discussed. © 2018 Wiley Periodicals, Inc.

A novel trapping system for the detection of reactive drug metabolites using the fungus Cunninghamella elegans and high resolution mass spectrometry.

PubMed

Rydevik, Axel; Hansson, Annelie; Hellqvist, Anna; Bondesson, Ulf; Hedeland, Mikael

2015-07-01

A new model is presented that can be used to screen for bioactivation of drugs. The evaluation of toxicity is an important step in the development of new drugs. One way to detect possible toxic metabolites is to use trapping agents such as glutathione. Often human liver microsomes are used as a metabolic model in initial studies. However, there is a need for alternatives that are easy to handle, cheap, and can produce large amounts of metabolites. In the presented study, paracetamol, mefenamic acid, and diclofenac, all known to form reactive metabolites in humans, were incubated with the fungus Cunninghamella elegans and the metabolites formed were characterized with ultra high performance liquid chromatography coupled to a quadrupole time of flight mass spectrometer. Interestingly, glutathione conjugates formed by the fungus were observed for all three drugs and their retention times and MS/MS spectra matched those obtained in a comparative experiment with human liver microsomes. These findings clearly demonstrated that the fungus is a suitable trapping model for toxic biotransformation products. Cysteine conjugates of all three test drugs were also observed with high signal intensities in the fungal incubates, giving the model a further indicator of drug bioactivation. To our knowledge, this is the first demonstration of the use of a fungal model for the formation and trapping of reactive drug metabolites. The investigated model is cheap, easy to handle, it does not involve experimental animals and it can be scaled up to produce large amounts of metabolites. Copyright © 2014 John Wiley & Sons, Ltd.

Neighborhood Walkable Urban Form and C-Reactive Protein

EPA Science Inventory

Background: Walkable urban form predicts physical activity and lower body mass index, which lower C-reactive protein (CRP). However, urban form is also related to pollution, noise, social and health behavior, crowding, and other stressors, which may complement or contravene walka...

The inositol-1,2-cyclic phosphate moiety of the cross-reacting determinant, carbohydrate chains, and proteinaceous components are all responsible for the cross-reactivity of trypanosome variant surface glycoproteins.

PubMed

Escalona, José L; Uzcanga, Graciela L; Carrasquel, Liomary M; Bubis, José

2018-01-24

Salivarian trypanosomes evade the host immune system by continually swapping their protective variant surface glycoprotein (VSG) coat. Given that VSGs from various trypanosome stocks exhibited cross-reactivity (Camargo et al., Vet. Parasitol. 207, 17-33, 2015), we analyzed here which components are the antigenic determinants for this cross-reaction. Soluble forms of VSGs were purified from four Venezuelan animal trypanosome isolates: TeAp-N/D1, TeAp-ElFrio01, TeAp-Mantecal01, and TeGu-Terecay323. By using the VSG soluble form from TeAp-N/D1, we found that neither the inositol-1,2-cyclic phosphate moiety of the cross-reacting determinant nor the carbohydrate chains were exclusively responsible for its cross-reactivity. Then, all four purified glycoproteins were digested with papain and the resulting peptides were separated by high-performance liquid chromatography. Dot blot evaluation of the fractions using sera from trypanosome-infected animals yielded peptides that possessed cross-reaction activity, demonstrating for the first time that proteinaceous epitopes are also responsible for the cross-reactivity of trypanosome VSGs.

Pore Formation Process of Porous Ti3SiC2 Fabricated by Reactive Sintering

PubMed Central

Zhang, Huibin; Liu, Xinli; Jiang, Yao

2017-01-01

Porous Ti3SiC2 was fabricated with high purity, 99.4 vol %, through reactive sintering of titanium hydride (TiH2), silicon (Si) and graphite (C) elemental powders. The reaction procedures and the pore structure evolution during the sintering process were systematically studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). Our results show that the formation of Ti3SiC2 from TiH2/Si/C powders experienced the following steps: firstly, TiH2 decomposed into Ti; secondly, TiC and Ti5Si3 intermediate phases were generated; finally, Ti3SiC2 was produced through the reaction of TiC, Ti5Si3 and Si. The pores formed in the synthesis procedure of porous Ti3SiC2 ceramics are derived from the following aspects: interstitial pores left during the pressing procedure; pores formed because of the TiH2 decomposition; pores formed through the reactions between Ti and Si and Ti and C powders; and the pores produced accompanying the final phase synthesized during the high temperature sintering process. PMID:28772515

9-Fluorenylmethyl (Fm) Disulfides: Biomimetic Precursors for Persulfides

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

Park, Chung-Min; Johnson, Brett A.; Duan, Jicheng

Protein S-sulfhydration has been recognized as an important post-translational modification that regulates H2S signals. However, the reactivity and biological implications of the products of S-sulfhydration, i.e. persulfides, are still unclear. This is mainly due to the instability of persulfides and difficulty to access these molecules. Under physiological conditions persulfides mainly exist in anionic forms because of their low pKa values. However, current methods do not allow for the direct generation of persulfide anions under biomimetic and non-H2S conditions. Herein we report the development of a functional disulfide, FmSSPy-A (Fm =9-fluorenylmethyl; Py = pyridinyl). This reagent can effectively convert both smallmore » molecule and protein thiols (-SH) to form –S-SFm adducts under mild conditions. It allows for a H2S-free and biomimetic protocol to generate highly reactive persulfides (in their anionic forms). We also demonstrated the high nucleophilicity of persulfides toward a number of thiol-blocking reagents. This method holds promise for further understanding the chemical biology of persulfides and S-sulfhydration.« less

Nanopore reactive adsorbents for the high-efficiency removal of waste species

DOEpatents

Yang, Arthur Jing-Min; Zhang, Yuehua

2005-01-04

A nanoporous reactive adsorbent incorporates a relatively small number of relatively larger reactant, e.g., metal, enzyme, etc., particles (10) forming a discontinuous or continuous phase interspersed among and surrounded by a continuous phase of smaller adsorbent particles (12) and connected interstitial pores (14) therebetween. The reactive adsorbent can effectively remove inorganic or organic impurities in a liquid by causing the liquid to flow through the adsorbent. For example, silver ions may be adsorbed by the adsorbent particles (12) and reduced to metallic silver by reducing metal, such as ions, as the reactant particles (10). The column can be regenerated by backwashing with the liquid effluent containing, for example, acetic acid.

Effective biotransformation and detoxification of anthraquinone dye reactive blue 4 by using aerobic bacterial granules.

PubMed

Chaudhari, Ashvini U; Paul, Dhiraj; Dhotre, Dhiraj; Kodam, Kisan M

2017-10-01

Treatment of textile wastewater containing anthraquinone dye is quite a huge challenge due to its complex aromatic structure and toxicity. Present study deals with the degradation and detoxification of anthraquinone dye reactive blue 4 using aerobic bacterial granules. Bacterial granules effectively decolorized reactive blue 4 at wide range of pH (4.0-11.0) and temperature (20-55 °C) as well as decolorized and tolerated high concentration of reactive blue 4 dye upto 1000 mg l -1 with V max 6.16 ± 0.82 mg l -1 h -1 and K m 227 ± 41 mg l -1 . Metagenomics study evaluates important role of Clostridia, Actinobacteria, and Proteobacterial members in biotransformation and tolerance of high concentrations of reactive blue 4 dye. Up-regulation of xenobiotic degradation and environmental information processing pathways during dye exposure signifies their noteworthy role in dye degradation. Biotransformation of dye was confirmed by significant decrease in the values of total suspended solids, biological and chemical oxygen demand. The metabolites formed after biotransformation was characterized by FT-IR and GC-MS analysis. The reactive blue 4 dye was found to be phytotoxic, cytotoxic and genotoxic whereas its biotransformed product were non-toxic. This study comprehensively illustrates that, bacterial aerobic granules can be used for eco-friendly remediation and detoxification of wastewater containing high organic load of anthraquinone dye. Copyright © 2017 Elsevier Ltd. All rights reserved.

Apparatus for making environmentally stable reactive alloy powders

DOEpatents

Anderson, I.E.; Lograsso, B.K.; Terpstra, R.L.

1996-12-31

Apparatus and method are disclosed for making powder from a metallic melt by atomizing the melt to form droplets and reacting the droplets downstream of the atomizing location with a reactive gas. The droplets are reacted with the gas at a temperature where a solidified exterior surface is formed thereon and where a protective refractory barrier layer (reaction layer) is formed whose penetration into the droplets is limited by the presence of the solidified surface so as to avoid selective reduction of key reactive alloyants needed to achieve desired powder end use properties. The barrier layer protects the reactive powder particles from environmental constituents such as air and water in the liquid or vapor form during subsequent fabrication of the powder to end-use shapes and during use in the intended service environment. 7 figs.

The reactive element effect of yttrium and yttrium silicon on high temperature oxidation of NiCrAl coating

NASA Astrophysics Data System (ADS)

Ramandhany, S.; Sugiarti, E.; Desiati, R. D.; Martides, E.; Junianto, E.; Prawara, B.; Sukarto, A.; Tjahjono, A.

2018-03-01

The microstructure formed on the bond coat affects the oxidation resistance, particularly the formation of a protective oxide layer. The adhesion of bond coat and TGO increased significantly by addition of reactive element. In the present work, the effect of yttrium and yttrium silicon as reactive element (RE) on NiCrAl coating was investigated. The NiCrAl (without RE) and NiCrAlX (X:Y or YSi) bond coating were deposited on Hastelloy C-276 substrate by High Velocity Oxygen Fuel (HVOF) method. Isothermal oxidation was carried out at 1000 °C for 100 hours. The results showed that the addition of RE could prevent the breakaway oxidation. Therefore, the coating with reactive element were more protective against high temperature oxidation. Furthermore, the oxidation rate of NiCrAlY coating was lower than NiCrAlYSi coating with the total mass change was ±2.394 mg/cm2 after 100 hours of oxidation. The thickness of oxide scale was approximately 1.18 μm consisting of duplex oxide scale of spinel NiCr2O4 in outer scale and protective α-Al2O3 in inner scale.

Evolution and current understanding of physicochemical characterization of particulate matter from reactivity controlled compression ignition combustion on a multicylinder light-duty engine

DOE PAGES

Storey, John Morse; Curran, Scott J.; Lewis, Samuel A.; ...

2016-08-04

Low-temperature compression ignition combustion can result in nearly smokeless combustion, as indicated by a smoke meter or other forms of soot measurement that rely on absorbance due to elemental carbon content. Highly premixed low-temperature combustion modes do not form particulate matter in the traditional pathways seen with conventional diesel combustion. Previous research into reactivity controlled compression ignition particulate matter has shown, despite a near zero smoke number, significant mass can be collected on filter media used for particulate matter certification measurement. In addition, particulate matter size distributions reveal that a fraction of the particles survive heated double-dilution conditions. This papermore » summarizes research completed at Oak Ridge National Laboratory to date on characterizing the nature, chemistry and aftertreatment considerations of reactivity controlled compression ignition particulate matter and presents new research highlighting the importance of injection strategy and fuel composition on reactivity controlled compression ignition particulate matter formation. Particle size measurements and the transmission electron microscopy results do show the presence of soot particles; however, the elemental carbon fraction was, in many cases, within the uncertainty of the thermal–optical measurement. Particulate matter emitted during reactivity controlled compression ignition operation was also collected with a novel sampling technique and analyzed by thermal desorption or pyrolysis gas chromatography mass spectroscopy. Particulate matter speciation results indicated that the high boiling range of diesel hydrocarbons was likely responsible for the particulate matter mass captured on the filter media. Finally, to investigate potential fuel chemistry effects, either ethanol or biodiesel were incorporated to assess whether oxygenated fuels may enhance particle emission reduction.« less

Evolution and current understanding of physicochemical characterization of particulate matter from reactivity controlled compression ignition combustion on a multicylinder light-duty engine

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

Storey, John Morse; Curran, Scott J.; Lewis, Samuel A.

Low-temperature compression ignition combustion can result in nearly smokeless combustion, as indicated by a smoke meter or other forms of soot measurement that rely on absorbance due to elemental carbon content. Highly premixed low-temperature combustion modes do not form particulate matter in the traditional pathways seen with conventional diesel combustion. Previous research into reactivity controlled compression ignition particulate matter has shown, despite a near zero smoke number, significant mass can be collected on filter media used for particulate matter certification measurement. In addition, particulate matter size distributions reveal that a fraction of the particles survive heated double-dilution conditions. This papermore » summarizes research completed at Oak Ridge National Laboratory to date on characterizing the nature, chemistry and aftertreatment considerations of reactivity controlled compression ignition particulate matter and presents new research highlighting the importance of injection strategy and fuel composition on reactivity controlled compression ignition particulate matter formation. Particle size measurements and the transmission electron microscopy results do show the presence of soot particles; however, the elemental carbon fraction was, in many cases, within the uncertainty of the thermal–optical measurement. Particulate matter emitted during reactivity controlled compression ignition operation was also collected with a novel sampling technique and analyzed by thermal desorption or pyrolysis gas chromatography mass spectroscopy. Particulate matter speciation results indicated that the high boiling range of diesel hydrocarbons was likely responsible for the particulate matter mass captured on the filter media. Finally, to investigate potential fuel chemistry effects, either ethanol or biodiesel were incorporated to assess whether oxygenated fuels may enhance particle emission reduction.« less

Roles of Reversible and Irreversible Aggregation in Sugar Processing

USDA-ARS?s Scientific Manuscript database

Colloids (1-1000 nm particles) in sugar cane/beet juice originate from non-sucrose impurities (polyphenolic colorants, residual soil, polysaccharides) of the plant materials; additional colloids form during the high temperature processing. Colloids are reactive towards aggregation, sorption, desorp...

Quantum-state resolved reactive scattering at the gas-liquid interface: F+squalane (C30H62) dynamics via high-resolution infrared absorption of nascent HF(v,J).

PubMed

Zolot, Alexander M; Dagdigian, Paul J; Nesbitt, David J

2008-11-21

Exothermic chemical reaction dynamics at the gas-liquid interface have been investigated by colliding a supersonic beam of F atoms [E(com)=0.7(3) kcalmol] with a continuously refreshed liquid hydrocarbon (squalane) surface under high vacuum conditions. Absolute HF(v,J) product densities are determined by infrared laser absorption spectroscopy, with velocity distributions along the probe axis derived from high resolution Dopplerimetry. Nascent HF(v

Quantum-state resolved reactive scattering at the gas-liquid interface: F +squalane (C30H62) dynamics via high-resolution infrared absorption of nascent HF(v,J)

NASA Astrophysics Data System (ADS)

Zolot, Alexander M.; Dagdigian, Paul J.; Nesbitt, David J.

2008-11-01

Exothermic chemical reaction dynamics at the gas-liquid interface have been investigated by colliding a supersonic beam of F atoms [Ecom=0.7(3)kcal/mol] with a continuously refreshed liquid hydrocarbon (squalane) surface under high vacuum conditions. Absolute HF(v,J) product densities are determined by infrared laser absorption spectroscopy, with velocity distributions along the probe axis derived from high resolution Dopplerimetry. Nascent HF(v ⩽3) products are formed in a highly nonequilibrium (inverted) vibrational distribution [⟨Evib⟩=13.2(2)kcal/mol], reflecting insufficient time for complete thermal accommodation with the surface prior to desorption. Colder, but still non-Boltzmann, rotational state populations [⟨Erot⟩=1.0(1)kcal/mol] indicate that some fraction of molecules directly scatter into the gas phase without rotationally equilibrating with the surface. Nascent HF also recoils from the liquid surface with excess translational energy, resulting in Doppler broadened linewidths that increase systematically with internal HF excitation. The data are consistent with microscopic branching in HF-surface dynamics following the reactive event, with (i) a direct reactive scattering fraction of newly formed product molecules leaving the surface promptly and (ii) a trapping desorption fraction that accommodates rotationally (though still not vibrationally) with the bulk liquid. Comparison with analogous gas phase F +hydrocarbon processes reveals that the liquid acts as a partial "heat sink" for vibrational energy flow on the time scale of the chemical reaction event.

[Inactivation and reactivation of antibiotic-resistant bacteria during and after UV disinfection in reclaimed water].

PubMed

Huang, Jing-Jing; Tang, Fang; Xi, Jin-Ying; Pang, Yu-Chen; Hu, Hong-Ying

2014-04-01

Prevalence of antibiotic-resistant bacteria in wastewater effluents is concerned as an emerging contaminant. To estimate inactivation and reactivation potentials of antibiotic-resistant bacteria by UV disinfection, inactivation and reactivation of penicillin-, ampicillin-, cephalexin-, chloramphenicol-and rifampicin-resistant bacteria in the secondary effluent were studied under different UV doses. The results showed that the inactivation ratios of penicillin-, ampicillin-, cephalexin-and chloramphenicol-resistant bacteria were higher than 4-log, which was closed to that of total heterotrophic bacteria; however, the inactivation ratio of rifampicin-resistant bacteria was lower (3.7-log) under 20 mJ x cm(-2) UV exposure. After 22 h standing incubation, antibiotic-resistant bacteria widely reactivated. The colony forming ability of antibiotic-resistant bacteria was as high as 3-log when exposed to 20 mJ x cm(-2) UV light. Hence, conventional UV dose can not effectively control reactivation of antibiotic-resistant bacteria in reclaimed water by UV disinfection.

Biological Reactive Intermediates (BRIs) Formed from Botanical Dietary Supplements

PubMed Central

Dietz, Birgit M.; Bolton, Judy L.

2013-01-01

The use of botanical dietary supplements is increasingly popular, due to their natural origin and the perceived assumption that they are safer than prescription drugs. While most botanical dietary supplements can be considered safe, a few contain compounds, which can be converted to reactive biological reactive intermediates (BRIs) causing toxicity. For example, sassafras oil contains safrole, which can be converted to a reactive carbocation forming genotoxic DNA adducts. Alternatively, some botanical dietary supplements contain stable BRIs such as simple Michael acceptors that react with chemosensor proteins such as Keap1 resulting in induction of protective detoxification enzymes. Examples include curcumin from turmeric, xanthohumol from hops, and Z-ligustilide from dang gui. Quinones (sassafras, kava, black cohosh), quinone methides (sassafras), and epoxides (pennyroyal oil) represent BRIs of intermediate reactivity, which could generate both genotoxic and/or chemopreventive effects. The biological targets of BRIs formed from botanical dietary supplements and their resulting toxic and/or chemopreventive effects are closely linked to the reactivity of BRIs as well as dose and time of exposure. PMID:20970412

Oblique patterned etching of vertical silicon sidewalls

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

Burckel, D. Bruce; Finnegan, Patrick S.; Henry, M. David

A method for patterning on vertical silicon surfaces in high aspect ratio silicontopography is presented. A Faraday cage is used to direct energetic reactive ions obliquely through a patterned suspended membrane positioned over the topography. The technique is capable of forming high-fidelity pattern (100 nm) features, adding an additional fabrication capability to standard top-down fabrication approaches.

Oblique patterned etching of vertical silicon sidewalls

NASA Astrophysics Data System (ADS)

Bruce Burckel, D.; Finnegan, Patrick S.; David Henry, M.; Resnick, Paul J.; Jarecki, Robert L.

2016-04-01

A method for patterning on vertical silicon surfaces in high aspect ratio silicon topography is presented. A Faraday cage is used to direct energetic reactive ions obliquely through a patterned suspended membrane positioned over the topography. The technique is capable of forming high-fidelity pattern (100 nm) features, adding an additional fabrication capability to standard top-down fabrication approaches.

Oblique patterned etching of vertical silicon sidewalls

DOE PAGES

Burckel, D. Bruce; Finnegan, Patrick S.; Henry, M. David; ...

2016-04-05

A method for patterning on vertical silicon surfaces in high aspect ratio silicontopography is presented. A Faraday cage is used to direct energetic reactive ions obliquely through a patterned suspended membrane positioned over the topography. The technique is capable of forming high-fidelity pattern (100 nm) features, adding an additional fabrication capability to standard top-down fabrication approaches.

Pathways and processes of risk in associations among maternal antisocial personality symptoms, interparental aggression, and preschooler's psychopathology.

PubMed

Davies, Patrick T; Sturge-Apple, Melissa L; Cicchetti, Dante; Manning, Liviah G; Vonhold, Sara E

2012-08-01

Two studies examined the nature and processes underlying the joint role of interparental aggression and maternal antisocial personality as predictors of children's disruptive behavior problems. Participants for both studies included a high-risk sample of 201 mothers and their 2-year-old children in a longitudinal, multimethod design. Addressing the form of the interplay between interparental aggression and maternal antisocial personality as risk factors for concurrent and prospective levels of child disruptive problems, the Study 1 findings indicated that maternal antisocial personality was a predictor of the initial levels of preschooler's disruptive problems independent of the effects of interparental violence, comorbid forms of maternal psychopathology, and socioeconomic factors. In attesting to the salience of interparental aggression in the lives of young children, latent difference score analyses further revealed that interparental aggression mediated the link between maternal antisocial personality and subsequent changes in child disruptive problems over a 1-year period. To identify the family mechanisms that account for the two forms of intergenerational transmission of disruptive problems identified in Study 1, Study 2 explored the role of children's difficult temperament, emotional reactivity to interparental conflict, adrenocortical reactivity in a challenging parent-child task, and experiences with maternal parenting as mediating processes. Analyses identified child emotional reactivity to conflict and maternal unresponsiveness as mediators in pathways between interparental aggression and preschooler's disruptive problems. The findings further supported the role of blunted adrenocortical reactivity as an allostatic mediator of the associations between parental unresponsiveness and child disruptive problems.

Environmentally stable reactive alloy powders and method of making same

DOEpatents

Anderson, I.E.; Lograsso, B.K.; Terpstra, R.L.

1998-09-22

Apparatus and method are disclosed for making powder from a metallic melt by atomizing the melt to form droplets and reacting the droplets downstream of the atomizing location with a reactive gas. The droplets are reacted with the gas at a temperature where a solidified exterior surface is formed thereon and where a protective refractory barrier layer (reaction layer) is formed whose penetration into the droplets is limited by the presence of the solidified surface so as to avoid selective reduction of key reactive alloys needed to achieve desired powder end use properties. The barrier layer protects the reactive powder particles from environmental constituents such as air and water in the liquid or vapor form during subsequent fabrication of the powder to end-use shapes and during use in the intended service environment. 7 figs.

New nanotube synthesis strategy--application of sodium nanotubes formed inside anodic aluminium oxide as a reactive template.

PubMed

Wang, Lung-Shen; Lee, Chi-Young; Chiu, Hsin-Tien

2003-08-07

Formation of Na nanotubes inside the channels of anodic aluminium oxide (AAO) membranes has been achieved by decomposing NaH thermally on AAO. The as-produced material, Na@AAO, is applied as a reactive template to prepare other tubular materials. Reacting Na@AAO with gaseous C6Cl6 generates carbon nanotubes (ca. 250 nm, wall thickness of 20 nm, tube length of 60 microm) inside the AAO channels. Highly aligned bundles of nearly amorphous carbon nanotubes are isolated after AAO is removed.

Carbon Nanostructure Examined by Lattice Fringe Analysis of High Resolution Transmission Electron Microscopy Images

NASA Technical Reports Server (NTRS)

VanderWal, Randy L.; Tomasek, Aaron J.; Street, Kenneth; Thompson, William K.

2002-01-01

The dimensions of graphitic layer planes directly affect the reactivity of soot towards oxidation and growth. Quantification of graphitic structure could be used to develop and test correlations between the soot nanostructure and its reactivity. Based upon transmission electron microscopy images, this paper provides a demonstration of the robustness of a fringe image analysis code for determining the level of graphitic structure within nanoscale carbon, i.e. soot. Results, in the form of histograms of graphitic layer plane lengths, are compared to their determination through Raman analysis.

Carbon Nanostructure Examined by Lattice Fringe Analysis of High Resolution Transmission Electron Microscopy Images

NASA Technical Reports Server (NTRS)

VanderWal, Randy L.; Tomasek, Aaron J.; Street, Kenneth; Thompson, William K.; Hull, David R.

2003-01-01

The dimensions of graphitic layer planes directly affect the reactivity of soot towards oxidation and growth. Quantification of graphitic structure could be used to develop and test correlations between the soot nanostructure and its reactivity. Based upon transmission electron microscopy images, this paper provides a demonstration of the robustness of a fringe image analysis code for determining the level of graphitic structure within nanoscale carbon, i.e., soot. Results, in the form of histograms of graphitic layer plane lengths, are compared to their determination through Raman analysis.

Non-enzymatic interactions of glyoxylate with lysine, arginine, and glucosamine: a study of advanced non-enzymatic glycation like compounds.

PubMed

Dutta, Udayan; Cohenford, Menashi A; Guha, Madhumita; Dain, Joel A

2007-02-01

Glyoxylate is a 2 carbon aldo acid that is formed in hepatic tissue from glycolate. Once formed, the molecule can be converted to glycine by alanine-glyoxylate aminotransferase (AGAT). In defects of AGAT, glyoxylate is transformed to oxalate, resulting in high levels of oxalate in the body. The objective of this study was 2-fold. First, it was to determine, if akin to D-glucose, D-fructose or DL-glyceraldehyde, glyoxylate was susceptible to non-enzymatic attack by amino containing molecules such as lysine, arginine or glucosamine. Second, if by virtue of its molecular structure and size, glyoxylate was as reactive a reagent in non-enzymatic reactions as DL-glyceraldehyde; i.e., a glycose that we previously demonstrated to be a more effective glycating agent than D-glucose or D-fructose. Using capillary electrophoresis (CE), high performance liquid chromatography and UV and fluorescence spectroscopy, glyoxylate was found to be a highly reactive precursor of advanced glycation like end products (AGLEs) and a more effective promoter of non-enzymatic end products than D-glucose, D-fructose or DL-glyceraldehyde.

Early life adversity reduces stress reactivity and enhances impulsive behavior: Implications for health behaviors

PubMed Central

Lovallo, William R.

2012-01-01

Altered reactivity to stress, either in the direction of exaggerated reactivity or diminished reactivity, may signal a dysregulation of systems intended to maintain homeostasis and a state of good health. Evidence has accumulated that diminished reactivity to psychosocial stress may signal poor health outcomes. One source of diminished cortisol and autonomic reactivity is the experience of adverse rearing during childhood and adolescence. The Oklahoma Family Health Patterns Project has examined a cohort of 426 healthy young adults with and without a family history of alcoholism. Regardless of family history, persons who had experienced high degrees of adversity prior to age 16 had a constellation of changes including reduced cortisol and heart rate reactivity, diminished cognitive capacity, and unstable regulation of affect, leading to behavioral impulsivity and antisocial tendencies. We present a model whereby this constellation of physiological, cognitive, and affective tendencies is consistent with altered central dopaminergic activity leading to changes in brain function that may foster impulsive and risky behaviors. These in turn may promote greater use of alcohol other drugs along with adopting poor health behaviors. This model provides a pathway from early life adversity to low stress reactivity that forms a basis for risky behaviors and poor health outcomes. PMID:23085387

Influence of high-temperature steam on the reactivity of CaO sorbent for CO₂ capture.

PubMed

Donat, Felix; Florin, Nicholas H; Anthony, Edward J; Fennell, Paul S

2012-01-17

Calcium looping is a high-temperature CO(2) capture technology applicable to the postcombustion capture of CO(2) from power station flue gas, or integrated with fuel conversion in precombustion CO(2) capture schemes. The capture technology uses solid CaO sorbent derived from natural limestone and takes advantage of the reversible reaction between CaO and CO(2) to form CaCO(3); that is, to achieve the separation of CO(2) from flue or fuel gas, and produce a pure stream of CO(2) suitable for geological storage. An important characteristic of the sorbent, affecting the cost-efficiency of this technology, is the decay in reactivity of the sorbent over multiple CO(2) capture-and-release cycles. This work reports on the influence of high-temperature steam, which will be present in flue (about 5-10%) and fuel (∼20%) gases, on the reactivity of CaO sorbent derived from four natural limestones. A significant increase in the reactivity of these sorbents was found for 30 cycles in the presence of steam (from 1-20%). Steam influences the sorbent reactivity in two ways. Steam present during calcination promotes sintering that produces a sorbent morphology with most of the pore volume associated with larger pores of ∼50 nm in diameter, and which appears to be relatively more stable than the pore structure that evolves when no steam is present. The presence of steam during carbonation reduces the diffusion resistance during carbonation. We observed a synergistic effect, i.e., the highest reactivity was observed when steam was present for both calcination and carbonation.

Spiral pattern in a radial displacement in a Hele-Shaw cell

NASA Astrophysics Data System (ADS)

Ban, Mitsumasa; Nagatsu, Yuichiro; Hayashi, Atsushi; Kato, Yoshihiro; Tada, Yutaka

2008-11-01

When a reactive and miscible less-viscous liquid displaces a more-viscous liquid in a Hele-Shaw cell, reactive miscible viscous fingering takes place. We have experimentally shown that the pattern created by the displacement of a more-viscous fluid by a less-viscous one in a radial Hele-Shaw cell develops not radially but spirally when a more-viscous sodium polyacrylate solution is displaced by a less-viscous trivalent iron ion (Fe^3+) solution with a sufficiently high concentration of Fe^3+. Another experiment in order to investigate the mechanism of spiral pattern formation revealed that an instantaneous chemical reaction takes place between the two fluids and at high Fe^3+ concentrations it produces a film of the gel at the contact plane. The gel is formed by three-dimensional network structures between the polyacrylate solution and the trivalent iron ion (Fe^3+) solution. We have proposed a physical model that the gel's film is responsible for the form of the spiral pattern.

A structurally driven analysis of thiol reactivity in mammalian albumins.

PubMed

Spiga, Ottavia; Summa, Domenico; Cirri, Simone; Bernini, Andrea; Venditti, Vincenzo; De Chiara, Matteo; Priora, Raffaella; Frosali, Simona; Margaritis, Antonios; Di Giuseppe, Danila; Di Simplicio, Paolo; Niccolai, Neri

2011-04-01

Understanding the structural basis of protein redox activity is still an open question. Hence, by using a structural genomics approach, different albumins have been chosen to correlate protein structural features with the corresponding reaction rates of thiol exchange between albumin and disulfide DTNB. Predicted structures of rat, porcine, and bovine albumins have been compared with the experimentally derived human albumin. High structural similarity among these four albumins can be observed, in spite of their markedly different reactivity with DTNB. Sequence alignments offered preliminary hints on the contributions of sequence-specific local environments modulating albumin reactivity. Molecular dynamics simulations performed on experimental and predicted albumin structures reveal that thiolation rates are influenced by hydrogen bonding pattern and stability of the acceptor C34 sulphur atom with donor groups of nearby residues. Atom depth evolution of albumin C34 thiol groups has been monitored during Molecular Dynamic trajectories. The most reactive albumins appeared also the ones presenting the C34 sulphur atom on the protein surface with the highest accessibility. High C34 sulphur atom reactivity in rat and porcine albumins seems to be determined by the presence of additional positively charged amino acid residues favoring both the C34 S⁻ form and the approach of DTNB. Copyright © 2011 Wiley Periodicals, Inc.

Tutorial: Reactive high power impulse magnetron sputtering (R-HiPIMS)

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

Anders, André

High Power Impulse Magnetron Sputtering (HiPIMS) is a coating technology that combines magnetron sputtering with pulsed power concepts. Furthermore, by applying power in pulses of high amplitude and a relatively low duty cycle, large fractions of sputtered atoms and near-target gases are ionized. In contrast to conventional magnetron sputtering, HiPIMS is characterized by self-sputtering or repeated gas recycling for high and low sputter yield materials, respectively, and both for most intermediate materials. The dense plasma in front of the target has the dual function of sustaining the discharge and providing plasma-assistance to film growth, affecting the microstructure of growing films.more » Many technologically interesting thin films are compound films, which are composed of one or more metals and a reactive gas, most often oxygen or nitrogen. When reactive gas is added, non-trivial consequences arise for the system because the target may become “poisoned,” i.e., a compound layer forms on the target surface affecting the sputtering yield and the yield of secondary electron emission and thereby all other parameters. It is emphasized that the target state depends not only on the reactive gas' partial pressure (balanced via gas flow and pumping) but also on the ion flux to the target, which can be controlled by pulse parameters. This is a critical technological opportunity for reactive HiPIMS (R-HiPIMS). The scope of this tutorial is focused on plasma processes and mechanisms of operation and only briefly touches upon film properties. It introduces R-HiPIMS in a systematic, step-by-step approach by covering sputtering, magnetron sputtering, reactive magnetron sputtering, pulsed reactive magnetron sputtering, HiPIMS, and finally R-HiPIMS. The tutorial is concluded by considering variations of R-HiPIMS known as modulated pulsed power magnetron sputtering and deep-oscillation magnetron sputtering and combinations of R-HiPIMS with superimposed dc magnetron sputtering.« less

Tutorial: Reactive high power impulse magnetron sputtering (R-HiPIMS)

DOE PAGES

Anders, André

2017-03-21

High Power Impulse Magnetron Sputtering (HiPIMS) is a coating technology that combines magnetron sputtering with pulsed power concepts. Furthermore, by applying power in pulses of high amplitude and a relatively low duty cycle, large fractions of sputtered atoms and near-target gases are ionized. In contrast to conventional magnetron sputtering, HiPIMS is characterized by self-sputtering or repeated gas recycling for high and low sputter yield materials, respectively, and both for most intermediate materials. The dense plasma in front of the target has the dual function of sustaining the discharge and providing plasma-assistance to film growth, affecting the microstructure of growing films.more » Many technologically interesting thin films are compound films, which are composed of one or more metals and a reactive gas, most often oxygen or nitrogen. When reactive gas is added, non-trivial consequences arise for the system because the target may become “poisoned,” i.e., a compound layer forms on the target surface affecting the sputtering yield and the yield of secondary electron emission and thereby all other parameters. It is emphasized that the target state depends not only on the reactive gas' partial pressure (balanced via gas flow and pumping) but also on the ion flux to the target, which can be controlled by pulse parameters. This is a critical technological opportunity for reactive HiPIMS (R-HiPIMS). The scope of this tutorial is focused on plasma processes and mechanisms of operation and only briefly touches upon film properties. It introduces R-HiPIMS in a systematic, step-by-step approach by covering sputtering, magnetron sputtering, reactive magnetron sputtering, pulsed reactive magnetron sputtering, HiPIMS, and finally R-HiPIMS. The tutorial is concluded by considering variations of R-HiPIMS known as modulated pulsed power magnetron sputtering and deep-oscillation magnetron sputtering and combinations of R-HiPIMS with superimposed dc magnetron sputtering.« less

Tutorial: Reactive high power impulse magnetron sputtering (R-HiPIMS)

NASA Astrophysics Data System (ADS)

Anders, André

2017-05-01

High Power Impulse Magnetron Sputtering (HiPIMS) is a coating technology that combines magnetron sputtering with pulsed power concepts. By applying power in pulses of high amplitude and a relatively low duty cycle, large fractions of sputtered atoms and near-target gases are ionized. In contrast to conventional magnetron sputtering, HiPIMS is characterized by self-sputtering or repeated gas recycling for high and low sputter yield materials, respectively, and both for most intermediate materials. The dense plasma in front of the target has the dual function of sustaining the discharge and providing plasma-assistance to film growth, affecting the microstructure of growing films. Many technologically interesting thin films are compound films, which are composed of one or more metals and a reactive gas, most often oxygen or nitrogen. When reactive gas is added, non-trivial consequences arise for the system because the target may become "poisoned," i.e., a compound layer forms on the target surface affecting the sputtering yield and the yield of secondary electron emission and thereby all other parameters. It is emphasized that the target state depends not only on the reactive gas' partial pressure (balanced via gas flow and pumping) but also on the ion flux to the target, which can be controlled by pulse parameters. This is a critical technological opportunity for reactive HiPIMS (R-HiPIMS). The scope of this tutorial is focused on plasma processes and mechanisms of operation and only briefly touches upon film properties. It introduces R-HiPIMS in a systematic, step-by-step approach by covering sputtering, magnetron sputtering, reactive magnetron sputtering, pulsed reactive magnetron sputtering, HiPIMS, and finally R-HiPIMS. The tutorial is concluded by considering variations of R-HiPIMS known as modulated pulsed power magnetron sputtering and deep-oscillation magnetron sputtering and combinations of R-HiPIMS with superimposed dc magnetron sputtering.

Effectiveness of reactive case detection for malaria elimination in three archetypical transmission settings: a modelling study.

PubMed

Gerardin, Jaline; Bever, Caitlin A; Bridenbecker, Daniel; Hamainza, Busiku; Silumbe, Kafula; Miller, John M; Eisele, Thomas P; Eckhoff, Philip A; Wenger, Edward A

2017-06-12

Reactive case detection could be a powerful tool in malaria elimination, as it selectively targets transmission pockets. However, field operations have yet to demonstrate under which conditions, if any, reactive case detection is best poised to push a region to elimination. This study uses mathematical modelling to assess how baseline transmission intensity and local interconnectedness affect the impact of reactive activities in the context of other possible intervention packages. Communities in Southern Province, Zambia, where elimination operations are currently underway, were used as representatives of three archetypes of malaria transmission: low-transmission, high household density; high-transmission, low household density; and high-transmission, high household density. Transmission at the spatially-connected household level was simulated with a dynamical model of malaria transmission, and local variation in vectorial capacity and intervention coverage were parameterized according to data collected from the area. Various potential intervention packages were imposed on each of the archetypical settings and the resulting likelihoods of elimination by the end of 2020 were compared. Simulations predict that success of elimination campaigns in both low- and high-transmission areas is strongly dependent on stemming the flow of imported infections, underscoring the need for regional-scale strategies capable of reducing transmission concurrently across many connected areas. In historically low-transmission areas, treatment of clinical malaria should form the cornerstone of elimination operations, as most malaria infections in these areas are symptomatic and onward transmission would be mitigated through health system strengthening; reactive case detection has minimal impact in these settings. In historically high-transmission areas, vector control and case management are crucial for limiting outbreak size, and the asymptomatic reservoir must be addressed through reactive case detection or mass drug campaigns. Reactive case detection is recommended only for settings where transmission has recently been reduced rather than all low-transmission settings. This is demonstrated in a modelling framework with strong out-of-sample accuracy across a range of transmission settings while including methodologies for understanding the most resource-effective allocations of health workers. This approach generalizes to providing a platform for planning rational scale-up of health systems based on locally-optimized impact according to simplified stratification.

Gas Phase Reactivity of Carboxylates with N-Hydroxysuccinimide Esters

PubMed Central

Peng, Zhou; McGee, William M.; Bu, Jiexun; Barefoot, Nathan Z.; McLuckey, Scott A.

2015-01-01

N-hydroxysuccinimide (NHS) esters have been used for gas phase conjugation reactions with peptides at nucleophilic sites, such as primary amines (N-terminus, ε-amine of lysine) or guanidines, by forming amide bonds through a nucleophilic attack on the carbonyl carbon. The carboxylate has recently been found to also be a reactive nucleophile capable of initiating a similar nucleophilic attack to form a labile anhydride bond. The fragile bond is easily cleaved, resulting in an oxygen transfer from the carboxylate-containing species to the reagent, nominally observed as a water transfer. This reactivity is shown for both peptides and non-peptidic species. Reagents isotopically labeled with O18 were used to confirm reactivity. This constitutes an example of distinct differences in reactivity of carboxylates between the gas-phase, where they are shown to be reactive, and the solution-phase, where they are not regarded as reactive with NHS esters. PMID:25338221

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

PubMed

Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

2011-01-07

Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully understanding the activity of gold are considered.

Reactive nitrogen partitioning and its relationship to winter ozone events in Utah

NASA Astrophysics Data System (ADS)

Wild, R. J.; Edwards, P. M.; Bates, T. S.; Cohen, R. C.; de Gouw, J. A.; Dubé, W. P.; Gilman, J. B.; Holloway, J.; Kercher, J.; Koss, A.; Lee, L.; Lerner, B.; McLaren, R.; Quinn, P. K.; Roberts, J. M.; Stutz, J.; Thornton, J. A.; Veres, P. R.; Warneke, C.; Williams, E.; Young, C. J.; Yuan, B.; Brown, S. S.

2015-08-01

High wintertime ozone levels have been observed in the Uintah Basin, Utah, a sparsely populated rural region with intensive oil and gas operations. The reactive nitrogen budget plays an important role in tropospheric ozone formation. Measurements were taken during three field campaigns in the winters of 2012, 2013, and 2014, which experienced varying climatic conditions. Average concentrations of ozone and total reactive nitrogen were observed to be 2.5 times higher in 2013 than 2012, with 2014 an intermediate year in most respects. However, photochemically active NOx(NO+NO2), remained remarkably similar all three years. Roughly half of the more oxidized forms of nitrogen were composed of nitric acid in 2013, with nighttime nitric acid formation through heterogeneous uptake of N2O5 contributing approximately 6 times more than daytime formation. The nighttime N2O5 lifetime between the high-ozone year 2013 and the low-ozone year 2012 is lower by a factor 2.6, and much of this is due to higher aerosol surface area in the high ozone year of 2013. A box-model simulation supports the importance of nighttime chemistry on the reactive nitrogen budget, showing a large sensitivity of NOx and ozone concentrations to nighttime processes.

Degradation of Organic UV filters in Chlorinated Seawater Swimming Pools: Transformation Pathways and Bromoform Formation.

PubMed

Manasfi, Tarek; Coulomb, Bruno; Ravier, Sylvain; Boudenne, Jean-Luc

2017-12-05

Organic ultraviolet (UV) filters are used in sunscreens and other personal-care products to protect against harmful effects of exposure to UV solar radiation. Little is known about the fate of UV filters in seawater swimming pools disinfected with chlorine. The present study investigated the occurrence and fate of five commonly used organic UV filters, namely dioxybenzone, oxybenzone, avobenzone, 2-ethylhexyl-4-methoxycinnamate, and octocrylene, in chlorinated seawater swimming pools. Pool samples were collected to monitor the variation of UV filter concentrations during pool opening hours. Furthermore, laboratory-controlled chlorination experiments were conducted in seawater spiked with UV filters to investigate the reactivity of UV filters. Extracts of chlorination reaction samples were analyzed using high-resolution mass spectrometry and electron-capture detection to identify the potentially formed byproducts. In the collected pool samples, all the UV filters except dioxybenzone were detected. Chlorination reactions showed that only octocrylene was stable in chlorinated seawater. The four reactive UV filters generated brominated transformation products and disinfection byproducts. This formation of brominated products resulted from reactions between the reactive UV filters and bromine, which is formed rapidly when chlorine is added to seawater. Based on the identified byproducts, the transformation pathways of the reactive UV filters were proposed for the first time. Bromoform was generated by all the reactive UV filters at different yields. Bromal hydrate was also detected as one of the byproducts generated by oxybenzone and dioxybenzone.

Reactive transport in a partially molten system with binary solid solution

NASA Astrophysics Data System (ADS)

Jordan, J.; Hesse, M. A.

2017-12-01

Melt extraction from the Earth's mantle through high-porosity channels is required to explain the composition of the oceanic crust. Feedbacks from reactive melt transport are thought to localize melt into a network of high-porosity channels. Recent studies invoke lithological heterogeneities in the Earth's mantle to seed the localization of partial melts. Therefore, it is necessary to understand the reaction fronts that form as melt flows across the lithological interface of a heterogeneity and the background mantle. Simplified melting models of such systems aide in the interpretation and formulation of larger scale mantle models. Motivated by the aforementioned facts, we present a chromatographic analysis of reactive melt transport across lithological boundaries, using theory for hyperbolic conservation laws. This is an extension of well-known linear trace element chromatography to the coupling of major elements and energy transport. Our analysis allows the prediction of the feedbacks that arise in reactive melt transport due to melting, freezing, dissolution and precipitation for frontal reactions. This study considers the simplified case of a rigid, partially molten porous medium with binary solid solution. As melt traverses a lithological contact-modeled as a Riemann problem-a rich set of features arise, including a reacted zone between an advancing reaction front and partial chemical preservation of the initial contact. Reactive instabilities observed in this study originate at the lithological interface rather than along a chemical gradient as in most studies of mantle dynamics. We present a regime diagram that predicts where reaction fronts become unstable, thereby allowing melt localization into high-porosity channels through reactive instabilities. After constructing the regime diagram, we test the one-dimensional hyperbolic theory against two-dimensional numerical experiments. The one-dimensional hyperbolic theory is sufficient for predicting the qualitative behavior of reactive melt transport simulations conducted in two-dimensions. The theoretical framework presented can be extended to more complex and realistic phase behavior, and is therefore a useful tool for understanding nonlinear feedbacks in reactive melt transport problems relevant to mantle dynamics.

New rapid-curing, stable polyimide polymers with high-temperature strength and thermal stability

NASA Technical Reports Server (NTRS)

Burns, E. A.; Jones, J. F.; Kendrick, W. R.; Lubowitz, H. R.; Thorpe, R. S.; Wilson, E. R.

1969-01-01

Additive-type polymerization reaction forms thermally stable polyimide polymers, thereby eliminating the volatile matter attendant with the condensation reaction. It is based on the utilization of reactive alicyclic rings positioned on the ends of polyimide prepolymers having relatively low molecular weights.

Plyometrics: A Legitimate Form of Power Training?

ERIC Educational Resources Information Center

Duda, Marty

1988-01-01

Plyometric exercises or drills combine speed and strength to produce an explosive-reactive movement or increased power. Some world-class athletes have used plyometric-training in sports such as high-jumping, hurdles, football, baseball, and hockey. The method is still considered experimental. Sample exercises are described. (JL)

Serological cross-reactivity among Sporothrix schenckii, Ceratocystis, Europhium, and Graphium species.

PubMed Central

Ishizaki, H; Wheat, R W; Kiel, D P; Conant, N F

1978-01-01

Ethanol-precipitable culture filtrate antigens of 100 strains of 75 species of the Sporothrix-Ceratocystis-Europhium-Graphium complex and 1 species of Botrytis were examined for neutral sugar components and for serological cross-reactivity with S. schenckii rabbit antiserum and human sporotrichosis sera by capillary precipitin and double immunodiffusion assay. Results revealed that cross-reactive species (60 of 77, ca. 80%) produced exoconidial forms and rhamnose- and mannose-containing polysaccharides and included Ceratocystis, the three known Europhium, and several Graphium-form species. Endoconidial-form Ceratocystis species did not cross-react. Images PMID:99369

Taming the Reactivity of Glycosyl Iodides To Achieve Stereoselective Glycosidation.

PubMed

Gervay-Hague, Jacquelyn

2016-01-19

Although glycosyl iodides have been known for more than 100 years, it was not until the 21st century that their full potential began to be harnessed for complex glycoconjugate synthesis. Mechanistic studies in the late 1990s probed glycosyl iodide formation by NMR spectroscopy and revealed important reactivity features embedded in protecting-group stereoelectronics. Differentially protected sugars having an anomeric acetate were reacted with trimethylsilyl iodide (TMSI) to generate the glycosyl iodides. In the absence of C-2 participation, generation of the glycosyl iodide proceeded by inversion of the starting anomeric acetate stereochemistry. Once formed, the glycosyl iodide readily underwent in situ anomerization, and in the presence of excess iodide, equilibrium concentrations of α- and β-iodides were established. Reactivity profiles depended upon the identity of the sugar and the protecting groups adorning it. Consistent with the modern idea of disarmed versus armed sugars, ester protecting groups diminished the reactivity of glycosyl iodides and ether protecting groups enhanced the reactivity. Thus, acetylated sugars were slower to form the iodide and anomerize than their benzylated analogues, and these disarmed glycosyl iodides could be isolated and purified, whereas armed ether-protected iodides could only be generated and reacted in situ. All other things being equal, the β-iodide was orders of magnitude more reactive than the thermodynamically more stable α-iodide, consistent with the idea of in situ anomerization introduced by Lemieux in the mid-20th century. Glycosyl iodides are far more reactive than the corresponding bromides, and with the increased reactivity comes increased stereocontrol, particularly when forming α-linked linear and branched oligosaccharides. Reactions with per-O-silylated glycosyl iodides are especially useful for the synthesis of α-linked glycoconjugates. Silyl ether protecting groups make the glycosyl iodide so reactive that even highly functionalized aglycon acceptors add. Following the coupling event, the TMS ethers are readily removed by methanolysis, and since all of the byproducts are volatile, multiple reactions can be performed in a single reaction vessel without isolation of intermediates. In this fashion, per-O-TMS monosaccharides can be converted to biologically relevant α-linked glycolipids in one pot. The stereochemical outcome of these reactions can also be switched to β-glycoside formation by addition of silver to chelate the iodide, thus favoring SN2 displacement of the α-iodide. While iodides derived from benzyl and silyl ether-protected oligosaccharides are susceptible to interglycosidic bond cleavage when treated with TMSI, the introduction of a single acetate protecting group prevents this unwanted side reaction. Partial acetylation of armed glycosyl iodides also attenuates HI elimination side reactions. Conversely, fully acetylated glycosyl iodides are deactivated and require metal catalysis in order for glycosidation to occur. Recent findings indicate that I2 activation of per-O-acetylated mono-, di-, and trisaccharides promotes glycosidation of cyclic ethers to give β-linked iodoalkyl glycoconjugates in one step. Products of these reactions have been converted into multivalent carbohydrate displays. With these synthetic pathways elucidated, chemical reactivity can be exquisitely controlled by the judicious selection of protecting groups to achieve high stereocontrol in step-economical processes.

Cinematographic investigations of the explosively driven dispersion and ignition of solid particles

NASA Astrophysics Data System (ADS)

Grégoire, Y.; Sturtzer, M.-O.; Khasainov, B. A.; Veyssière, B.

2014-07-01

We present results of an experimental study of blast wave propagation and particle dispersion induced by a free-field detonation of spherical charges made of a 125 g C-4 explosive surrounded by inert or reactive particles. Visualization of the flow was performed with a high-frame-rate video camera. Background oriented Schlieren (BOS) methods were adapted to process the images that allowed the detection of the shock waves. BOS analysis also revealed that particles form agglomerates, which may generate precursor perturbations on the recorded pressure signals. While inert glass particles notably delay the shock, the combustion of aluminium particles can accelerate it, especially if they are small atomized or flaked particles. When a mixture of inert glass particles with reactive particles is dispersed, the agglomerates are formed by coalescence of both materials.

Nitrogen-rich heterocycles as reactivity retardants in shocked insensitive explosives.

PubMed

Manaa, M Riad; Reed, Evan J; Fried, Laurence E; Goldman, Nir

2009-04-22

We report the first quantum-based multiscale simulations to study the reactivity of shocked perfect crystals of the insensitive energetic material triaminotrinitrobenzene (TATB). Tracking chemical transformations of TATB experiencing overdriven shock speeds of 9 km/s for up to 0.43 ns and 10 km/s for up to 0.2 ns reveal high concentrations of nitrogen-rich heterocyclic clusters. Further reactivity of TATB toward the final decomposition products of fluid N(2) and solid carbon is inhibited due to the formation of these heterocycles. Our results thus suggest a new mechanism for carbon-rich explosive materials that precedes the slow diffusion-limited process of forming the bulk solid from carbon clusters and provide fundamental insight at the atomistic level into the long reaction zone of shocked TATB.

Selective photocatalytic transformations on microporous titanosilicate ETS-10 driven by size and polarity of molecules.

PubMed

Shiraishi, Yasuhiro; Tsukamoto, Daijiro; Hirai, Takayuki

2008-11-04

Photocatalytic activity of microporous titanosilicate ETS-10 has been studied in water. The photoactivated ETS-10 shows catalytic activity driven by size and polarity of substrates. ETS-10 efficiently catalyzes a conversion of substrates with a size larger than the pore diameter of ETS-10. In contrast, the reactivity of small substrates depends strongly on substrate polarity; less polar substrates show higher reactivity on ETS-10. Electron spin resonance analysis reveals that large substrates or less polar substrates scarcely diffuse inside the highly polarized micropores of ETS-10 and, hence, react efficiently with hydroxyl radicals (*OH) formed on titanol (Ti-OH) groups exposed on the external surface of ETS-10. In contrast, small polar substrates diffuse easily inside the micropores of ETS-10 and scarcely react with *OH, resulting in low reactivity. The photocatalytic activity of ETS-10 is successfully applicable to selective transformations of large reactants or less polar reactants to small polar products, enabling highly selective dehalogenation and hydroxylation of aromatics.

Analysis and Chemistry of Novel Protein Oxidation Markers in Vivo.

PubMed

Henning, Christian; Liehr, Kristin; Girndt, Matthias; Ulrich, Christof; Glomb, Marcus A

2018-05-09

Proteins continually undergo spontaneous oxidation reactions, which lead to changes in structure and function. The quantitative assessment of protein oxidation adducts provides information on the level of exposure to reactive precursor compounds with a high oxidizing potential and reactive oxygen species (ROS). In the present work, we introduce N 6 -(2-hydroxyethyl)lysine as a novel marker based on the ratio of glycolaldehyde and its oxidized form glyoxal. The high analytical potential was proven with a first set of patients undergoing hemodialysis versus healthy controls, in comparison with well-established parameters for oxidative stress. In vitro experiments with N 1 - t-BOC-lysine and N 1 - t-BOC-arginine enlightened the mechanistic relationship of glycolaldehyde and glyoxal. Oxidation was strongly dependent on the catalytic action of the ε-amino moiety of lysine. Investigations on the formation of N 6 -carboxymethyl lysine revealed glycolaldehyde-imine as the more reactive precursor, even though an additional oxidative step is required. As a result, a novel and very effective alternative mechanism was unraveled.

Method of extruding and packaging a thin sample of reactive material including forming the extrusion die

DOEpatents

Lewandowski, Edward F.; Peterson, Leroy L.

1985-01-01

This invention teaches a method of cutting a narrow slot in an extrusion die with an electrical discharge machine by first drilling spaced holes at the ends of where the slot will be, whereby the oil can flow through the holes and slot to flush the material eroded away as the slot is being cut. The invention further teaches a method of extruding a very thin ribbon of solid highly reactive material such as lithium or sodium through the die in an inert atmosphere of nitrogen, argon or the like as in a glovebox. The invention further teaches a method of stamping out sample discs from the ribbon and of packaging each disc by sandwiching it between two aluminum sheets and cold welding the sheets together along an annular seam beyond the outer periphery of the disc. This provides a sample of high purity reactive material that can have a long shelf life.

Method of extruding and packaging a thin sample of reactive material, including forming the extrusion die

DOEpatents

Lewandowski, E.F.; Peterson, L.L.

1981-11-30

This invention teaches a method of cutting a narrow slot in an extrusion die with an electrical discharge machine by first drilling spaced holes at the ends of where the slot will be, whereby the oil can flow through the holes and slot to flush the material eroded away as the slot is being cut. The invention further teaches a method of extruding a very thin ribbon of solid highly reactive material such as lithium or sodium through the die in an inert atmosphere of nitrogen, argon, or the like as in a glovebox. The invention further teaches a method of stamping out sample discs from the ribbon and of packaging each disc by sandwiching it between two aluminum sheets and cold welding the sheets together along an annular seam beyond the outer periphery of the disc. This provides a sample of high purity reactive material that can have a long shelf life.

[Hyper-reactive malarial splenomegaly].

PubMed

Maazoun, F; Deschamps, O; Barros-Kogel, E; Ngwem, E; Fauchet, N; Buffet, P; Froissart, A

2015-11-01

Hyper-reactive malarial splenomegaly is a rare and severe form of chronic malaria. This condition is a common cause of splenomegaly in endemic areas. The pathophysiology of hyper-reactive malarial splenomegaly involves an intense immune reaction (predominantly B cell-driven) to repeated/chronic infections with Plasmodium sp. The diagnosis may be difficult, due to a poorly specific clinical presentation (splenomegaly, fatigue, cytopenias), a long delay between residence in a malaria-endemic area and onset of symptoms, and a frequent absence of parasites on conventional thin and thick blood smears. A strongly contributive laboratory parameter is the presence of high levels of total immunoglobulin M. When the diagnostic of hyper-reactive malarial splenomegaly is considered, search for anti-Plasmodium antibodies and Plasmodium nucleic acids (genus and species) by PCR is useful. Diagnosis of hyper-reactive malarial splenomegaly relies on the simultaneous presence of epidemiological, clinical, biological and follow-up findings. Regression of both splenomegaly and hypersplenism following antimalarial therapy allows the differential diagnosis with splenic lymphoma, a common complication of hyper-reactive malarial splenomegaly. Although rare in Western countries, hyper-reactive malarial splenomegaly deserves increased medical awareness to reduce the incidence of incorrect diagnosis, to prevent progression to splenic lymphoma and to avoid splenectomy. Copyright © 2015 Société nationale française de médecine interne (SNFMI). Published by Elsevier SAS. All rights reserved.

High temperature ablative foam

NASA Technical Reports Server (NTRS)

Liu, Matthew T. (Inventor)

1992-01-01

An ablative foam composition is formed of approximately 150 to 250 parts by weight polymeric isocyanate having an isocyanate functionality of 2.6 to 3.2; approximately 15 to 30 parts by weight reactive flame retardant having a hydroxyl number range from 200-260; approximately 10 to 40 parts by weight non-reactive flame retardant; approximately 10 to 40 parts by weight nonhydrolyzable silicone copolymer having a hydroxyl number range from 75-205; and approximately 3 to 16 parts by weight amine initiated polyether resin having an isocyanate functionality greater than or equal to 3.0 and a hydroxyl number range from 400-800.

The Reactive-Causal Architecture: Introducing an Emotion Model along with Theories of Needs

NASA Astrophysics Data System (ADS)

Aydin, Ali Orhan; Orgun, Mehmet Ali

In the entertainment application area, one of the major aims is to develop believable agents. To achieve this aim, agents should be highly autonomous, situated, flexible, and display affect. The Reactive-Causal Architecture (ReCau) is proposed to simulate these core attributes. In its current form, ReCau cannot explain the effects of emotions on intelligent behaviour. This study aims is to further improve the emotion model of ReCau to explain the effects of emotions on intelligent behaviour. This improvement allows ReCau to be emotional to support the development of believable agents.

[Mechanisms of immune deposit formation in glomerulonephritis].

PubMed

Bussolati, B; Camussi, G

1996-03-01

Recent experimental studies allowed the identification of several mechanisms of immune deposit formation, which are able to reproduce the morphological and clinical pattern of human glomerulonephritis. Moreover, it was shown that most of the lesions considered, in the past, as due to circulating immune complexes (IC), are instead caused by the "in situ" formation of IC. As a result of these studies, the following schematic classification was proposed: 1) immune deposits formed by glomerular localization of IC primarily formed in the circulation; 2) immune deposits formed "in situ" by reaction of circulating antibodies with fixed structural antigens; 3) immune deposits formed "in situ" by antibodies reactive with movable structural antigens; 4) immune deposits formed "in situ" by antibodies reactive with sequestered antigens leaking out of tissues; 5) IC formed "in situ" by antibodies reactive with exogenous or non-glomerular endogenous antigens planted in the glomeruli; 6) ANCA-associated glomerular disease.

Current status of free radicals and electronically excited metastable species as high energy propellants

NASA Technical Reports Server (NTRS)

Rosen, G.

1973-01-01

A survey is presented of free radicals and electronically excited metastable species as high energy propellants for rocket engines. Nascent or atomic forms of diatomic gases are considered free radicals as well as the highly reactive diatomic triatomic molecules that posess unpaired electrons. Manufacturing and storage problems are described, and a review of current experimental work related to the manufacture of atomic hydrogen propellants is presented.

Preparation of a highly concentrated, completely monomeric, active sarcoplasmic reticulum Ca2+-ATPase.

PubMed

Lüdi, H; Hasselbach, W

1985-11-21

Sarcoplasmic reticulum vesicles from fast skeletal muscle were partially delipidated with sodium cholate at high ionic strength and sedimented in a discontinuous sucrose gradient. Phospholipid content was reduced from 0.777 mumol/mg protein to 0.242 mumol/mg protein. As judged from gel electrophoresis and high pressure liquid gel chromatography, accessory proteins were removed during centrifugation and the Ca2+-ATPase was obtained in an almost pure form. Addition of myristoylglycerophosphocholine (1 mg/mg protein) reactivates ATPase and dinitrophenylphosphatase activity to the same degree obtained with native vesicles. Using the analytical ultracentrifuge it could be demonstrated that the reactivated Ca2+-ATPase was present exclusively in a monomeric state. These results were obtained at high and low ionic strength and up to a protein concentration of 10 mg/ml. Therefore this preparation should be very useful to investigate differences between oligomeric and monomeric Ca2+-ATPase.

High rate discharge studies of Li/SO2 cells

NASA Astrophysics Data System (ADS)

Dallek, S.; Bis, R. F.; Bowers, F. M.

Experimental D-size spirally-wound 3V 10 A-hr cells were used in the reported study. The cells were instrumented with four iron-constantan thermocouples. It was found that during a discharge of a thermally insulated cell, the greatest amount of heat builds up in the center of the cell. The heat build-up appears to be purely resistive in nature. Concerning the safe use of these cells, it has been demonstrated that at very high rates of discharge, e.g., 10 A, cells may vent violently and cause a fire. At this high rate of discharge, the internal cell temperature exceeded the melting point of the lithium anode which is in the form of an unsupported strip. Thus, contact of the highly reactive molten lithium with other reactive species in the cell is possible under these conditions and could result in a very exothermic chemical reaction.

Reactivation of Mucosal and Cutaneous Leishmaniasis in a Renal Transplanted Patient

PubMed Central

Tuon, Felipe F.; Bombonatto, Giovana Marina; Battaglin, Eveline Roesler; Sakumoto, Marcus Henrique; Amato, Valdir Sabbaga; de Camargo, Raphael Abegão; Nicodemo, Antônio Carlos

2014-01-01

Mucosal leishmaniasis (ML) is a chronic form of tegumentary leishmaniasis, which causes destructive lesions of nasal, pharyngeal, and laryngeal mucosa. We describe a case of leishmaniasis reactivation with simultaneous cutaneous and mucosal forms in a renal transplanted patient with no history of prior leishmaniasis. Reactivation after renal transplantation was not reported in Brazil. A 67-year-old woman receiving prednisone 20 mg/day, tacrolimus 1 mg/day, and mycophenolic acid 360 mg/day presented with nose edema with erythema and cutaneous lesions. Amastigotes were identified on biopsies and the polymerase chain reaction confirmed Leishmania (Viannia) braziliensis. The patient was treated with liposomal amphotericin B but died 3 weeks after as a result of bacterial septic shock. In conclusion, tegumentary leishmaniasis can reactivate with simultaneous cutaneous and mucosal forms in a renal transplanted patient during the immunosuppressant therapy. PMID:24732458

Parallel computation safety analysis irradiation targets fission product molybdenum in neutronic aspect using the successive over-relaxation algorithm

NASA Astrophysics Data System (ADS)

Susmikanti, Mike; Dewayatna, Winter; Sulistyo, Yos

2014-09-01

One of the research activities in support of commercial radioisotope production program is a safety research on target FPM (Fission Product Molybdenum) irradiation. FPM targets form a tube made of stainless steel which contains nuclear-grade high-enrichment uranium. The FPM irradiation tube is intended to obtain fission products. Fission materials such as Mo99 used widely the form of kits in the medical world. The neutronics problem is solved using first-order perturbation theory derived from the diffusion equation for four groups. In contrast, Mo isotopes have longer half-lives, about 3 days (66 hours), so the delivery of radioisotopes to consumer centers and storage is possible though still limited. The production of this isotope potentially gives significant economic value. The criticality and flux in multigroup diffusion model was calculated for various irradiation positions and uranium contents. This model involves complex computation, with large and sparse matrix system. Several parallel algorithms have been developed for the sparse and large matrix solution. In this paper, a successive over-relaxation (SOR) algorithm was implemented for the calculation of reactivity coefficients which can be done in parallel. Previous works performed reactivity calculations serially with Gauss-Seidel iteratives. The parallel method can be used to solve multigroup diffusion equation system and calculate the criticality and reactivity coefficients. In this research a computer code was developed to exploit parallel processing to perform reactivity calculations which were to be used in safety analysis. The parallel processing in the multicore computer system allows the calculation to be performed more quickly. This code was applied for the safety limits calculation of irradiated FPM targets containing highly enriched uranium. The results of calculations neutron show that for uranium contents of 1.7676 g and 6.1866 g (× 106 cm-1) in a tube, their delta reactivities are the still within safety limits; however, for 7.9542 g and 8.838 g (× 106 cm-1) the limits were exceeded.

Total OH reactivity measurements for the OH-initiated oxidation of aromatic hydrocarbons in the presence of NOx

NASA Astrophysics Data System (ADS)

Sato, Kei; Nakashima, Yoshihiro; Morino, Yu; Imamura, Takashi; Kurokawa, Jun-ichi; Kajii, Yoshizumi

2017-12-01

The total OH reactivity of the secondary products formed from the OH-initiated oxidation of toluene, p-xylene, and 1,3,5-trimethylbenzene was directly measured in the presence of NOx using a laboratory environmental chamber in order to investigate unidentified reactive species in urban air. The total OH reactivity was also calculated from the concentrations of the reactants and products, which were monitored by Fourier-transform infrared spectroscopy. The difference between the measured and calculated OH reactivity, the so-called missing OH reactivity, comprised 58-81% of the total OH reactivity of the secondary products. These results suggest that the secondary products formed from the oxidation of aromatic hydrocarbons may be important candidates in accounting for the missing OH reactivity in the analyses of urban environments. The Master Chemical Mechanism (MCM) calculations were performed to predict the temporal variation in the total OH reactivity for the oxidation of aromatic hydrocarbons. The MCM calculations successfully reproduced the observed total OH reactivity when the particle and semi-volatile product concentrations were negligibly low. The MCM calculations were used to identify the missing secondary products. The results suggest that important components of the missing OH reactivity are unsaturated multifunctional products such as unsaturated dicarbonyls, unsaturated epoxydicarbonyls, and furanones.

Photo Protection of Haematococcus pluvialis Algae by Astaxanthin: Unique Properties of Astaxanthin Deduced by EPR, Optical and Electrochemical Studies

PubMed Central

Focsan, A. Ligia; Polyakov, Nikolay E.; Kispert, Lowell D.

2017-01-01

The antioxidant astaxanthin is known to accumulate in Haematococcus pluvialis algae under unfavorable environmental conditions for normal cell growth. The accumulated astaxanthin functions as a protective agent against oxidative stress damage, and tolerance to excessive reactive oxygen species (ROS) is greater in astaxanthin-rich cells. The detailed mechanisms of protection have remained elusive, however, our Electron Paramagnetic Resonance (EPR), optical and electrochemical studies on carotenoids suggest that astaxanthin’s efficiency as a protective agent could be related to its ability to form chelate complexes with metals and to be esterified, its inability to aggregate in the ester form, its high oxidation potential and the ability to form proton loss neutral radicals under high illumination in the presence of metal ions. The neutral radical species formed by deprotonation of the radical cations can be very effective quenchers of the excited states of chlorophyll under high irradiation. PMID:29065482

Instrumental and Reactive Functions and Overt and Relational Forms of Aggression: Developmental Trajectories and Prospective Associations during Middle School

ERIC Educational Resources Information Center

Ojanen, Tiina; Kiefer, Sarah

2013-01-01

This study examined the development of adolescent self-reported instrumental-overt, instrumental-relational, reactive-overt, and reactive-relational aggression during middle school ("N" = 384; 12-14 years; 53% boys). Growth modeling indicated average increases in instrumental-relational aggression, and decreases in reactive-overt and…

AB INITIO Simulations of Desorption and Reactivity of Glycine at a Water-Pyrite Interface at ``Iron-Sulfur World'' Prebiotic Conditions

NASA Astrophysics Data System (ADS)

Pollet, Rodolphe; Boehme, Christian; Marx, Dominik

2006-08-01

Glycine at the interface of a pyrite surface (001) FeS2, and bulk water at high pressure and temperature conditions relevant to the “iron-sulfur world” scenario of the origin of life is investigated by theoretical means. Car-Parrinello molecular dynamics is used in order to study the desorption process of the zwitterionic form of this amino acid using two different adsorption modes, where either only one or both oxygens of the carboxylate group are anchored to surface iron atoms. It is found that the formation of stabilizing hydrogen bonds plays a key role in the detachment process, leading to longer retention times for the bidentate adsorption mode. In addition, the chemical reactivity of this heterogeneous system is probed by calculating the Fukui functions as site-specific reactivity indices. The most prominent targets for both nucleophilic and electrophilic reactions to occur are surface atoms, whereas the reactivity of glycine is only slightly affected upon anchoring.

Parallel computation of multigroup reactivity coefficient using iterative method

NASA Astrophysics Data System (ADS)

Susmikanti, Mike; Dewayatna, Winter

2013-09-01

One of the research activities to support the commercial radioisotope production program is a safety research target irradiation FPM (Fission Product Molybdenum). FPM targets form a tube made of stainless steel in which the nuclear degrees of superimposed high-enriched uranium. FPM irradiation tube is intended to obtain fission. The fission material widely used in the form of kits in the world of nuclear medicine. Irradiation FPM tube reactor core would interfere with performance. One of the disorders comes from changes in flux or reactivity. It is necessary to study a method for calculating safety terrace ongoing configuration changes during the life of the reactor, making the code faster became an absolute necessity. Neutron safety margin for the research reactor can be reused without modification to the calculation of the reactivity of the reactor, so that is an advantage of using perturbation method. The criticality and flux in multigroup diffusion model was calculate at various irradiation positions in some uranium content. This model has a complex computation. Several parallel algorithms with iterative method have been developed for the sparse and big matrix solution. The Black-Red Gauss Seidel Iteration and the power iteration parallel method can be used to solve multigroup diffusion equation system and calculated the criticality and reactivity coeficient. This research was developed code for reactivity calculation which used one of safety analysis with parallel processing. It can be done more quickly and efficiently by utilizing the parallel processing in the multicore computer. This code was applied for the safety limits calculation of irradiated targets FPM with increment Uranium.

Pumpable/injectable phosphate-bonded ceramics

DOEpatents

Singh, Dileep; Wagh, Arun S.; Perry, Lamar; Jeong, Seung-Young

2001-01-01

A pumpable ceramic composition is provided comprising an inorganic oxide, potassium phosphate, and an oxide coating material. Also provided is a method for preparing pumpable ceramic-based waste forms comprising selecting inorganic oxides based on solubility, surface area and morphology criteria; mixing the selected oxides with phosphate solution and waste to form a first mixture; combining an additive to the first mixture to create a second mixture; adding water to the second mixture to create a reactive mixture; homogenizing the reactive mixture; and allowing the reactive mixture to cure.

Sensitivity-Based VOC Reactivity Calculation

EPA Science Inventory

Volatile Organic Compound (VOC) reactivity scales are used to compare the ozone-forming potentials of various compounds. The comparison allows for substitution of compounds to lessen formation of ozone from paints, solvents, and other products. Current reactivity scales for VOC c...

Cover crop, N-rate impacts on corn yield and soil N

USDA-ARS?s Scientific Manuscript database

Nitrogen fertilizer is a significant input expense for producers, as conversion of stable nitrogen into plant available reactive forms such as NH4 or NO3 is energy intensive and costly. These reactive forms of nitrogen (Nr), critical for crop production, can escape from agricultural systems into sur...

Epitaxial CoSi2 on MOS devices

DOEpatents

Lim, Chong Wee; Shin, Chan Soo; Petrov, Ivan Georgiev; Greene, Joseph E.

2005-01-25

An Si.sub.x N.sub.y or SiO.sub.x N.sub.y liner is formed on a MOS device. Cobalt is then deposited and reacts to form an epitaxial CoSi.sub.2 layer underneath the liner. The CoSi.sub.2 layer may be formed through a solid phase epitaxy or reactive deposition epitaxy salicide process. In addition to high quality epitaxial CoSi.sub.2 layers, the liner formed during the invention can protect device portions during etching processes used to form device contacts. The liner can act as an etch stop layer to prevent excessive removal of the shallow trench isolation, and protect against excessive loss of the CoSi.sub.2 layer.

LC-MS-based characterization of the peptide reactivity of chemicals to improve the in vitro prediction of the skin sensitization potential.

PubMed

Natsch, Andreas; Gfeller, Hans

2008-12-01

A key step in the skin sensitization process is the formation of a covalent adduct between skin sensitizers and endogenous proteins and/or peptides in the skin. Based on this mechanistic understanding, there is a renewed interest in in vitro assays to determine the reactivity of chemicals toward peptides in order to predict their sensitization potential. A standardized peptide reactivity assay yielded a promising predictivity. This published assay is based on high-performance liquid chromatography with ultraviolet detection to quantify peptide depletion after incubation with test chemicals. We had observed that peptide depletion may be due to either adduct formation or peptide oxidation. Here we report a modified assay based on both liquid chromatography-mass spectrometry (LC-MS) analysis and detection of free thiol groups. This approach allows simultaneous determination of (1) peptide depletion, (2) peptide oxidation (dimerization), (3) adduct formation, and (4) thiol reactivity and thus generates a more detailed characterization of the reactivity of a molecule. Highly reactive molecules are further discriminated with a kinetic measure. The assay was validated on 80 chemicals. Peptide depletion could accurately be quantified both with LC-MS detection and depletion of thiol groups. The majority of the moderate/strong/extreme sensitizers formed detectable peptide adducts, but many sensitizers were also able to catalyze peptide oxidation. Whereas adduct formation was only observed for sensitizers, this oxidation reaction was also observed for two nonsensitizing fragrance aldehydes, indicating that peptide depletion might not always be regarded as sufficient evidence for rating a chemical as a sensitizer. Thus, this modified assay gives a more informed view of the peptide reactivity of chemicals to better predict their sensitization potential.

Kinetics of Thermal Denaturation and Aggregation of Bovine Serum Albumin

PubMed Central

Borzova, Vera A.; Markossian, Kira A.; Chebotareva, Natalia A.; Kleymenov, Sergey Yu.; Poliansky, Nikolay B.; Muranov, Konstantin O.; Stein-Margolina, Vita A.; Shubin, Vladimir V.; Markov, Denis I.; Kurganov, Boris I.

2016-01-01

Thermal aggregation of bovine serum albumin (BSA) has been studied using dynamic light scattering, asymmetric flow field-flow fractionation and analytical ultracentrifugation. The studies were carried out at fixed temperatures (60°C, 65°C, 70°C and 80°C) in 0.1 M phosphate buffer, pH 7.0, at BSA concentration of 1 mg/ml. Thermal denaturation of the protein was studied by differential scanning calorimetry. Analysis of the experimental data shows that at 65°C the stage of protein unfolding and individual stages of protein aggregation are markedly separated in time. This circumstance allowed us to propose the following mechanism of thermal aggregation of BSA. Protein unfolding results in the formation of two forms of the non-native protein with different propensity to aggregation. One of the forms (highly reactive unfolded form, Uhr) is characterized by a high rate of aggregation. Aggregation of Uhr leads to the formation of primary aggregates with the hydrodynamic radius (Rh,1) of 10.3 nm. The second form (low reactive unfolded form, Ulr) participates in the aggregation process by its attachment to the primary aggregates produced by the Uhr form and possesses ability for self-aggregation with formation of stable small-sized aggregates (Ast). At complete exhaustion of Ulr, secondary aggregates with the hydrodynamic radius (Rh,2) of 12.8 nm are formed. At 60°C the rates of unfolding and aggregation are commensurate, at 70°C the rates of formation of the primary and secondary aggregates are commensurate, at 80°C the registration of the initial stages of aggregation is complicated by formation of large-sized aggregates. PMID:27101281

Recent mouse models and vaccine candidates for preventing chronic/latent tuberculosis infection and its reactivation.

PubMed

Pedroza-Roldán, César; Flores-Valdez, Mario Alberto

2017-08-31

Tuberculosis (TB) remains a major challenge in public health worldwide. Until today, the only widely used and approved vaccine is the Mycobacterium bovis bacille Calmette-Guerin (BCG). This vaccine provides a highly variable level of protection against the active, pulmonary form of tuberculosis, and practically none against the latent form of TB infection. This disparity in protection has been extensively studied, and for this reason, several groups have focused their research on the quest for attenuated vaccines based on M. tuberculosis or on the identification of latency-associated antigens that can be incorporated into modified BCG, or that can be used as adjuvanted subunit vaccines. In order to seek new potential antigens relevant for infection, some researchers have performed experiments with highly sensitive techniques such as transcriptomic and proteomic analyses using sputum samples from humans or by using mouse models resembling several aspects of TB. In this review, we focus on reports of new mouse models or mycobacterial antigens recently tested for developing vaccine candidates against chronic/latent tuberculosis and its reactivation.

Low to moderate temperature nanolaminate heater

DOEpatents

Eckels, J Del [Livermore, CA; Nunes, Peter J [Danville, CA; Simpson, Randall L [Livermore, CA; Hau-Riege, Stefan [Fremont, CA; Walton, Chris [Oakland, CA; Carter, J Chance [Livermore, CA; Reynolds, John G [San Ramon, CA

2011-01-11

A low to moderate temperature heat source comprising a high temperature energy source modified to output low to moderate temperatures wherein the high temperature energy source modified to output low to moderate temperatures is positioned between two thin pieces to form a close contact sheath. In one embodiment the high temperature energy source modified to output low to moderate temperatures is a nanolaminate multilayer foil of reactive materials that produces a heating level of less than 200.degree. C.

Magnetic Iron Oxide Nanowires Formed by Reactive Dewetting.

PubMed

Bennett, Roger A; Etman, Haitham A; Hicks, Hannah; Richards, Leah; Wu, Chen; Castell, Martin R; Dhesi, Sarnjeet S; Maccherozzi, Francesco

2018-04-11

The growth and reactive dewetting of ultrathin films of iron oxides supported on Re(0001) surfaces have been imaged in situ in real time. Initial growth forms a nonmagnetic stable FeO (wüstite like) layer in a commensurate network upon which high aspect ratio nanowires of several microns in length but less than 40 nm in width can be fabricated. The nanowires are closely aligned with the substrate crystallography and imaging by X-ray magnetic circular dichroism shows that each contain a single magnetic domain. The driving force for dewetting appears to be the minimization of strain energy of the Fe 3 O 4 crystallites and follows the Tersoff and Tromp model in which strain is minimized at constant height by extending in one epitaxially matched direction. Such wires are promising in spintronic applications and we predict that the growth will also occur on other hexagonal substrates.

A Springloaded Metal-Ligand Mesocate Allows Access to Trapped Intermediates of Self-Assembly.

PubMed

Bogie, Paul M; Holloway, Lauren R; Lyon, Yana; Onishi, Nicole C; Beran, Gregory J O; Julian, Ryan R; Hooley, Richard J

2018-04-02

A strained, "springloaded" Fe 2 L 3 iminopyridine mesocate shows highly variable reactivity upon postassembly reaction with competitive diamines. The strained assembly is reactive toward transimination in minutes at ambient temperature and allows observation of kinetically trapped intermediates in the self-assembly pathway. When diamines are used that can only form less favored cage products upon full equilibration, trapped ML 3 fragments with pendant, "hanging" NH 2 groups are selectively formed instead. Slight variations in diamine structure have large effects on the product outcome: less rigid diamines convert the mesocate to more favored self-assembled cage complexes under mild conditions and allow observation of heterocomplex intermediates in the displacement pathway. The mesocate allows control of equilibrium processes and direction of product outcomes via small, iterative changes in added subcomponent structure and provides a method of accessing metal-ligand cage structures not normally observed in multicomponent Fe-iminopyridine self-assembly.

Gonadotropin-releasing hormone (Gn-RH) in striped mullet (Mugil cephalus), milkfish (Chanos chanos), and rainbow trout (Salmo gairdneri): comparison with salmon Gn-RH.

PubMed

Sherwood, N M; Harvey, B; Brownstein, M J; Eiden, L E

1984-08-01

Immunoreactive gonadotropin-releasing hormone (Gn-RH) was extracted from brains of striped mullet, milkfish, rainbow trout, and chum salmon with acetone/HCl and petroleum ether. High pressure liquid chromatography and cross-reactivity studies show mullet, milkfish, and trout brains to contain a peptide chromatographically and immunologically identical to synthetic salmon Gn-RH, while the mammalian form of Gn-RH is detectable in none of these fishes. Gn-RH is present in immature 7-month-old and 4-year-old milkfish. A second immunoreactive peptide is separable by HPLC in all the fish studied. This "early-eluting" form of Gn-RH is unlikely to be a precursor; its cross-reactivity with antisera R-42 and #185 suggests that any modification is in the C-terminal region. Several possible roles for this peptide are advanced.

Gonadotropin-releasing hormone (Gn-RH) in striped mullet (Mugil cephalus), milkfish (Chanos chanos), and rainbow trout (Salmo gairdneri): comparison with salmon Gn-RH

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

Sherwood, N.M.; Harvey, B.; Brownstein, M.J.

Immunoreactive gonadotropin-releasing hormone (Gn-RH) was extracted from brains of striped mullet, milkfish, rainbow trout, and chum salmon with acetone/HCl and petroleum ether. High pressure liquid chromatography and cross-reactivity studies show mullet, milkfish, and trout brains to contain a peptide chromatographically and immunologically identical to synthetic salmon Gn-RH, while the mammalian form of Gn-RH is detectable in none of these fishes. Gn-RH is present in immature 7-month-old and 4-year-old milkfish. A second immunoreactive peptide is separable by HPLC in all the fish studied. This early-eluting form of Gn-RH is unlikely to be a precursor; its cross-reactivity with antisera R-42 and number185more » suggests that any modification is in the C-terminal region. Several possible roles for this peptide are advanced.« less

A measurement of total reactive nitrogen, NOy, together with NO₂, NO, and O₃ via cavity ring-down spectroscopy.

PubMed

Wild, Robert J; Edwards, Peter M; Dubé, William P; Baumann, Karsten; Edgerton, Eric S; Quinn, Patricia K; Roberts, James M; Rollins, Andrew W; Veres, Patrick R; Warneke, Carsten; Williams, Eric J; Yuan, Bin; Brown, Steven S

2014-08-19

We present a sensitive, compact detector that measures total reactive nitrogen (NOy), as well as NO2, NO, and O3. In all channels, NO2 is directly detected by laser diode based cavity ring-down spectroscopy (CRDS) at 405 nm. Ambient O3 is converted to NO2 in excess NO for the O3 measurement channel. Likewise, ambient NO is converted to NO2 in excess O3. Ambient NOy is thermally dissociated at ∼700 °C to form NO2 or NO in a heated quartz inlet. Any NO present in ambient air or formed from thermal dissociation of other reactive nitrogen compounds is converted to NO2 in excess O3 after the thermal converter. We measured thermal dissociation profiles for six of the major NOy components and compared ambient measurements with other instruments during field campaigns in Utah and Alabama. Alabama measurements were made in a rural location with high biogenic emissions, and Utah measurements were made in the wintertime in unusual conditions that form high ozone levels from emissions related to oil and gas production. The NOy comparison in Alabama, to an accepted standard measurement method (a molybdenum catalytic converter/chemiluminescence instrument), agreed to within 12%, which we define as an upper limit to the accuracy of the NOy channel. The 1σ precision is <30 pptv at 1 s and <4 pptv at 1 min time resolution for all measurement channels. The accuracy is 3% for the NO2 and O3 channels and 5% for the NO channel. The precision and accuracy of this instrument make it a versatile alternative to standard chemiluminescence-based NOy instruments.

Method for producing highly conformal transparent conducting oxides

DOEpatents

Elam, Jeffrey W.; Mane, Anil U.

2016-07-26

A method for forming a transparent conducting oxide product layer. The method includes use of precursors, such as tetrakis-(dimethylamino) tin and trimethyl indium, and selected use of dopants, such as SnO and ZnO for obtaining desired optical, electrical and structural properties for a highly conformal layer coating on a substrate. Ozone was also input as a reactive gas which enabled rapid production of the desired product layer.

Reasoning and planning in dynamic domains: An experiment with a mobile robot

NASA Technical Reports Server (NTRS)

Georgeff, M. P.; Lansky, A. L.; Schoppers, M. J.

1987-01-01

Progress made toward having an autonomous mobile robot reason and plan complex tasks in real-world environments is described. To cope with the dynamic and uncertain nature of the world, researchers use a highly reactive system to which is attributed attitudes of belief, desire, and intention. Because these attitudes are explicitly represented, they can be manipulated and reasoned about, resulting in complex goal-directed and reflective behaviors. Unlike most planning systems, the plans or intentions formed by the system need only be partly elaborated before it decides to act. This allows the system to avoid overly strong expectations about the environment, overly constrained plans of action, and other forms of over-commitment common to previous planners. In addition, the system is continuously reactive and has the ability to change its goals and intentions as situations warrant. Thus, while the system architecture allows for reasoning about means and ends in much the same way as traditional planners, it also posseses the reactivity required for survival in complex real-world domains. The system was tested using SRI's autonomous robot (Flakey) in a scenario involving navigation and the performance of an emergency task in a space station scenario.

Novel Pathways of Nitroaromatic Metabolism: Hydroxylamine Formation, Reactivity and Potential for Ring Fission for Destruction of TNT-CU1214

DTIC Science & Technology

2005-08-15

phase was terminated when HPLC analysis showed that the initial TNT was in the form of DHA6NT and aminophenols , products that have been reported...terminated when HPLC analysis showed that the initial TNT was in the form of DHA6NT and aminophenols , products that have been reported previously (2...Department of Defense HPLC High Performance Liquid Chromatography IPTG Isopropyl-β-D-1-thiogalactopyranoside LB Luria-Bertani Broth NB Nitrobenzene

Reflective functioning, physiological reactivity, and overcontrol in mothers: Links with school-aged children's reflective functioning.

PubMed

Borelli, Jessica L; Hong, Kajung; Rasmussen, Hannah F; Smiley, Patricia A

2017-09-01

Theorists argue that parental reflective functioning (PRF) is activated in response to emotions, potentially supporting parenting sensitivity even when arousal is high. That is, when parents become emotionally reactive when interacting with their children, those who can use PRF to understand their children's mental states should be able to parent sensitively, which, in turn, should promote children's ability to understand their own mental states. We test this theory by examining whether, in the face of physiological reactivity, mothers' PRF inhibits one form of parenting insensitivity, overcontrol (OC), and whether this process in turn predicts children's RF. A diverse sample of school-age children (N = 106, Mage = 10.27 years) completed a standardized failure paradigm while their mothers were asked to passively observe. Following the stressor, mothers and children independently completed interviews regarding the task, which were later coded for RF with respect to children's mental states. Mothers provided saliva samples before and after the stressor, and after the interview, which were later assayed for cortisol reactivity; maternal behavior during the stressor task was coded for OC. Among mothers with low levels of RF, greater increases in cortisol were associated with more displays of OC, whereas among mothers with high PRF, greater cortisol reactivity was associated with fewer OC behaviors. For low PRF mothers, higher reactivity and OC predicted lower children's PRF for their own experiences. The findings provide initial evidence for a protective function of PRF, and may point toward the importance of promoting PRF in intervention programs to reduce parental OC. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

The role of exposure in posttraumatic stress in youths following the 1995 bombing.

PubMed

Pfefferbaum, B; Moore, V L; McDonald, N B; Maynard, B T; Gurwitch, R H; Nixon, S J

1999-04-01

This study investigated the relative impact of various forms of exposure to the 1995 Oklahoma City bombing in middle and high school students seven weeks after the incident. We assessed 3210 youths with an instrument that probed for physical, television, and emotional exposure to the bombing and subsequent posttraumatic stress symptomatology and television reactivity. The majority of youths were exposed through physical proximity--hearing and/or feeling the blast--and through television viewing. These types of exposure, as well as emotional exposure, constituted important variables in the development of posttraumatic stress symptoms and television reactivity. Youths with immediate family casualties were more symptomatic than those without.

Formation of Reactive Br Species by Freezing in Solutions of NaBr-Metal-Hydrogen Peroxide

NASA Astrophysics Data System (ADS)

Kinjo, M.; Arakaki, T.

2005-12-01

The role of reactive halogen species (e.g. BrOH) in the destruction of stratospheric ozone is well known and largely understood. In recent years, it became clear that reactive Br species can also play a significant role in tropospheric ozone destruction, but sources of reactive Br species in the troposphere are not well understood. When an aqueous solution is frozen, solutes in the solution are excluded from the ice phase and the solutes are concentrated in the solution phase. Freezing processes cause red-ox reactions in the solution. We tried to understand the effects of freezing processes of solutions on formation of reactive Br species. Hydrogen peroxide (HOOH) and metallic ions were added to a mixing solution of NaBr and allyl alcohol (AA). If reactive Br species are formed, they react with AA, and free Br ion concentration decreases in the solution. When HOOH and Fe(III) or Cu(II) were added to the NaBr and AA solution and frozen, free Br ion concentration decreased. It is possible that OH radical formation from reaction between HOOH and Fe(II) or Cu(I) was induced by freezing processes and the OH radical probably oxidized Br ion to reactive Br species. Study of the effects of pH showed that decrease of Br ion concentration was the highest at pH = 4.0. Freezing processes could be an important source of reactive Br species in high altitude clouds and Polar Regions.

Microphysical, microchemical and adhesive properties of lunar material. 3: Gas interaction with lunar material

NASA Technical Reports Server (NTRS)

Grossman, J. J.; Mukherjee, N. R.; Ryan, J. A.

1972-01-01

Knowledge of the reactivity of lunar material surfaces is important for understanding the effects of the lunar or space environment upon this material, particularly its nature, behavior and exposure history in comparison to terrestrial materials. Adsorptive properties are one of the important techniques for such studies. Gas adsorption measurements were made on an Apollo 12 ultrahigh vacuum-stored sample and Apollo 14 and 15 N2-stored samples. Surface area measurements were made on the latter two. Adsorbate gases used were N2, A, O2 and H2O. Krypton was used for the surface area determinations. Runs were made at room and liquid nitrogen temperature in volumetric and gravimetric systems. It was found that the adsorptive/desorptive behavior was in general significantly different from that of terrestrial materials of similar type and form. Specifically (1) the UHV-stored sample exhibited very high initial adsorption indicative of high surface reactivity, and (2) the N2-stored samples at room and liquid nitrogen temperatures showed that more gas was desorbed than introduced during adsorption, indicative of gas release from the samples. The high reactivity is a scribed cosmic ray track and solar wind damage.

Development of Highly Durable and Reactive Regenerable Magnesium-Based Sorbents for CO2 Separation in Coal Gasification Process

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

Javad Abbasian; Armin Hassanzadeh Khayyat; Rachid B. Slimane

The specific objective of this project was to develop physically durable and chemically regenerable MgO-based sorbents that can remove carbon dioxide from raw coal gas at operating condition prevailing in IGCC processes. A total of sixty two (62) different sorbents were prepared in this project. The sorbents were prepared either by various sol-gel techniques (22 formulations) or modification of dolomite (40 formulations). The sorbents were prepared in the form of pellets and in granular forms. The solgel based sorbents had very high physical strength, relatively high surface area, and very low average pore diameter. The magnesium content of the sorbentsmore » was estimated to be 4-6 % w/w. To improve the reactivity of the sorbents toward CO{sub 2}, The sorbents were impregnated with potassium salts. The potassium content of the sorbents was about 5%. The dolomite-based sorbents were prepared by calcination of dolomite at various temperature and calcination environment (CO{sub 2} partial pressure and moisture). Potassium carbonate was added to the half-calcined dolomite through wet impregnation method. The estimated potassium content of the impregnated sorbents was in the range of 1-6% w/w. In general, the modified dolomite sorbents have significantly higher magnesium content, larger pore diameter and lower surface area, resulting in significantly higher reactivity compared to the sol-gel sorbents. The reactivities of a number of sorbents toward CO{sub 2} were determined in a Thermogravimetric Analyzer (TGA) unit. The results indicated that at the low CO{sub 2} partial pressures (i.e., 1 atm), the reactivities of the sorbents toward CO{sub 2} are very low. At elevated pressures (i.e., CO{sub 2} partial pressure of 10 bar) the maximum conversion of MgO obtained with the sol-gel based sorbents was about 5%, which corresponds to a maximum CO{sub 2} absorption capacity of less than 1%. The overall capacity of modified dolomite sorbents were at least one order of magnitude higher than those of the sol-gel based sorbents. The results of the tests conducted with various dolomite-based sorbent indicate that the reactivity of the modified dolomite sorbent increases with increasing potassium concentration, while higher calcination temperature adversely affects the sorbent reactivity. Furthermore, the results indicate that as long as the absorption temperature is well below the equilibrium temperature, the reactivity of the sorbent improves with increasing temperature (350-425 C). As the temperature approaches the equilibrium temperature, because of the significant increase in the rate of reverse (i.e., regeneration) reaction, the rate of CO{sub 2} absorption decreases. The results of cyclic tests show that the reactivity of the sorbent gradually decreases in the cyclic process. To improve long-term durability (i.e., reactivity and capacity) of the sorbent, the sorbent was periodically re-impregnated with potassium additive and calcined. The results indicate that, in general, re-treatment improves the performance of the sorbent, and that, the extent of improvement gradually decreases in the cyclic process. The presence of steam significantly enhances the sorbent reactivity and significantly decreases the rate of decline in sorbent deactivation in the cyclic process.« less

Calculation of singlet oxygen formation from one photon absorbing photosensitizers used in PDT

NASA Astrophysics Data System (ADS)

Potasek, M.; Parilov, Evgueni; Beeson, K.

2013-03-01

Advances in biophotonic medicine require new information on photodynamic mechanisms. In photodynamic therapy (PDT), a photosensitizer (PS) is injected into the body and accumulates at higher concentrations in diseased tissue compared to normal tissue. The PS absorbs light from a light source and generates excited-state triplet states of the PS. The excited triplet states of the PS can then react with ground state molecular oxygen to form excited singlet - state oxygen or form other highly reactive species. The reactive species react with living cells, resulting in cel l death. This treatment is used in many forms of cancer including those in the prostrate, head and neck, lungs, bladder, esophagus and certain skin cancers. We developed a novel numerical method to model the photophysical and photochemical processes in the PS and the subsequent energy transfer to O2, improving the understanding of these processes at a molecular level. Our numerical method simulates light propagation and photo-physics in PS using methods that build on techniques previously developed for optical communications and nonlinear optics applications.

Genetic and Environmental Stability Differs in Reactive and Proactive Aggression

PubMed Central

Tuvblad, Catherine; Raine, Adrian; Zheng, Mo; Baker, Laura A.

2009-01-01

The aim of this study was to examine stability and change in genetic and environmental influences on reactive (impulsive and affective) and proactive (planned and instrumental) aggression from childhood to early adolescence. The sample was drawn from an ongoing longitudinal twin study of risk factors for antisocial behavior at the University of Southern California (USC). The twins were measured on two occasions: ages 9–10 years (N = 1,241) and 11–14 years (N = 874). Reactive and proactive aggressive behaviors were rated by parents. The stability in reactive aggression was due to genetic and nonshared environmental influences, whereas the continuity in proactive aggression was primarily genetically mediated. Change in both reactive and proactive aggression between the two occasions was mainly explained by nonshared environmental influences, although some evidence for new genetic variance at the second occasion was found for both forms of aggression. These results suggest that proactive and reactive aggression differ in their genetic and environmental stability, and provide further evidence for some distinction between reactive and proactive forms of aggression. PMID:19688841

Soil emissions of gaseous reactive nitrogen from North American arid lands: an overlooked source.

NASA Astrophysics Data System (ADS)

Sparks, J. P.; McCalley, C. K.; Strahm, B. D.

2008-12-01

The biosphere-atmosphere exchange and transformation of nitrogen has important ramifications for both terrestrial biogeochemistry and atmospheric chemistry. Several important mechanisms within this process (e.g., photochemistry, nitrogen deposition, aerosol formation) are strongly influenced by the emission of reactive nitrogen compounds from the Earth's surface. Therefore, a quantification of emission sources is a high priority for future conceptual understanding. One source largely overlooked in most global treatments are the soil emissions from arid and semi-arid landscapes worldwide. Approximately 35-40% of global terrestrial land cover is aridland and emission of reactive nitrogen from soils in these regions has the potential to strongly influence both regional and global biogeochemistry. Here we present estimates of soil emission of oxidized (NO, total NOy including NO2 and HONO) and reduced (NH3) forms of reactive nitrogen from two North American arid regions: the Mojave Desert and the Colorado Plateau. Soil fluxes in these regions are highly dependent on soil moisture conditions. Soil moisture is largely driven by pulsed rain events with fluxes increasing 20-40 fold after a rain event. Using field measurements made across seasons under an array of moisture conditions, precipitation records, and spatially explicit cover type information we have estimated annual estimates for the Mojave Desert (1.5 ± 0.7 g N ha-1 yr-1), the shale derived (1.4 ± 0.9 g N ha-1 yr-1), and sandy soil derived (2.8 ± 1.2 g N ha-1 yr-1) regions of the Colorado Plateau. The chemical composition of soil emissions varies significantly both with season and soil moisture content. Emissions from dry soils tend to be dominated by ammonia and forms of NOy other than NO. In contrast, NO becomes a dominant portion of the flux post rain events (~30% of the total flux). This variability in chemical form has significant implications for the tropospheric fate of the emitted N. NO and other nitrogen oxides are likely to participate in photochemistry, ozone production, and production of organic nitrates and nitric acid. In contrast, NH3 is likely to locally redeposit or form secondary aerosols in the presence of sulphate. Given the vastly different influence of oxidized versus reduced forms of N on atmospheric chemistry, the variable chemical partitioning of soil emissions based on season and water availability observed in this study is likely to improve the performance of regional photochemistry models.

A carnosine intervention study in overweight human volunteers: bioavailability and reactive carbonyl species sequestering effect

NASA Astrophysics Data System (ADS)

Regazzoni, Luca; de Courten, Barbora; Garzon, Davide; Altomare, Alessandra; Marinello, Cristina; Jakubova, Michaela; Vallova, Silvia; Krumpolec, Patrik; Carini, Marina; Ukropec, Jozef; Ukropcova, Barbara; Aldini, Giancarlo

2016-06-01

Carnosine is a natural dipeptide able to react with reactive carbonyl species, which have been recently associated with the onset and progression of several human diseases. Herein, we report an intervention study in overweight individuals. Carnosine (2 g/day) was orally administered for twelve weeks in order to evaluate its bioavailability and metabolic fate. Two carnosine adducts were detected in the urine samples of all subjects. Such adducts are generated from a reaction with acrolein, which is one of the most toxic and reactive compounds among reactive carbonyl species. However, neither carnosine nor adducts have been detected in plasma. Urinary excretion of adducts and carnosine showed a positive correlation although a high variability of individual response to carnosine supplementation was observed. Interestingly, treated subjects showed a significant decrease in the percentage of excreted adducts in reduced form, accompanied by a significant increase of the urinary excretion of both carnosine and carnosine-acrolein adducts. Altogether, data suggest that acrolein is entrapped in vivo by carnosine although the response to its supplementation is possibly influenced by individual diversities in terms of carnosine dietary intake, metabolism and basal production of reactive carbonyl species.

Review of Abiotic Degradation of Chlorinated Solvents by Reactive Iron Minerals

EPA Science Inventory

Abiotic degradation of chlorinated solvents by reactive iron minerals such as iron sulfides, magnetite, green rust, and other Fe(II)-containing minerals has been observed in both laboratory and field conditions. These reactive iron minerals typically form under iron and sulfate ...

Layered reactive particles with controlled geometries, energies, and reactivities, and methods for making the same

DOEpatents

Fritz, Gregory M.; Weihs, Timothy P.; Grzyb, Justin A.

2016-07-05

An energetic composite having a plurality of reactive particles each having a reactive multilayer construction formed by successively depositing reactive layers on a rod-shaped substrate having a longitudinal axis, dividing the reactive-layer-deposited rod-shaped substrate into a plurality of substantially uniform longitudinal segments, and removing the rod-shaped substrate from the longitudinal segments, so that the reactive particles have a controlled, substantially uniform, cylindrically curved or otherwise rod-contoured geometry which facilitates handling and improves its packing fraction, while the reactant multilayer construction controls the stability, reactivity and energy density of the energetic composite.

Layered reactive particles with controlled geometries, energies, and reactivities, and methods for making the same

DOEpatents

Fritz, Gregory M; Knepper, Robert Allen; Weihs, Timothy P; Gash, Alexander E; Sze, John S

2013-04-30

An energetic composite having a plurality of reactive particles each having a reactive multilayer construction formed by successively depositing reactive layers on a rod-shaped substrate having a longitudinal axis, dividing the reactive-layer-deposited rod-shaped substrate into a plurality of substantially uniform longitudinal segments, and removing the rod-shaped substrate from the longitudinal segments, so that the reactive particles have a controlled, substantially uniform, cylindrically curved or otherwise rod-contoured geometry which facilitates handling and improves its packing fraction, while the reactant multilayer construction controls the stability, reactivity and energy density of the energetic composite.

Morphological Characteristics of Particulate Material Formed from High Velocity Impact of Depleted Uranium Projectiles with Armor Targets

DTIC Science & Technology

1978-11-01

Magnification Showing Aggregation of Ultrafine Particles ; Gap Between Bars Represents 0.5 pm. .......... ... 15 iv LIST OF FIGURES (CONCLUDED) Figure Title...subsequent forma- tion of smaller particulates. An unexpected phenomenon was the formation of ultrafine particles less than 0.1 pm in diameter. These...and the highly reactive nature of pyrophoric depleted uranium. Ti ese ultrafine particles exhibited an extreme tendency to coalesce, probably due to

Aminative umpolung of aldehydes to α-amino anion equivalents for Pd-catalyzed allylation: an efficient synthesis of homoallylic amines.

PubMed

Ding, Lei; Chen, Jing; Hu, Yifan; Xu, Juan; Gong, Xing; Xu, Dongfang; Zhao, Baoguo; Li, Hexing

2014-02-07

An attractive strategy for generation of α-amino anions from aldehydes with applications in synthesis of homoallylic amines is described. Aromatic aldehydes can be converted to α-amino anion equivalents via amination with 2,2-diphenylglycine and subsequent decarboxylation. The in situ generated α-imino anions are highly reactive for Pd-catalyzed allylation, forming the corresponding homoallylic amines in high yields with excellent regioselectivity.

THERMAL NEUTRONIC REACTOR

DOEpatents

Spinrad, B.I.

1960-01-12

A novel thermal reactor was designed in which a first reflector formed from a high atomic weight, nonmoderating material is disposed immediately adjacent to the reactor core. A second reflector composed of a moderating material is disposed outwardly of the first reflector. The advantage of this novel reflector arrangement is that the first reflector provides a high slow neutron flux in the second reflector, where irradiation experiments may be conducted with a small effect on reactor reactivity.

Unique Reactivity of Transition Metal Atoms Embedded in Graphene to CO, NO, O₂ and O Adsorption: A First-Principles Investigation.

PubMed

Chu, Minmin; Liu, Xin; Sui, Yanhui; Luo, Jie; Meng, Changgong

2015-10-27

Taking the adsorption of CO, NO, O₂ and O as probes, we investigated the electronic structure of transition metal atoms (TM, TM = Fe, Co, Ni, Cu and Zn) embedded in graphene by first-principles-based calculations. We showed that these TM atoms can be effectively stabilized on monovacancy defects on graphene by forming plausible interactions with the C atoms associated with dangling bonds. These interactions not only give rise to high energy barriers for the diffusion and aggregation of the embedded TM atoms to withstand the interference of reaction environments, but also shift the energy levels of TM-d states and regulate the reactivity of the embedded TM atoms. The adsorption of CO, NO, O₂ and O correlates well with the weight averaged energy level of TM-d states, showing the crucial role of interfacial TM-C interactions on manipulating the reactivity of embedded TM atoms. These findings pave the way for the developments of effective monodispersed atomic TM composites with high stability and desired performance for gas sensing and catalytic applications.

Hydropersulfides: H-Atom Transfer Agents Par Excellence.

PubMed

Chauvin, Jean-Philippe R; Griesser, Markus; Pratt, Derek A

2017-05-10

Hydropersulfides (RSSH) are formed endogenously via the reaction of the gaseous biotransmitter hydrogen sulfide (H 2 S) and disulfides (RSSR) and/or sulfenic acids (RSOH). RSSH have been investigated for their ability to store H 2 S in vivo and as a line of defense against oxidative stress, from which it is clear that RSSH are much more reactive to two-electron oxidants than thiols. Herein we describe the results of our investigations into the H-atom transfer chemistry of RSSH, contrasting it with the well-known H-atom transfer chemistry of thiols. In fact, RSSH are excellent H-atom donors to alkyl (k ∼ 5 × 10 8 M -1 s -1 ), alkoxyl (k ∼ 1 × 10 9 M -1 s -1 ), peroxyl (k ∼ 2 × 10 6 M -1 s -1 ), and thiyl (k > 1 × 10 10 M -1 s -1 ) radicals, besting thiols by as little as 1 order and as much as 4 orders of magnitude. The inherently high reactivity of RSSH to H-atom transfer is based largely on thermodynamic factors; the weak RSS-H bond dissociation enthalpy (∼70 kcal/mol) and the associated high stability of the perthiyl radical make the foregoing reactions exothermic by 15-34 kcal/mol. Of particular relevance in the context of oxidative stress is the reactivity of RSSH to peroxyl radicals, where favorable thermodynamics are bolstered by a secondary orbital interaction in the transition state of the formal H-atom transfer that drives the inherent reactivity of RSSH to match that of α-tocopherol (α-TOH), nature's premier radical-trapping antioxidant. Significantly, the reactivity of RSSH eclipses that of α-TOH in H-bond-accepting media because of their low H-bond acidity (α 2 H ∼ 0.1). This affords RSSH a unique versatility compared to other highly reactive radical-trapping antioxidants (e.g., phenols, diarylamines, hydroxylamines, sulfenic acids), which tend to have high H-bond acidities. Moreover, the perthiyl radicals that result are highly persistent under autoxidation conditions and undergo very rapid dimerization (k = 5 × 10 9 M -1 s -1 ) in lieu of reacting with O 2 or autoxidizable substrates.

Functional Characterization of Resting and Adenovirus-Induced Reactive Astrocytes in Three-Dimensional Culture

PubMed Central

Woo, Junsung; Im, Sun-Kyoung; Chun, Heejung; Jung, Soon-Young; Oh, Soo-Jin; Choi, Nakwon

2017-01-01

Brain is a rich environment where neurons and glia interact with neighboring cells as well as extracellular matrix in three-dimensional (3D) space. Astrocytes, which are the most abundant cells in the mammalian brain, reside in 3D space and extend highly branched processes that form microdomains and contact synapses. It has been suggested that astrocytes cultured in 3D might be maintained in a less reactive state as compared to those growing in a traditional, two-dimensional (2D) monolayer culture. However, the functional characterization of the astrocytes in 3D culture has been lacking. Here we cocultured neurons and astrocytes in 3D and examined the morphological, molecular biological, and electrophysiological properties of the 3D-cultured hippocampal astrocytes. In our 3D neuron-astrocyte coculture, astrocytes showed a typical morphology of a small soma with many branches and exhibited a unique membrane property of passive conductance, more closely resembling their native in vivo counterparts. Moreover, we also induced reactive astrocytosis in culture by infecting with high-titer adenovirus to mimic pathophysiological conditions in vivo. Adenoviral infection induced morphological changes in astrocytes, increased passive conductance, and increased GABA content as well as tonic GABA release, which are characteristics of reactive gliosis. Together, our study presents a powerful in vitro model resembling both physiological and pathophysiological conditions in vivo, and thereby provides a versatile experimental tool for studying various neurological diseases that accompany reactive astrocytes. PMID:28680301

Mitochondria as a source and target of lipid peroxidation products in healthy and diseased heart.

PubMed

Anderson, Ethan J; Katunga, Lalage A; Willis, Monte S

2012-02-01

The heart is a highly oxidative organ in which cardiomyocyte turnover is virtually absent, making it particularly vulnerable to accumulation of lipid peroxidation products (LPP) formed as a result of oxidative damage. Reactive oxygen and nitrogen species are the most common electrophiles formed during lipid peroxidation and lead to the formation of both stable and unstable LPP. Of the LPP formed, highly reactive aldehydes are a well-recognized causative factor in ageing and age-associated diseases, including cardiovascular disease and diabetes. Recent studies have identified that the mitochondria are both a primary source and target of LPP, with specific emphasis on aldehydes in cardiomyocytes and how these affect the electron transport system and Ca(2+) balance. Numerous studies have found that there are functional consequences in the heart following exposure to specific aldehydes (acrolein, trans-2-hexanal, 4-hydroxynonenal and acetaldehyde). Because these LPP are known to form in heart failure, cardiac ischaemia-reperfusion injury and diabetes, they may have an underappreciated role in the pathophysiology of these disease processes. Lipid peroxidation products are involved in the transcriptional regulation of endogenous anti-oxidant systems. Recent evidence demonstrates that transient increases in LPP may be beneficial in cardioprotection by contributing to mitohormesis (i.e. induction of anti-oxidant systems) in cardiomyocytes. Thus, exploitation of the cardioprotective actions of the LPP may represent a novel therapeutic strategy for future treatment of heart disease. © 2011 The Authors. Clinical and Experimental Pharmacology and Physiology © 2011 Blackwell Publishing Asia Pty Ltd.

40 CFR 63.3941 - How do I demonstrate initial compliance with the emission limitations?

Code of Federal Regulations, 2010 CFR

2010-07-01

... PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR... organic HAP. For reactive adhesives in which some of the HAP react to form solids and are not emitted to... reactive adhesives in which some of the HAP react to form solids and are not emitted to the atmosphere, you...

Brief Report: Sensory Reactivity in Children with Phelan-McDermid Syndrome

ERIC Educational Resources Information Center

Mieses, A. M.; Tavassoli, T.; Li, E.; Soorya, L.; Lurie, S.; Wang, A. T.; Siper, P. M.; Kolevzon, A.

2016-01-01

Phelan-McDermid syndrome (PMS), a monogenic form of autism spectrum disorder (ASD), results from deletion or mutation of the "SHANK3" gene. Atypical sensory reactivity is now included in the diagnostic criteria for ASD. Examining the sensory phenotype in monogenic forms of ASD, such as PMS, may help identify underlying mechanisms of…

Photoswitchable Fluorescent Diarylethene Derivatives with Thiophene 1,1-Dioxide Groups: Effect of Alkyl Substituents at the Reactive Carbons

PubMed Central

Sumi, Takaki; Irie, Masahiro

2017-01-01

Photoswitching and fluorescent properties of sulfone derivatives of 1,2-bis(2-alkyl-4-methyl-5-phenyl-3-thienyl)perfluorocyclopentene, 1–5, having methyl, ethyl, n-propyl, i-propyl, and i-butyl substituents at the reactive carbons (2- and 2′-positions) of the thiophene 1,1-dioxide rings were studied. Diarylethenes 1–5 underwent isomerization reactions between open-ring and closed-ring forms upon alternate irradiation with ultraviolet (UV) and visible light and showed fluorescence in the closed-ring forms. The alkyl substitution at the reactive carbons affects the fluorescent property of the closed-ring isomers. The closed-ring isomers 2b–5b with ethyl, n-propyl, i-propyl, and i-butyl substituents show higher fluorescence quantum yields than 1b with methyl substituents. In polar solvents, the fluorescence quantum yield of 1b markedly decreases, while 2b–5b maintain the relatively high fluorescence quantum yields. Although the cycloreversion quantum yields of the derivatives with methyl, ethyl, n-propyl, and i-propyl substituents are quite low and in the order of 10−5, introduction of i-butyl substituents was found to increase the yield up to the order of 10−3. These results indicate that appropriate alkyl substitution at the reactive carbons is indispensable for properly controlling the photoswitching and fluorescent properties of the photoswitchable fluorescent diarylethenes, which are potentially applicable to super-resolution fluorescence microscopies. PMID:28869489

Practical ultrasonic transducers for high-temperature applications using bismuth titanate and Ceramabind 830

NASA Astrophysics Data System (ADS)

Xu, Janet L.; Batista, Caio F. G.; Tittmann, Bernhard R.

2018-04-01

Structural health monitoring of large valve bodies in high-temperature environments such as power plants faces several limitations: commercial transducers are not rated for such high temperatures, gel couplants will evaporate, and measurements cannot be made in-situ. To solve this, we have furthered the work of Ledford in applying a practical transducer in liquid form which hardens and air dries directly onto the substrate. The transducer material is a piezoceramic film composed of bismuth titanate and a high-temperature binding agent, Ceramabind 830. The effects of several fabrication conditions were studied to optimize transducer performance and ensure repeatability. These fabrication conditions include humidity, binder ratio, water ratio, substrate roughness, and film thickness. The final product is stable for both reactive and non-reactive substrates, has a quick fabrication time, and has an operating temperature up to the Curie temperature of BIT, 650°C, well beyond the safe operating temperature of PZT (150°C).

Self-Reported Trait Mindfulness and Affective Reactivity: A Motivational Approach Using Multiple Psychophysiological Measures

PubMed Central

Cosme, Danielle; Wiens, Stefan

2015-01-01

As a form of attention, mindfulness is qualitatively receptive and non-reactive, and is thought to facilitate adaptive emotional responding. One suggested mechanism is that mindfulness facilitates disengagement from an affective stimulus and thereby decreases affective reactivity. However, mindfulness has been conceptualized as a state, intervention, and trait. Because evidence is mixed as to whether self-reported trait mindfulness decreases affective reactivity, we used a multi-method approach to study the relationship between individual differences in self-reported trait mindfulness and electrocortical, electrodermal, electromyographic, and self-reported responses to emotional pictures. Specifically, while participants (N = 51) passively viewed pleasant, neutral, and unpleasant IAPS pictures, we recorded high-density (128 channels) electrocortical, electrodermal, and electromyographic data to the pictures as well as to acoustic startle probes presented during the pictures. Afterwards, participants rated their subjective valence and arousal while viewing the pictures again. If trait mindfulness spontaneously reduces general emotional reactivity, then for individuals reporting high rather than low mindfulness, response differences between emotional and neutral pictures would show relatively decreased early posterior negativity (EPN) and late positive potential (LPP) amplitudes, decreased skin conductance responses, and decreased subjective ratings for valence and arousal. High mindfulness would also be associated with decreased emotional modulation of startle eyeblink and P3 amplitudes. Although results showed clear effects of emotion on the dependent measures, in general, mindfulness did not moderate these effects. For most measures, effect sizes were small with rather narrow confidence intervals. These data do not support the hypothesis that individual differences in self-reported trait mindfulness are related to spontaneous emotional responses during picture viewing. PMID:25749431

Fermi Level Unpinning of GaSb (100) using Plasma Enhanced Atomic Layer Deposition of Al2O3

DTIC Science & Technology

2010-01-01

of high-/GaSb semiconductor interface. GaSb has a highly reactive surface and on exposure to air it will form a native oxide layer composed of Ga2O3 ...and Sb2O3 2GaSb+3O2→ Ga2O3 +Sb2O3. The Sb2O3 can fur- ther react with the GaSb surface forming elemental Sb and Ga2O3 Sb2O3+2GaSb→ Ga2O3 +4Sb.5,6...rights_and_permissions mentioned before, Sb2O3 reacts with GaSb forming Ga2O3 and elemental Sb.6 The kinetics of this reaction is enhanced at higher temperatures200 °C.14

Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl.

PubMed

Schnegelsberg, Christoph; Bachmann, Sebastian; Kolter, Marlene; Auth, Thomas; John, Michael; Stalke, Dietmar; Koszinowski, Konrad

2016-06-01

Grignard reagents RMgCl and their so-called turbo variant, the highly reactive RMgCl⋅LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity-enhancing effect. A combination of electrospray-ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion-ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl⋅LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron-rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for producing organic products containing silicon, hydrogen, nitrogen, and carbon by the direct reaction between elemental silicon and organic amines and products formed thereby

DOEpatents

Pugar, E.A.; Morgan, P.E.D.

1988-04-04

A process is disclosed for producing, at a low temperature, a high purity organic reaction product consisting essentially of silicon, hydrogen, nitrogen, and carbon. The process comprises reacting together a particulate elemental high purity silicon with a high purity reactive amine reactant in a liquid state at a temperature of from about O/degree/C up to about 300/degree/C. A high purity silicon carbide/silicon nitride ceramic product can be formed from this intermediate product, if desired, by heating the intermediate product at a temperature of from about 1200-1700/degree/C for a period from about 15 minutes up to about 2 hours or the organic reaction product may be employed in other chemical uses.

Chemical Functionalization of Graphene Family Members

NASA Astrophysics Data System (ADS)

Vacchi, Isabella Anna; Ménard-Moyon, Cécilia; Bianco, Alberto

2017-01-01

Thanks to their outstanding physicochemical properties, graphene and its derivatives are interesting nanomaterials with a high potential in several fields. Graphene, graphene oxide, and reduced graphene oxide, however, differ partially in their characteristics due to their diverse surface composition. Those differences influence the chemical reactivity of these materials. In the following chapter the reactivity and main functionalization reactions performed on graphene, graphene oxide, and reduced graphene oxide are discussed. A part is also dedicated to the main analytical techniques used for characterization of these materials. Functionalization of graphene and its derivatives is highly important to modulate their characteristics and design graphene-based conjugates with novel properties. Functionalization can be covalent by forming strong and stable bonds with the graphene surface, or non-covalent via π-π, electrostatic, hydrophobic, and/or van der Waals interactions. Both types of functionalization are currently exploited.

Structure for HTS composite conductors and the manufacture of same

DOEpatents

Cotton, J.D.; Riley, G.N. Jr.

1999-06-01

A superconducting oxide composite structure including a superconducting oxide member, a metal layer surrounding the superconducting oxide member, and an insulating layer of a complex oxide formed in situ adjacent to the superconducting oxide member and the metal layer is provided together with a method of forming such a superconducting oxide composite structure including encapsulating a superconducting oxide member or precursor within a metal matrix layer from the group of: (1) a reactive metal sheath adjacent to the superconducting oxide member or precursor, the reactive metal sheath surrounded by a second metal layer or (2) an alloy containing a reactive metal; to form an intermediate product, and, heating the intermediate product at temperatures and for time sufficient to form an insulating layer of a complex oxide in situ, the insulating layer to the superconducting oxide member or precursor and the metal matrix layer. 10 figs.

Structure for hts composite conductors and the manufacture of same

DOEpatents

Cotton, James D.; Riley, Jr., Gilbert Neal

1999-01-01

A superconducting oxide composite structure including a superconducting oxide member, a metal layer surrounding the superconducting oxide member, and an insulating layer of a complex oxide formed in situ adjacent to the superconducting oxide member and the metal layer is provided together with a method of forming such a superconducting oxide composite structure including encapsulating a superconducting oxide member or precursor within a metal matrix layer from the group of: (i) a reactive metal sheath adjacent to the superconducting oxide member or precursor, the reactive metal sheath surrounded by a second metal layer or (ii) an alloy containing a reactive metal; to form an intermediate product, and, heating the intermediate product at temperatures and for time sufficient to form an insulating layer of a complex oxide in situ, the insulating layer to the superconducting oxide member or precursor and the metal matrix layer.

[Changes of vascular reactivity and reactive oxygen species in conditions of varying duration of permanent stay in the alienation zone in mice].

PubMed

Tkachenko, M M; Kotsiuruba, A V; Baziliuk, O V; Horot', I V; Sahach, V F

2010-01-01

Peculiarities of changes in the vascular reactivity and in the content of reactive forms of oxygen and stable metabolites of nitric oxide (NO) were studied in the aorta preparations of C57BL/6 and BALB/c mice of the two age groups (6 and 18 mo.), which were born and permanently kept in the Chernobyl alienation zone. The results obtained showed a disturbance of acetylcholine-induced endothelium-dependent reactions of relaxation of smooth muscles of the thoracic aorta. A lower level of NO synthesis and lower level of oxidative arginase metabolism of arginine corresponded to a higher degree of damage of endothelium-dependent reactions of relaxation of the thoracic aorta smooth muscles. A decrease of NO synthesis in conditions of permanent effects of low doses of radiation was conditioned by an increase of generation of reactive forms of oxygen, namely, superoxide and hydroxyl radicals, which might be formed in mitochondria. In conditions of permanent effects of low doses of radiation a lesser level of protein nitrosothilation, same as lesser one of generation of OH-radical, corresponded to a higher level of damage of endothelium-dependent reactions.

Aerobic exercise reduces biomarkers related to cardiovascular risk among cleaners: effects of a worksite intervention RCT.

PubMed

Korshøj, Mette; Ravn, Marie Højbjerg; Holtermann, Andreas; Hansen, Åse Marie; Krustrup, Peter

2016-02-01

Blue-collar workers have an increased risk of cardiovascular disease. Accordingly, elevated levels of biomarkers related to risk of cardiovascular disease, such as high-sensitive C-reactive protein, have been observed among blue-collar workers. The objective was to examine whether an aerobic exercise worksite intervention changes the level of inflammation biomarkers among cleaners. The design was a cluster-randomized controlled trial with 4-month worksite intervention. Before the 116 cleaners aged 18-65 years were randomized, they signed an informed consent form. The reference group (n = 59) received lectures, and the aerobic exercise group (n = 57) performed worksite aerobic exercise (30 min twice a week). Levels of biomarkers (high-sensitive C-reactive protein, fibrinogen, cholesterol, low- and high-density lipoprotein cholesterol and triglyceride) were collected at baseline and after 4 months. A repeated-measure, multi-adjusted, mixed-model intention-to-treat analysis was applied to compare between-group differences. The study was registered as ISRCTN86682076. Significant (p < 0.05) between-group reductions from baseline to follow-up were found for high-sensitive C-reactive protein (-0.54 ± 0.20 µg/ml; 95% CI -0.94, -0.14), low-density lipoprotein cholesterol (-0.32 ± 0.11 mmol/L; 95% CI -0.54, -0.10) and the ratios of LDL/HDL (-0.30 ± 0.08; 95% CI -0.46, -0.14), and LDL/TC cholesterol (-0.04 ± 0.02; 95% CI -0.07, -0.01). This study indicates that an aerobic exercise intervention among cleaners leads to reduced levels of high-sensitive C-reactive protein and low-density lipoprotein cholesterol, and an unaltered level of fibrinogen. The aerobic exercise seems to improve inflammatory levels and lipoprotein profile among cleaners, with no signs of cardiovascular overload.

Effects of point defect concentrations of the reactive element oxides on the oxidation kinetics of pure Ni and Ni-Cr alloys

NASA Astrophysics Data System (ADS)

Yan, Ruey-Fong

The addition of some reactive element oxides, e.g. Ysb2Osb3 or ZrOsb2, has significant effects, e.g. improvement in scale adhesion and reduction in oxidation rate, on the oxidation behavior of chromia and alumina scale forming alloys at high temperatures. However, there is little agreement about how a small addition of an oxygen-active element can cause such profound effects. It was the goal of this project to study the growth kinetics of an oxide scale when different reactive-element oxides were added to pure Ni and Ni-Cr alloys and, consequently, to aid in clarifying the mechanism of reactive element effects. The oxidation kinetics were measured using a thermogravimetric analysis (TGA) method and the material characterization of oxide scale was conducted. The relationship between point defect structures and oxidation kinetics was discussed. The results in this research showed that Ysb2Osb3 and ZrOsb2 exhibited the reactive element effects on the oxidation behaviors of Ni and Ni-Cr alloys. In addition, the point defect concentrations of the reactive element oxide, Ysb2Osb3, were changed by doping of different valent oxides. The modification of point defect concentrations of the reactive element oxide dispersed phases did change the oxidation kinetics of the pure Ni and Ni-Cr alloys containing Ysb2Osb3. These results indicate that the transport properties of the reactive element oxide dispersed phases are one of the important factors in determining the growth rate of an oxide scale.

A novel approach to enhance antibody sensitivity and specificity by peptide cross-linking

PubMed Central

Namiki, Takeshi; Valencia, Julio C.; Hall, Matthew D.; Hearing, Vincent J.

2008-01-01

Most current techniques employed to improve antigen-antibody signals in western blotting and in immunohistochemistry rely on sample processing prior to staining (e.g. microwaving) or using a more robust reporter (e.g. a secondary antibody with biotin-streptavidin). We have developed and optimized a new approach intended to stabilize the complexes formed between antigens and their respective primary antibodies by cupric ions at high pH. This technique improves the affinity and lowers cross-reactivity with non-specific bands of ∼20% of antibodies tested (5/25). Here we report that this method can enhance antigen-antibody specificity and can improve the utility of some poorly reactive primary antibodies. PMID:18801330

Reverse-mode thermoresponsive light attenuators produced by optical anisotropic composites of nematic liquid crystals and reactive mesogens

NASA Astrophysics Data System (ADS)

Kakiuchida, Hiroshi; Ogiwara, Akifumi

2018-04-01

Polymer network liquid crystals (PNLCs) whose optical transmittance state switches between transparence at low temperatures and haze at high temperatures were fabricated from mixtures of nematic liquid crystals (LCs) and reactive mesogens (RMs). This PNLC structure is simple but effective, namely, consists of micro-scale domains of orientation-ordered LCs and anisotropically polymerized RMs. The domains form through photopolymerization induced phase separation with inhomogeneous irradiation projected by laser speckling techniques. This irradiation method enables you to control the size and shape of phase-separation domains, and these PNLCs can be applied to novel thermoresponsive optical devices; optical isolators, thermometric sheets, and smart windows.

Magnetic nuclear core restraint and control

DOEpatents

Cooper, Martin H.

1979-01-01

A lateral restraint and control system for a nuclear reactor core adaptable to provide an inherent decrease of core reactivity in response to abnormally high reactor coolant fluid temperatures. An electromagnet is associated with structure for radially compressing the core during normal reactor conditions. A portion of the structures forming a magnetic circuit are composed of ferromagnetic material having a curie temperature corresponding to a selected coolant fluid temperature. Upon a selected signal, or inherently upon a preselected rise in coolant temperature, the magnetic force is decreased a given amount sufficient to relieve the compression force so as to allow core radial expansion. The expanded core configuration provides a decreased reactivity, tending to shut down the nuclear reaction.

Magnetic nuclear core restraint and control

DOEpatents

Cooper, Martin H.

1978-01-01

A lateral restraint and control system for a nuclear reactor core adaptable to provide an inherent decrease of core reactivity in response to abnormally high reactor coolant fluid temperatures. An electromagnet is associated with structure for radially compressing the core during normal reactor conditions. A portion of the structures forming a magnetic circuit are composed of ferromagnetic material having a curie temperature corresponding to a selected coolant fluid temperature. Upon a selected signal, or inherently upon a preselected rise in coolant temperature, the magnetic force is decreased a given amount sufficient to relieve the compression force so as to allow core radial expansion. The expanded core configuration provides a decreased reactivity, tending to shut down the nuclear reaction.

Cold atmospheric plasma (CAP), a novel physicochemical source, induces neural differentiation through cross-talk between the specific RONS cascade and Trk/Ras/ERK signaling pathway.

PubMed

Jang, Ja-Young; Hong, Young June; Lim, Junsup; Choi, Jin Sung; Choi, Eun Ha; Kang, Seongman; Rhim, Hyangshuk

2018-02-01

Plasma, formed by ionization of gas molecules or atoms, is the most abundant form of matter and consists of highly reactive physicochemical species. In the physics and chemistry fields, plasma has been extensively studied; however, the exact action mechanisms of plasma on biological systems, including cells and humans, are not well known. Recent evidence suggests that cold atmospheric plasma (CAP), which refers to plasma used in the biomedical field, may regulate diverse cellular processes, including neural differentiation. However, the mechanism by which these physicochemical signals, elicited by reactive oxygen and nitrogen species (RONS), are transmitted to biological system remains elusive. In this study, we elucidated the physicochemical and biological (PCB) connection between the CAP cascade and Trk/Ras/ERK signaling pathway, which resulted in neural differentiation. Excited atomic oxygen in the plasma phase led to the formation of RONS in the PCB network, which then interacted with reactive atoms in the extracellular liquid phase to form nitric oxide (NO). Production of large amounts of superoxide radical (O 2 - ) in the mitochondria of cells exposed to CAP demonstrated that extracellular NO induced the reversible inhibition of mitochondrial complex IV. We also demonstrated that cytosolic hydrogen peroxide, formed by O 2 - dismutation, act as an intracellular messenger to specifically activate the Trk/Ras/ERK signaling pathway. This study is the first to elucidate the mechanism linking physicochemical signals from the CAP cascade to the intracellular neural differentiation signaling pathway, providing physical, chemical and biological insights into the development of therapeutic techniques to treat neurological diseases. Copyright © 2017 Elsevier Ltd. All rights reserved.

Welding bulk metallic glass using nanostructured reactive multilayer foils

NASA Astrophysics Data System (ADS)

Trenkle, Jonathan C.

We have used Al/Ni reactive foils to weld Zr57Ti 5Cu20Ni8Al10 metallic glasses. The welds are a composite morphology comprised of glass ligaments and intermetallic AlNi (the product of the reactive foil). The presence of the presumably brittle intermetallic (in lieu of the glass) is expected to limit the mechanical properties of the welds. Based on fracture toughness measurements and the crack propagation paths, we conclude that virtually all of the toughness can be ascribed to the presence of the metallic glass ligaments. Increasing the pressure applied during welding increases the fraction of the joint made of these ligaments and so increases the fracture toughness as well. To eliminate the intermetallic from the weld altogether, we attempted to fabricate reactive mulitlayer foils that form an amorphous product by melting and cooling rapidly during a self-propagating reaction. We began with reactive foils with overall composition Zr2Ni but quickly determined that the foils did not fully melt. We then attempted to lower the melting temperature and increase the glass forming ability and the heat of mixing by adding Al and Cu. These foils again did not fully melt. Finally we systematically determined that foils of overall compositions Hf37Ni63, Ni 80P20, and Ni60P40, which are all known binary metallic glasses, will potentially melt during a self-propagating reaction. Knowledge of the phase transformations during a self-propagating reaction is necessary to engineer reactive foils for future applications. Furthermore, reactive foils provide an opportunity to study phase transformations under high heating rates not easily achievable. Characterizing the processes in the reaction zone however is challenging, requiring both temporal resolution better than ˜ 100 mus (the time required for the reaction front to pass a fixed location) and spatial resolution of < 100 mum (the approximate width of the reaction zone). Using synchrotron x-ray radiation, we have studied these phase transformations in situ in Al/Ni multilayers. Unlike previous annealing and quenching studies in these multilayers, we observed no metastable or intermediate phases.

Exploring the cause of initially reactive bovine brains on rapid tests for BSE

PubMed Central

Dudas, Sandor; James, Jace; Anderson, Renee; Czub, Stefanie

2015-01-01

ABSTRACT Bovine spongiform encephalopathy (BSE) is an invariably fatal prion disease of cattle. The identification of the zoonotic potential of BSE prompted safety officials to initiate surveillance testing for this disease. In Canada, BSE surveillance is primarily focused on high risk cattle including animals which are dead, down and unable to rise, diseased or distressed. This targeted surveillance results in the submission of brain samples with a wide range of tissue autolysis and associated contaminants. These contaminants have the potential to interfere with important steps of surveillance tests resulting in initially positive test results requiring additional testing to confirm the disease status of the animal. The current tests used for BSE screening in Canada utilize the relative protease resistance of the prion protein gained when it misfolds from PrPC to PrPSc as part of the disease process. Proteinase K completely digests PrPC in normal brains, but leaves most of the PrPSc in BSE positive brains intact which is detected using anti-prion antibodies. These tests are highly reliable but occasionally give rise to initially reactive/false positive results. Test results for these reactive samples were close to the positive/negative cut-off on a sub set of test platforms. This is in contrast to all of the previous Canadian positive samples whose numeric values on these same test platforms were 10 to 100 fold greater than the test positive/negative cut-off. Here we explore the potential reason why a sample is repeatedly positive on a sub-set of rapid surveillance tests, but negative on other test platforms. In order to better understand and identify what might cause these initial reactions, we have conducted a variety of rapid and confirmatory assays as well as bacterial isolation and identification on BSE positive, negative and initially reactive samples. We observed high levels of viable bacterial contamination in initially reactive samples suggesting that the reactivity may be related to bacterial factors. Several bacteria isolated from the initially reactive samples have characteristics of biofilm forming bacteria and this extracellular matrix might play a role in preventing complete digestion of PrPC in these samples. PMID:26689488

High pressure chemistry of red phosphorus by photoactivated simple molecules

NASA Astrophysics Data System (ADS)

Ceppatelli, Matteo; Bini, Roberto; Fanetti, Samuele; Caporali, Maria; Peruzzini, Maurizio

2013-06-01

High pressure (HP) is very effective in reducing intermolecular distances and inducing unexpected chemical reactions. In particular the photoactivation of the reactants in HP conditions can lead to very efficient and selective processes. The chemistry of phosphorus is currently based on the white molecular form. The red polymeric allotrope, despite more stable and much less toxic, has not attracted much attention so far. However, switching from the white to the red form would benefit any industrial procedure, especially from an environmental point of view. On the other side, water and ethanol are renewable, environmental friendly and largely available molecules, usable as reactants and photoactivators in HP conditions. Here we report a study on the HP photoinduced reactivity of red phosphorus with water and ethanol, showing the possibility of very efficient and selective processes, leading to molecular hydrogen and valuable phosphorus compounds. The reactions have been studied by means of FTIR and Raman spectroscopy and pressure has been generated using DAC and SAC. HP reactivity has been activated by the two-photon absorption of near-UV wavelengths and occured in total absence of solvents, catalysts and radical initiators, at room T and mild pressure conditions (0.2-1.5 GPa).

Grotthuss Transport of Iodide in EMIM/I3 Ionic Crystal.

PubMed

McDaniel, Jesse G; Yethiraj, Arun

2018-01-11

Highly ionic environments can mediate unusual chemical reactions that would otherwise be considered impossible based on chemical intuition. For example, the formation of a chemical bond between two iodide anions to form a divalent polyiodide anion is seemingly prohibited due to Coulombic repulsion. Using ab initio molecular dynamics simulations, we show that in the 1-ethyl-3-methylimidazolium (EMIM)/I 3 ionic crystal, the reactive formation of divalent and even trivalent polyiodide anions occurs with extremely small energetic barriers, due to the electrostatic field of the ionic lattice. A practical consequence of this anomalous reactivity is that iodide anions are efficiently transported within the crystal through a "Grotthuss-exchange" mechanism involving bond-breaking and forming events. We characterize two distinct transport pathways, involving both I 4 2- and I 7 3- intermediates, with fast transport of iodide resulting from the release of an I - anion on the opposite side of the intermediate species from the initial bond formation. The ordered cation arrangement in the crystal provides the necessary electrostatic screening for close approach of anions, suggesting a new counterintuitive approach to obtain high ionic conductivity. This new design principle could be used to develop better solid-state electrolytes for batteries, fuel cells, and supercapacitors.

Quantitation of Thioprolines in Grape Wine by Isotope Dilution-Liquid Chromatography-Tandem Mass Spectrometry.

PubMed

Liu, Jingjing; Meng, Xiangpeng; Chan, Wan

2016-02-17

Cysteine reacts with reactive carbonyls to form thioprolines, which have been demonstrated to possess various pharmaceutical properties. Therefore, thioproline formation is considered as a major detoxification pathway for carcinogenic reactive carbonyls. In this study, we report the initial identification of thiazolidine-4-carboxylic acid (1) and 2-methylthiazolidine-4-carboxylic acid (2), two very common thioprolines, formed by reacting formaldehyde and acetaldehyde with cysteine in grape wine samples. We have developed an isotope dilution-liquid chromatography-tandem mass spectrometry method featuring high sensitivity (limit of detection of ≤1.5 ng/mL) and selectivity to quantitate compounds 1 and 2. The method after validated to be highly accurate (recovery of ≥92%) and precise [intraday relative standard deviation (RSD) of ≤4.1% and interday RSD of ≤9.7%] was applied to determine the varying compound 1 and 2 contents in grape wine samples. Results revealed the grape type and storage duration-dependent formation of thioprolines in grape wines. Overall, the results are expected to facilitate compound-dependent investigations of the health benefits of grape wine, and our findings could be adopted to predict the age of grape wine.

Stolon regression

PubMed Central

Cherry Vogt, Kimberly S

2008-01-01

Many colonial organisms encrust surfaces with feeding and reproductive polyps connected by vascular stolons. Such colonies often show a dichotomy between runner-like forms, with widely spaced polyps and long stolon connections, and sheet-like forms, with closely spaced polyps and short stolon connections. Generative processes, such as rates of polyp initiation relative to rates of stolon elongation, are typically thought to underlie this dichotomy. Regressive processes, such as tissue regression and cell death, may also be relevant. In this context, we have recently characterized the process of stolon regression in a colonial cnidarian, Podocoryna carnea. Stolon regression occurs naturally in these colonies. To characterize this process in detail, high levels of stolon regression were induced in experimental colonies by treatment with reactive oxygen and reactive nitrogen species (ROS and RNS). Either treatment results in stolon regression and is accompanied by high levels of endogenous ROS and RNS as well as morphological indications of cell death in the regressing stolon. The initiating step in regression appears to be a perturbation of normal colony-wide gastrovascular flow. This suggests more general connections between stolon regression and a wide variety of environmental effects. Here we summarize our results and further discuss such connections. PMID:19704785

New Directions in Measuring Reactive and Proactive Aggression: Validation of a Teacher Questionnaire

ERIC Educational Resources Information Center

Polman, Hanneke; de Castro, Bram Orobio; Thomaes, Sander; van Aken, Marcel

2009-01-01

The well-known distinction between reactive and proactive aggression is theoretically important but empirically controversial. Recently, aggression researchers have argued that we should separate the form and function of aggression to make a clearer distinction between reactive and proactive aggression. This article describes the validation of a…

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE PAGES

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; ...

2017-02-16

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

Influence of LaFeO 3 Surface Termination on Water Reactivity

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

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

The formation of reactive species having hydroxyl radical-like reactivity from UV photolysis of N-nitrosodimethylamine (NDMA): kinetics and mechanism.

PubMed

Kwon, Bum Gun; Kim, Jong-Oh; Namkung, Kyu Cheol

2012-10-15

This study focuses on the detailed mechanism by which N-nitrosodimethylamine (NDMA) is photolyzed to form oxidized products, i.e., NO(2)(-) and NO(3)(-), and reveals a key reactive species produced during the photolysis of NDMA. Under acidic conditions, NO(2)(-) formed from the photodecomposition of NDMA was more prevalent than NO(3)(-). In this result, key species for the formation of NO(2)(-) are presumably N(2)O(3) and N(2)O(4) as termination products as well as NO and O(2) as reactants. Conversely, under alkaline conditions, NO(3)(-) was more prevalent than NO(2)(-). For this result, a key species for NO(3)(-) formation is presumably peroxynitrite (ONOO(-)). A detailed mechanistic study was performed with a competition reaction (or kinetics) between NDMA and p-nitrosodimethylaniline (PNDA) probe for hydroxyl radical (OH). It is fortuitous that the second-order rate constant for NDMA with an unknown reactive species (URS) was 5.13×10(8) M(-1) s(-1), which was similar to its published value for the reaction of NDMA+OH. Our study results showed that a key reactive species generated during NDMA photo-decomposition had hydroxyl radical-like reactivity and in particular, under alkaline conditions, it is most likely ONOO(-) as a source of nitrate ion. Therefore, for the first time, we experimentally report that an URS having OH-like reactivity can be formed during photochemical NDMA decomposition. This URS could contribute to the formations of NO(2)(-) and NO(3)(-). Copyright © 2012 Elsevier B.V. All rights reserved.

The Ascorbate-glutathione-α-tocopherol Triad in Abiotic Stress Response

PubMed Central

Szarka, András; Tomasskovics, Bálint; Bánhegyi, Gábor

2012-01-01

The life of any living organism can be defined as a hurdle due to different kind of stresses. As with all living organisms, plants are exposed to various abiotic stresses, such as drought, salinity, extreme temperatures and chemical toxicity. These primary stresses are often interconnected, and lead to the overproduction of reactive oxygen species (ROS) in plants, which are highly reactive and toxic and cause damage to proteins, lipids, carbohydrates and DNA, which ultimately results in oxidative stress. Stress-induced ROS accumulation is counteracted by enzymatic antioxidant systems and non-enzymatic low molecular weight metabolites, such as ascorbate, glutathione and α-tocopherol. The above mentioned low molecular weight antioxidants are also capable of chelating metal ions, reducing thus their catalytic activity to form ROS and also scavenge them. Hence, in plant cells, this triad of low molecular weight antioxidants (ascorbate, glutathione and α-tocopherol) form an important part of abiotic stress response. In this work we are presenting a review of abiotic stress responses connected to these antioxidants. PMID:22605990

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

Kelli Kazuberns; Sushil Gupta; Mihaela Grigore

Blast furnace efficiency may be improved by optimizing coke reactivity. Some but not all forms of mineral matter in the coke modify its reactivity, but changes in mineral matter that occur within coke while in the blast furnace have not been fully quantified. To determine changes in mineral matter forms in the blast furnace, coke samples from a dissection study in the LKAB experimental blast furnace (EBF) were characterized using SEM/EDS analysis, EPMA (microprobe), and low-temperature ashing/quantitative XRD analysis. Variations in alkali concentration, particularly potassium, dominated the compositional changes. At high concentrations of potassium, the mineral matter was largely potassium-bearingmore » but even more potassium was diffused throughout the coke and not associated with mineral matter. There was little difference in potassium concentration between the core and surface of the coke pieces, suggesting that potassium diffused rapidly through the whole coke. Iron, calcium, silicon, and aluminum concentrations were relatively constant in comparison, although the mineralogy of all elements changed significantly with changing temperature. 23 refs., 20 figs., 9 tabs.« less

Dispersoid reinforced alloy powder and method of making

DOEpatents

Anderson, Iver E; Rieken, Joel

2013-12-10

A method of making dispersion-strengthened alloy particles involves melting an alloy having a corrosion and/or oxidation resistance-imparting alloying element, a dispersoid-forming element, and a matrix metal wherein the dispersoid-forming element exhibits a greater tendency to react with an introduced reactive species than does the alloying element and wherein one or more atomizing parameters is/are modified to controllably reduce the amount of the reactive species, such as oxygen, introduced into the atomized particles so as to reduce anneal times and improve reaction (conversion) to the desired strengthening dispersoids in the matrix. The atomized alloy particles are solidified as solidified alloy particles or as a solidified deposit of alloy particles. Bodies are made from the dispersion strengthened alloy particles, deposit thereof, exhibit enhanced fatigue and creep resistance and reduced wear as well as enhanced corrosion and/or oxidation resistance at high temperatures by virtue of the presence of the corrosion and/or oxidation resistance imparting alloying element in solid solution in the particle alloy matrix.

The path to achieving molecular dispersion in an extremely dense reactive mixture

NASA Astrophysics Data System (ADS)

Patel, Jigneshkumar; Xiang, Zou; Hsu, Shaw; Schoch, Andrew

2015-03-01

In any multicomponent reactive system, a uniform and continuous dispersion of reactants is necessary to achieve a complete reaction. In this study, we have examined the role of one additional component to disperse two seemingly unlikely reactants, including a highly crystalline hexamethylenetetramine (hexa) and strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to decipher the role of specific intermolecular interactions in order for this additional component to dissolve the highly crystalline hexa and to plasticize the phenol formaldehyde resin in this crosslinking reaction. It is clear that the presence of the third component increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of hexa. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to understand the miscibility behavior of this multicomponent system. By designing the additional component to form a hydrogen bond with one or more N of the highly symmetric hexamethylenetetramine, it is then possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. The understanding of this system is applicable to a broad range of reactive systems.

Fracture Reactivation in Chemically Reactive Rock Systems

NASA Astrophysics Data System (ADS)

Eichhubl, P.; Hooker, J. N.

2013-12-01

Reactivation of existing fractures is a fundamental process of brittle failure that controls the nucleation of earthquake ruptures, propagation and linkage of hydraulic fractures in oil and gas production, and the evolution of fault and fracture networks and thus of fluid and heat transport in the upper crust. At depths below 2-3 km, and frequently shallower, brittle processes of fracture growth, linkage, and reactivation compete with chemical processes of fracture sealing by mineral precipitation, with precipitation rates similar to fracture opening rates. We recently found rates of fracture opening in tectonically quiescent settings of 10-20 μm/m.y., rates similar to euhedral quartz precipitation under these conditions. The tendency of existing partially or completely cemented fractures to reactivate will vary depending on strain rate, mineral precipitation kinetics, strength contrast between host rock and fracture cement, stress conditions, degree of fracture infill, and fracture network geometry. Natural fractures in quartzite of the Cambrian Eriboll Formation, NW Scotland, exhibit a complex history of fracture formation and reactivation, with reactivation involving both repeated crack-seal opening-mode failure and shear failure of fractures that formed in opening mode. Fractures are partially to completely sealed with crack-seal or euhedral quartz cement or quartz cement fragmented by shear reactivation. Degree of cementation controls the tendency of fractures for later shear reactivation, to interact elastically with adjacent open fractures, and their intersection behavior. Using kinematic, dynamic, and diagenetic criteria, we determine the sequence of opening-mode fracture formation and later shear reactivation. We find that sheared fracture systems of similar orientation display spatially varying sense of slip We attribute these inconsistent directions of shear reactivation to 1) a heterogeneous stress field in this highly fractured rock unit and 2) variations in the degree of fracture cement infill in fractures of same orientation, allowing fractures to reactivate at times when adjacent, more cemented fractures remain dormant. The observed interaction of chemical and mechanical fracture growth and sealing processes in this chemically reactive and heavily deformed rock unit results in a complex fracture network geometry not generally observed in less chemically reactive, shallower crustal environments.

Timing of isoclinal folds in multiply deformed high metamorphic grade region using FIA succession

NASA Astrophysics Data System (ADS)

Cao, Hui; Cai, Zhihui

2013-04-01

Multiply deformed and isoclinally folded interlayered high metamorphic grade gneisses and schists can be very difficult rocks for resolving early formed stratigraphic and structural relationships. When such rocks contain porphyroblasts a new approach is possible because of the way in which porphyroblast growth is affected by crenulation versus reactivation of compositional layering. The asymmetries of the overprinting foliations preserved as inclusion trails that define the FIAs can be used to investigate whether an enigmatic isoclinal fold is an antiform or synform. This approach also reveals when the fold first formed during the tectonic history of the region. Isoclinally folded rocks in the Arkansas River region of Central Colorado contain relics of fold hinges that have been very difficult to ascertain whether they are antiforms or synforms because of younger refolding effects and the locally truncated nature of coarse compositional layering. With the realization that rocks with a schistosity parallel to bedding (S0 parallel S1) have undergone lengthy histories of deformation that predate the obvious first deformation came recognition that large scale regional folds can form early during this process and be preserved throughout orogenesis. This extensive history is lost within the matrix because of reactivational shear on the compositional layering. However, it can be extracted by measuring FIAs. Recent work using this approach has revealed that the trends of axial planes of all map scale folds, when plotted on a rose diagram, strikingly reflect the FIA trends. That is, although it was demonstrated that the largest scale regional folds commonly form early in the total history, other folds can form and be preserved from subsequent destruction in the strain shadows of plutons or through the partitioning of deformation due to heterogeneities at depth.

Vacuum Plasma Spray Forming of Tungsten Lorentz Force Accelerator Components

NASA Technical Reports Server (NTRS)

Zimmerman, Frank R.

2001-01-01

The Vacuum Plasma Spray (VPS) Laboratory at NASA's Marshall Space Flight Center has developed and demonstrated a fabrication technique using the VPS process to form anode sections for a Lorentz force accelerator from tungsten. Lorentz force accelerators are an attractive form of electric propulsion that provides continuous, high-efficiency propulsion at useful power levels for such applications as orbit transfers or deep space missions. The VPS process is used to deposit refractory metals such as tungsten onto a graphite mandrel of the desired shape. Because tungsten is reactive at high temperatures, it is thermally sprayed in an inert environment where the plasma gun melts and accelerates the metal powder onto the mandrel. A three-axis robot inside the chamber controls the motion of the plasma spray torch. A graphite mandrel acts as a male mold, forming the required contour and dimensions of the inside surface of the anode. This paper describes the processing techniques, design considerations, and process development associated with the VPS forming of the Lorentz force accelerator.

Dissolved CO2 Increases Breakthrough Porosity in Natural Porous Materials.

PubMed

Yang, Y; Bruns, S; Stipp, S L S; Sørensen, H O

2017-07-18

When reactive fluids flow through a dissolving porous medium, conductive channels form, leading to fluid breakthrough. This phenomenon is caused by the reactive infiltration instability and is important in geologic carbon storage where the dissolution of CO 2 in flowing water increases fluid acidity. Using numerical simulations with high resolution digital models of North Sea chalk, we show that the breakthrough porosity is an important indicator of dissolution pattern. Dissolution patterns reflect the balance between the demand and supply of cumulative surface. The demand is determined by the reactive fluid composition while the supply relies on the flow field and the rock's microstructure. We tested three model scenarios and found that aqueous CO 2 dissolves porous media homogeneously, leading to large breakthrough porosity. In contrast, solutions without CO 2 develop elongated convective channels known as wormholes, with low breakthrough porosity. These different patterns are explained by the different apparent solubility of calcite in free drift systems. Our results indicate that CO 2 increases the reactive subvolume of porous media and reduces the amount of solid residual before reactive fluid can be fully channelized. Consequently, dissolved CO 2 may enhance contaminant mobilization near injection wellbores, undermine the mechanical sustainability of formation rocks and increase the likelihood of buoyance driven leakage through carbonate rich caprocks.

Heavy metal removal capacity of individual components of permeable reactive concrete

NASA Astrophysics Data System (ADS)

Holmes, Ryan R.; Hart, Megan L.; Kevern, John T.

2017-01-01

Permeable reactive barriers (PRBs) are a well-known technique for groundwater remediation using industrialized reactive media such as zero-valent iron and activated carbon. Permeable reactive concrete (PRC) is an alternative reactive medium composed of relatively inexpensive materials such as cement and aggregate. A variety of multimodal, simultaneous processes drive remediation of metals from contaminated groundwater within PRC systems due to the complex heterogeneous matrix formed during cement hydration. This research investigated the influence coarse aggregate, portland cement, fly ash, and various combinations had on the removal of lead, cadmium, and zinc in solution. Absorption, adsorption, precipitation, co-precipitation, and internal diffusion of the metals are common mechanisms of removal in the hydrated cement matrix and independent of the aggregate. Local aggregates can be used as the permeable structure also possessing high metal removal capabilities, however calcareous sources of aggregate are preferred due to improved removal with low leachability. Individual adsorption isotherms were linear or curvilinear up, indicating a preferred removal process. For PRC samples, metal saturation was not reached over the range of concentrations tested. Results were then used to compare removal against activated carbon and aggregate-based PRBs by estimating material costs for the remediation of an example heavy metal contaminated Superfund site located in the Midwestern United States, Joplin, Missouri.

Effective rate constants for nanostructured heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Hendy, Shaun; Gaston, Nicola; Zhang, Philip; Lund, Nat

2012-02-01

There is currently a high level of interest in the use of nanostructured materials for catalysis. For instance, gold, which is largely inert in the bulk, can exhibit strong catalytic activity when in nanoparticle form. With precious metal catalysts such as Pt and Pd in high demand, the use of these materials in nanoparticle form can also substantially reduce costs by exposure of more surface area for the same volume of material. When reactants are plentiful, the effective activity of a nanoparticulate catalyst will increase roughly with its surface area. However, under diffusion-limited conditions, the reactant must diffuse to active sites on the catalyst, so a high surface area and a high density of active sites may bring diminishing returns if reactant is consumed faster than it arrives. Here we apply a mathematical homogenisation approach to derive simple expressions for the effective reactivity of a nanostructured catalyst under diffusion limited conditions that relate the intrinsic rate constants of the surfaces presented by the catalyst to an effective rate constant. When highly active catalytic sites, such as step edges or other defects are present, we show that distinct limiting cases emerge depending on the degree of overlap of the reactant depletion zone about each site. In gases, the size of this depletion zone is approximately the mean free path, so the effective reactivity will depend on the structure of the catalyst on that scale. We discuss implications for the optimal design of nanoparticle catalysts.

PROCESS FOR THE PRODUCTION OF AN ACTIVATED FORM OF UO$sub 2$

DOEpatents

Polissar, M.J.

1957-09-24

A process for producing a highly active form of UO/sub 2/ characterized both by rapid oxidation in air and by rapid chlorination with CCl/sub 4/ vapor at an elevated temperature is reported. In accordance with the process, commercial UO/sub 2/, is subjected to a series of oxidation-reduction operations to produce a form of UC/sub 2/ of enhanced reactivity. By treatimg commercial UO/sub 2/ at a temperature between 335 and 485 deg C with methane, then briefly with an oxygen containing gas and followimg this by a second treatment with a methane containing gas, the original relatively stable charge of UO/sub 2/ will be transformed into an active form of UO/sub 2/.

α1-Antitrypsin Portland, a bioengineered serpin highly selective for furin: Application as an antipathogenic agent

PubMed Central

Jean, François; Stella, Kori; Thomas, Laurel; Liu, Gseping; Xiang, Yang; Reason, Andrew J.; Thomas, Gary

1998-01-01

The important role of furin in the proteolytic activation of many pathogenic molecules has made this endoprotease a target for the development of potent and selective antiproteolytic agents. Here, we demonstrate the utility of the protein-based inhibitor α1-antitrypsin Portland (α1-PDX) as an antipathogenic agent that can be used prophylactically to block furin-dependent cell killing by Pseudomonas exotoxin A. Biochemical analysis of the specificity of a bacterially expressed His- and FLAG-tagged α1-PDX (α1-PDX/hf) revealed the selectivity of the α1-PDX/hf reactive site loop for furin (Ki, 600 pM) but not for other proprotein convertase family members or other unrelated endoproteases. Kinetic studies show that α1-PDX/hf inhibits furin by a slow tight-binding mechanism characteristic of serpin molecules and functions as a suicide substrate inhibitor. Once bound to furin’s active site, α1-PDX/hf partitions with equal probability to undergo proteolysis by furin at the C-terminal side of the reactive center -Arg355-Ile-Pro-Arg358-↓ or to form a kinetically trapped SDS-stable complex with the enzyme. This partitioning between the complex-forming and proteolytic pathways contributes to the ability of α1-PDX/hf to differentially inhibit members of the proprotein convertase family. Finally, we propose a structural model of the α1-PDX-reactive site loop that explains the high degree of enzyme selectivity of this serpin and which can be used to generate small molecule furin inhibitors. PMID:9636142

Erythrocyte haemolysate interacts with ATP-Fe to form a complex containing iron, ATP and 13 800 MW polypeptide.

PubMed

Weaver, J; Zhan, H; Pollack, S

1993-01-01

Iron first entering the reticulocyte is bound to ATP in the low MW cytosolic pool; some is also 'loosely bound' to haemoglobin, coeluting with haemoglobin from a molecular sieve column though not incorporated into haem. When haemolysate is mixed with ATP-Fe in vitro a similar high MW iron-containing complex is formed: the ATP-Fe interacts with a non-haemoglobin constituent of the haemolysate to form a high MW ATP-Fe complex in which the ratio of ATP:Fe (originally 6:1) is reversed, so that the complex contains more iron than ATP. The high MW ATP-Fe complex is formed even when ATP is in 150-fold molar excess and is formed without detectable hydrolysis of the ATP. The activity of haemolysate in forming the high MW ATP-Fe complex is not diminished by dialysis; all of the activity is recovered in the haemoglobin-containing fraction obtained from an Ultrogel AcA 44 column. The activity does not derive from haemoglobin since 85% of the activity is removed when haemoglobin is purified from haemolysate with DEAE-Sephadex. The chelatable iron pool of the cell probably includes both the high MW ATP-Fe complex and low MW ATP-Fe. Shunting of ATP-Fe to a high MW aggregate reduces the amount of iron present in the highly reactive low MW form and thus probably serves to limit the formation of cell damaging radicals.

Efficient plasmid DNA cleavage by a mononuclear copper(II) complex.

PubMed

Sissi, Claudia; Mancin, Fabrizio; Gatos, Maddalena; Palumbo, Manlio; Tecilla, Paolo; Tonellato, Umberto

2005-04-04

The Cu(II) complex of the ligand all-cis-2,4,6-triamino-1,3,5-trihydroxycyclohexane (TACI) is a very efficient catalyst of the cleavage of plasmid DNA in the absence of any added cofactor. The maximum rate of degradation of the supercoiled plasmid DNA form, obtained at pH 8.1 and 37 degrees C, in the presence of 48 microM TACI.Cu(II), is 2.3 x 10(-3) s(-1), corresponding to a half-life time of only 5 min for the cleavage of form I (supercoiled) to form II (relaxed circular). The dependence of the rate of plasmid DNA cleavage from the TACI.Cu(II) complex concentration follows an unusual and very narrow bell-like profile, which suggests an high DNA affinity of the complexes but also a great tendency to form unreactive dimers. The reactivity of the TACI.Cu(II) complexes is not affected by the presence of several scavengers for reactive oxygen species or when measured under anaerobic conditions. Moreover, no degradation of the radical reporter Rhodamine B is observed in the presence of such complexes. These results are consistent with the operation of a prevailing hydrolytic pathway under the normal conditions used, although the failure to obtain enzymatic religation of the linearized DNA does not allow one to rule out the occurrence of a nonhydrolytic oxygen-independent cleavage. A concurrent oxidative mechanism becomes competitive upon addition of reductants or in the presence of high levels of molecular oxygen: under such conditions, in fact, a remarkable increase in the rate of DNA cleavage is observed.

Reactivity of He with ionic compounds under high pressure.

PubMed

Liu, Zhen; Botana, Jorge; Hermann, Andreas; Valdez, Steven; Zurek, Eva; Yan, Dadong; Lin, Hai-Qing; Miao, Mao-Sheng

2018-03-05

Until very recently, helium had remained the last naturally occurring element that was known not to form stable solid compounds. Here we propose and demonstrate that there is a general driving force for helium to react with ionic compounds that contain an unequal number of cations and anions. The corresponding reaction products are stabilized not by local chemical bonds but by long-range Coulomb interactions that are significantly modified by the insertion of helium atoms, especially under high pressure. This mechanism also explains the recently discovered reactivity of He and Na under pressure. Our work reveals that helium has the propensity to react with a broad range of ionic compounds at pressures as low as 30 GPa. Since most of the Earth's minerals contain unequal numbers of positively and negatively charged atoms, our work suggests that large quantities of He might be stored in the Earth's lower mantle.

Caracterisation of Titanium Nitride Layers Deposited by Reactive Plasma Spraying

NASA Astrophysics Data System (ADS)

Roşu, Radu Alexandru; Şerban, Viorel-Aurel; Bucur, Alexandra Ioana; Popescu, Mihaela; Uţu, Dragoş

2011-01-01

Forming and cutting tools are subjected to the intense wear solicitations. Usually, they are either subject to superficial heat treatments or are covered with various materials with high mechanical properties. In recent years, thermal spraying is used increasingly in engineering area because of the large range of materials that can be used for the coatings. Titanium nitride is a ceramic material with high hardness which is used to cover the cutting tools increasing their lifetime. The paper presents the results obtained after deposition of titanium nitride layers by reactive plasma spraying (RPS). As deposition material was used titanium powder and as substratum was used titanium alloy (Ti6Al4V). Macroscopic and microscopic (scanning electron microscopy) images of the deposited layers and the X ray diffraction of the coatings are presented. Demonstration program with layers deposited with thickness between 68,5 and 81,4 μm has been achieved and presented.

Microgravity

NASA Image and Video Library

2001-01-24

A 3 mm-diameter droplet of aluminum oxide, heated to 2371 deg. C (4,300 deg. F), is suspended in midair by six acoustic transducers. A gas jet (from the nozzle below the drop) helps position the drop for study, and a 500-watt laser melts the sample. Glasses made from aluminum oxide are highly promising for optical transmission and other properties. They are also highly reactive when molten. Containerless processing allows studies of how to form amorphous (glassy) rather than crystalline metal oxides. Credit: Bill Jellison, Containerless Research, Inc.

Amine-reactive forms of a luminescent diethylenetriaminepentaacetic acid chelate of terbium and europium: attachment to DNA and energy transfer measurements.

PubMed

Li, M; Selvin, P R

1997-01-01

An isothiocyanate form of a lanthanide chelate which is highly luminescent when bound to terbium or europium has been synthesized. The chelate consists of diethylenetriaminepentaacetic acid (DTPA) covalently joined to a chromophore, 7-amino-4-methyl-2(1H)-quinolinone (cs124), and to L-p-aminophenylalanine, in which the aromatic amine was further converted to an isothiocyanate group. Ethylenediamine was also used in place of aminophenylalanine, but the isothiocyanate formed from the aliphatic amine was significantly less reactive. Site-specific attachments to triglycine and to the 5' ends of amine-modified DNA oligomers have been made. In addition, as an alternative method of coupling to macromolecules, DTPA anhydride-cs124 can be used to react specifically with a 5' amine group on base-deprotected synthetic DNA oligomers. Synthesis and purification is relatively straightforward in both cases, and luminescent properties are favorable for several applications, including as nonisotopic labels, as long-lifetime alternatives to fluorophores in imaging and diagnostics and particularly as donors in luminescence resonance energy transfer. Energy transfer measurements are consistent with previously reported measurements using different attachment mechanisms.

Current Thoughts on Reactive Element Effects in Alumina-Forming Systems: In Memory of John Stringer

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

Naumenko, D.; Pint, B. A.; Quadakkers, W. J.

In memory of John Stringer (1934–2014), one of the leaders in studying the reactive element (RE) effects, this paper reviews the current status of understanding of the effect of RE dopants on high-temperature oxidation behavior, with an emphasis on recent research related to deploying alumina-forming alloys and coatings with optimal performance in commercial systems. Additionally, to the well-known interaction between indigenous sulfur and RE additions, effects have been observed with C, N, and O found in commercial alloys and coatings. While there are many similarities between alumina-forming alloys and coatings, the latter bring additional complicating factors such as the effectsmore » of O incorporation during thermal spraying MCrAlY coatings, coating roughness, and heat treatments that must be considered in optimizing the beneficial dopant addition. We can see analogies between RE effects in alloys and in the substrates beneath diffusion M–Al coatings. Recently, there has been more interest in the influence of mixed oxidant environments, since these may modify the manifestation of the RE effect. Some thoughts are provided on optimizing the RE benefit and modeling oxidation of RE-doped alloys.« less

Current Thoughts on Reactive Element Effects in Alumina-Forming Systems: In Memory of John Stringer

DOE PAGES

Naumenko, D.; Pint, B. A.; Quadakkers, W. J.

2016-05-06

In memory of John Stringer (1934–2014), one of the leaders in studying the reactive element (RE) effects, this paper reviews the current status of understanding of the effect of RE dopants on high-temperature oxidation behavior, with an emphasis on recent research related to deploying alumina-forming alloys and coatings with optimal performance in commercial systems. Additionally, to the well-known interaction between indigenous sulfur and RE additions, effects have been observed with C, N, and O found in commercial alloys and coatings. While there are many similarities between alumina-forming alloys and coatings, the latter bring additional complicating factors such as the effectsmore » of O incorporation during thermal spraying MCrAlY coatings, coating roughness, and heat treatments that must be considered in optimizing the beneficial dopant addition. We can see analogies between RE effects in alloys and in the substrates beneath diffusion M–Al coatings. Recently, there has been more interest in the influence of mixed oxidant environments, since these may modify the manifestation of the RE effect. Some thoughts are provided on optimizing the RE benefit and modeling oxidation of RE-doped alloys.« less

Selective derivatization and sequestration of ribose from a prebiotic mix.

PubMed

Springsteen, Greg; Joyce, Gerald F

2004-08-11

Observations regarding the catalytic potential of RNA and the role of RNA in biology have formed the basis for the "RNA world" hypothesis, which suggests that a genetic system based on self-replicating polyribonucleotides preceded modern biology. However, attempts to devise a realistic prebiotic synthesis of nucleic acids from simple starting materials have been plagued by problems of poor chemical selectivity, lack of stereo- and regiospecificity, and similar rates of formation and degradation of some of the key intermediates. For example, ribose would have been only a small component of a highly complex mix of sugars resulting from the condensation of formaldehyde in a prebiotic world. In addition, ribose is more reactive and degrades more rapidly compared with most other monosaccharides. This study demonstrates an approach for the preferential sequestration of ribose relative to other sugars that takes advantage of its greater reactivity. Cyanamide reacts especially rapidly with ribose to form a stable bicyclic adduct. This product crystallizes spontaneously in aqueous solution, whereas the corresponding products derived from threose, galactose, glucose, mannose, and each of the other pentoses do not. Furthermore, when employing a racemic mixture of d- and l-ribose, enantiomerically twinned crystals are formed that contain discrete homochiral domains.

Alcohol, Aldehydes, Adducts and Airways

PubMed Central

Sapkota, Muna; Wyatt, Todd A.

2015-01-01

Drinking alcohol and smoking cigarettes results in the formation of reactive aldehydes in the lung, which are capable of forming adducts with several proteins and DNA. Acetaldehyde and malondialdehyde are the major aldehydes generated in high levels in the lung of subjects with alcohol use disorder who smoke cigarettes. In addition to the above aldehydes, several other aldehydes like 4-hydroxynonenal, formaldehyde and acrolein are also detected in the lung due to exposure to toxic gases, vapors and chemicals. These aldehydes react with nucleophilic targets in cells such as DNA, lipids and proteins to form both stable and unstable adducts. This adduction may disturb cellular functions as well as damage proteins, nucleic acids and lipids. Among several adducts formed in the lung, malondialdehyde DNA (MDA-DNA) adduct and hybrid malondialdehyde-acetaldehyde (MAA) protein adducts have been shown to initiate several pathological conditions in the lung. MDA-DNA adducts are pre-mutagenic in mammalian cells and induce frame shift and base-pair substitution mutations, whereas MAA protein adducts have been shown to induce inflammation and inhibit wound healing. This review provides an insight into different reactive aldehyde adducts and their role in the pathogenesis of lung disease. PMID:26556381

Alcohol, Aldehydes, Adducts and Airways.

PubMed

Sapkota, Muna; Wyatt, Todd A

2015-11-05

Drinking alcohol and smoking cigarettes results in the formation of reactive aldehydes in the lung, which are capable of forming adducts with several proteins and DNA. Acetaldehyde and malondialdehyde are the major aldehydes generated in high levels in the lung of subjects with alcohol use disorder who smoke cigarettes. In addition to the above aldehydes, several other aldehydes like 4-hydroxynonenal, formaldehyde and acrolein are also detected in the lung due to exposure to toxic gases, vapors and chemicals. These aldehydes react with nucleophilic targets in cells such as DNA, lipids and proteins to form both stable and unstable adducts. This adduction may disturb cellular functions as well as damage proteins, nucleic acids and lipids. Among several adducts formed in the lung, malondialdehyde DNA (MDA-DNA) adduct and hybrid malondialdehyde-acetaldehyde (MAA) protein adducts have been shown to initiate several pathological conditions in the lung. MDA-DNA adducts are pre-mutagenic in mammalian cells and induce frame shift and base-pair substitution mutations, whereas MAA protein adducts have been shown to induce inflammation and inhibit wound healing. This review provides an insight into different reactive aldehyde adducts and their role in the pathogenesis of lung disease.

Synthesis of highly reactive subnano-sized zero-valent iron using smectite clay templates.

PubMed

Gu, Cheng; Jia, Hanzhong; Li, Hui; Teppen, Brian J; Boyd, Stephen A

2010-06-01

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH(4), resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of approximately 5 A. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the X-ray diffraction (XRD) results since the diameter of elemental Fe is 2.5 A. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene/non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnanoscale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, for example, as components of constructed reactive domains such as reactive caps for contaminated sediments.

Synthesis of Highly Reactive Subnano-sized Zero-valent Iron using Smectite Clay Templates

PubMed Central

Gu, Cheng; Jia, Hanzhang; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.

2010-01-01

A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH4, resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of discrete regions of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of ~ 5 Å. The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the XRD results since the diameter of elemental Fe is 2.5 Å. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene:non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnano-scale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, e.g. as components of constructed reactive domains such as reactive caps for contaminated sediments. PMID:20446730

High Concentrations of Angiopoietin-Like Protein 4 Detected in Serum from Patients with Rheumatoid Arthritis Can Be Explained by Non-Specific Antibody Reactivity.

PubMed

Makoveichuk, Elena; Ruge, Toralph; Nilsson, Solveig; Södergren, Anna; Olivecrona, Gunilla

2017-01-01

Angiopoietin-like protein 4 (ANGPTL4) is suggested to be a master regulator of plasma triglyceride metabolism. Our aim was to study whether the previously reported high levels of ANGPTL4 detected in serum from patients with rheumatoid arthritis (RA) by ELISA was due to any specific molecular form of this protein (oligomers, monomers or fragments). ANGPTL4 levels were first determined in serum from 68 RA patients and 43 age and sex matched control subjects and the mean values differed by a factor of 5.0. Then, ANGPTL4 was analyzed after size exclusion chromatography (SEC) of serum samples. With serum from one of the RA patients with high levels of ANGPTL4, the dominant reactivity was found in fractions corresponding to high-molecular weight proteins. In addition, a minor peak of reactivity eluting late from the column was found both in the patient and in controls. By the use of HeteroBlock®, and by careful selection of antibodies, we documented non-specific reactions for ANGPTL4 in 39% of samples from the RA patients, most likely due to cross-reactivity of the antibodies with rheumatoid factor (RF). The corresponding figure for control subjects was 6.3%. After corrections for non-specific reactions, the mean level of ANGPTL4 in serum from RA patients was still significantly higher than in control individuals (mean levels were 101±62 and 67±39 ng/ml respectively, P = 0.02). We re-analyzed samples from our previously published studies on ANGPL4 levels in patients on hemodialysis and patients with diabetes type 2. These samples did not show false positive reactions. The levels of ANGPTL4 were comparable to those detected previously.

10 CFR 71.55 - General requirements for fissile material packages.

Code of Federal Regulations, 2011 CFR

2011-01-01

... system so that, under the following conditions, maximum reactivity of the fissile material would be... to cause maximum reactivity consistent with the chemical and physical form of the material; and (4...

10 CFR 71.55 - General requirements for fissile material packages.

Code of Federal Regulations, 2013 CFR

2013-01-01

... system so that, under the following conditions, maximum reactivity of the fissile material would be... to cause maximum reactivity consistent with the chemical and physical form of the material; and (4...

10 CFR 71.55 - General requirements for fissile material packages.

Code of Federal Regulations, 2014 CFR

2014-01-01

... system so that, under the following conditions, maximum reactivity of the fissile material would be... to cause maximum reactivity consistent with the chemical and physical form of the material; and (4...

Towards Greater Specificity in Identifying Associations Among Interparental Aggression, Child Emotional Reactivity to Conflict, and Child Problems

PubMed Central

Davies, Patrick T.; Cicchetti, Dante; Martin, Meredith J.

2012-01-01

This study examined specific forms of emotional reactivity to conflict and temperamental emotionality as explanatory mechanisms in pathways among interparental aggression and child psychological problems. Participants of the multi-method, longitudinal study included 201 two-year-old children and their mothers who had experienced elevated violence in the home. Consistent with emotional security theory, autoregressive structural equation model analyses indicated that children’s fearful reactivity to conflict was the only consistent mediator in the associations among interparental aggression and their internalizing and externalizing symptoms one year later. Pathways remained significant across maternal and observer ratings of children’s symptoms and with the inclusion of other predictors and mediators, including children’s sad and angry forms of reactivity to conflict, temperamental emotionality, gender, and socioeconomic status. PMID:22716918

Nonquaternary Cholinesterase Reactivators.

DTIC Science & Technology

1982-08-30

c, a plot (not shown) of pKa versus Hammet substituent constant (a )42 is also linear and conforms p to equation (5) pKa - (7.63 ±0.02) - (.63 ±0.05...dissociates to the active oximate form, we have defined an effective bimolecular reactivation rate constant as in equation (6) keff ’ kb [1 + antilog(pKa...type 1 compounds generally exhibit low activity as reactivators. In terms of keff values [see equation (6)] for reactivation of ethyl methylphosphonyl

Prediction of Breakthrough Curves for Conservative and Reactive Transport from the Structural Parameters of Highly Heterogeneous Media

NASA Astrophysics Data System (ADS)

Hansen, S. K.; Haslauer, C. P.; Cirpka, O. A.; Vesselinov, V. V.

2016-12-01

It is desirable to predict the shape of breakthrough curves downgradient of a solute source from subsurface structural parameters (as in the small-perturbation macrodispersion theory) both for realistically heterogeneous fields, and at early time, before any sort of Fickian model is applicable. Using a combination of a priori knowledge, large-scale Monte Carlo simulation, and regression techniques, we have developed closed-form predictive expressions for pre- and post-Fickian flux-weighted solute breakthrough curves as a function of distance from the source (in integral scales) and variance of the log hydraulic conductivity field. Using the ensemble of Monte Carlo realizations, we have simultaneously computed error envelopes for the estimated flux-weighted breakthrough, and for the divergence of point breakthrough curves from the flux-weighted average, as functions of the predictive parameters. We have also obtained implied late-time macrodispersion coefficients for highly heterogeneous environments from the breakthrough statistics. This analysis is relevant for the modelling of reactive as well as conservative transport, since for many kinetic sorption and decay reactions, Laplace-domain modification of the breakthrough curve for conservative solute produces the correct curve for the reactive system.

Contrasting neural effects of aging on proactive and reactive response inhibition.

PubMed

Bloemendaal, Mirjam; Zandbelt, Bram; Wegman, Joost; van de Rest, Ondine; Cools, Roshan; Aarts, Esther

2016-10-01

Two distinct forms of response inhibition may underlie observed deficits in response inhibition in aging. We assessed whether age-related neurocognitive impairments in response inhibition reflect deficient reactive inhibition (outright stopping) or also deficient proactive inhibition (anticipatory response slowing), which might be particularly evident with high information load. We used functional magnetic resonance imaging in young (n = 25, age range 18-32) and older adults (n = 23, 61-74) with a stop-signal task. Relative to young adults, older adults exhibited impaired reactive inhibition (i.e., longer stop-signal reaction time) and increased blood oxygen level-dependent (BOLD) signal for successful versus unsuccessful inhibition in the left frontal cortex and cerebellum. Furthermore, older adults also exhibited impaired proactive slowing, but only as a function of information load. This load-dependent behavioral deficit was accompanied by a failure to increase blood oxygen level-dependent (BOLD) signal under high information load in lateral frontal cortex, presupplementary motor area and striatum. Our findings suggest that inhibitory deficits in older adults are caused both by reduced stopping abilities and by diminished preparation capacity during information overload. Copyright © 2016 Elsevier Inc. All rights reserved.

Asymmetric photoredox transition-metal catalysis activated by visible light.

PubMed

Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

2014-11-06

Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the 'green' synthesis of non-racemic chiral molecules.

Asymmetric photoredox transition-metal catalysis activated by visible light

NASA Astrophysics Data System (ADS)

Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

2014-11-01

Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the `green' synthesis of non-racemic chiral molecules.

Structural network heterogeneities and network dynamics: a possible dynamical mechanism for hippocampal memory reactivation.

NASA Astrophysics Data System (ADS)

Jablonski, Piotr; Poe, Gina; Zochowski, Michal

2007-03-01

The hippocampus has the capacity for reactivating recently acquired memories and it is hypothesized that one of the functions of sleep reactivation is the facilitation of consolidation of novel memory traces. The dynamic and network processes underlying such a reactivation remain, however, unknown. We show that such a reactivation characterized by local, self-sustained activity of a network region may be an inherent property of the recurrent excitatory-inhibitory network with a heterogeneous structure. The entry into the reactivation phase is mediated through a physiologically feasible regulation of global excitability and external input sources, while the reactivated component of the network is formed through induced network heterogeneities during learning. We show that structural changes needed for robust reactivation of a given network region are well within known physiological parameters.

Structural network heterogeneities and network dynamics: A possible dynamical mechanism for hippocampal memory reactivation

NASA Astrophysics Data System (ADS)

Jablonski, Piotr; Poe, Gina R.; Zochowski, Michal

2007-01-01

The hippocampus has the capacity for reactivating recently acquired memories and it is hypothesized that one of the functions of sleep reactivation is the facilitation of consolidation of novel memory traces. The dynamic and network processes underlying such a reactivation remain, however, unknown. We show that such a reactivation characterized by local, self-sustained activity of a network region may be an inherent property of the recurrent excitatory-inhibitory network with a heterogeneous structure. The entry into the reactivation phase is mediated through a physiologically feasible regulation of global excitability and external input sources, while the reactivated component of the network is formed through induced network heterogeneities during learning. We show that structural changes needed for robust reactivation of a given network region are well within known physiological parameters.

Formation and chemical reactivity of carbon fibers prepared by defluorination of graphite fluoride

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1994-01-01

Defluorination of graphite fluoride (CFX) by heating to temperatures of 250 to 450 C in chemically reactive environments was studied. This is a new and possibly inexpensive process to produce new carbon-based materials. For example, CF 0.68 fibers, made from P-100 carbon fibers, can be defluorinated in BrH2C-CH = CH-CH2Br (1,4-dibromo-2butene) heated to 370 C, and graphitized to produce fibers with an unusually high modulus and a graphite layer structure that is healed and cross-linked. Conversely, a sulfur-doped, visibly soft carbon fiber was produced by defluorinating CF 0.9 fibers, made from P-25, in sulfur (S) vapor at 370 C and then heating to 660 C in nitrogen (N2). Furthermore, defluorination of the CF 0.68 fibers in bromine (Br2) produced fragile, structurally damaged carbon fibers. Heating these fragile fibers to 1100 C in N2 caused further structural damage, whereas heating to 150 C in bromoform (CHBr3) and then to 1100 C in N2 healed the structural defects. The defluorination product of CFX, tentatively called activated graphite, has the composition and molecular structure of graphite, but is chemically more reactive. Activated graphite is a scavenger of manganese (Mn), and can be intercalated with magnesium (Mg). Also, it can easily collect large amounts of an alloy made from copper (Cu) and type 304 stainless steel to form a composite. Finally, there are indications that activated graphite can wet metals or ceramics, thereby forming stronger composites with them than the pristine carbon fibers can form.

Reactivity induced at 25 K by low-energy electron irradiation of condensed NH3-CH3COOD (1 : 1) mixture.

PubMed

Lafosse, Anne; Bertin, Mathieu; Domaracka, Alicja; Pliszka, Damian; Illenberger, Eugen; Azria, Roger

2006-12-21

Chemical reactivity is observed following electron irradiation of a binary mixture of ammonia (NH(3)) and acetic acid (CH(3)COOD) at 25 K, without any subsequent thermal activation, as evidenced by vibrational high resolution electron energy loss spectroscopy (HREELS). Analysis of the HREEL spectra and comparison with infrared and Raman data of different molecules are compatible with glycine formation in its zwitterionic form. The onset for electron induced reaction is found to be at about approximately 13 eV. The mechanisms may involve NH radicals interaction with CH(3)COOD molecules. Then glycine formation does not imply any displacement of reactants, so that it involves only NH(3) and CH(3)COOD neighboring molecules.

Raman Spectral Band Oscillations in Large Graphene Bubbles

NASA Astrophysics Data System (ADS)

Huang, Yuan; Wang, Xiao; Zhang, Xu; Chen, Xianjue; Li, Baowen; Wang, Bin; Huang, Ming; Zhu, Chongyang; Zhang, Xuewei; Bacsa, Wolfgang S.; Ding, Feng; Ruoff, Rodney S.

2018-05-01

Raman spectra of large graphene bubbles showed size-dependent oscillations in spectral intensity and frequency, which originate from optical standing waves formed in the vicinity of the graphene surface. At a high laser power, local heating can lead to oscillations in the Raman frequency and also create a temperature gradient in the bubble. Based on Raman data, the temperature distribution within the graphene bubble was calculated, and it is shown that the heating effect of the laser is reduced when moving from the center of a bubble to its edge. By studying graphene bubbles, both the thermal conductivity and chemical reactivity of graphene were assessed. When exposed to hydrogen plasma, areas with bubbles are found to be more reactive than flat graphene.

Pyrolysis process for producing condensed stabilized hydrocarbons utilizing a beneficially reactive gas

DOEpatents

Durai-Swamy, Kandaswamy

1982-01-01

In a process for recovery of values contained in solid carbonaceous material, the solid carbonaceous material is comminuted and then subjected to pyrolysis, in the presence of a carbon containing solid particulate source of heat and a beneficially reactive transport gas in a transport flash pyrolysis reactor, to form a pyrolysis product stream. The pyrolysis product stream contains a gaseous mixture and particulate solids. The solids are separated from the gaseous mixture to form a substantially solids-free gaseous stream which comprises volatilized hydrocarbon free radicals newly formed by pyrolysis. Preferably the solid particulate source of heat is formed by oxidizing part of the separated particulate solids. The beneficially reactive transport gas inhibits the reactivity of the char product and the carbon-containing solid particulate source of heat. Condensed stabilized hydrocarbons are obtained by quenching the gaseous mixture stream with a quench fluid which contains a capping agent for stabilizing and terminating newly formed volatilized hydrocarbon free radicals. The capping agent is partially depleted of hydrogen by the stabilization and termination reaction. Hydrocarbons of four or more carbon atoms in the gaseous mixture stream are condensed. A liquid stream containing the stabilized liquid product is then treated or separated into various fractions. A liquid containing the hydrogen depleted capping agent is hydrogenated to form a regenerated capping agent. At least a portion of the regenerated capping agent is recycled to the quench zone as the quench fluid. In another embodiment capping agent is produced by the process, separated from the liquid product mixture, and recycled.

Oxytocin receptor antagonist atosiban impairs consolidation, but not reconsolidation of contextual fear memory in rats.

PubMed

Abdullahi, Payman Rasise; Eskandarian, Sharaf; Ghanbari, Ali; Rashidy-Pour, Ali

2018-05-23

There is increasing evidence that oxytocin is involved in learning and memory process. This study investigated the effects of blockade of oxytocin receptors using the selective oxytocin receptor antagonist atosiban (ATO) on contextual fear memory consolidation and reconsolidation in male rats. Post-training injections of different doses of ATO (1, 10, 100 or 1000 µg/kg) impaired the 48 h retention performance in a dose-dependent manner. The same doses of ATO following memory reactivation did not impair subsequent expression of contextual fear memories which formed under low or high shock intensities and tested 24 h or one week following memory reactivation. Also, no effect was found when ATO was administrated in the absence of memory reactivation. Our finding is the first report that indicates endogenous oxytocin released during training play an important role in the consolidation, but not reconsolidation of contextual fear memory in rats. Copyright © 2018. Published by Elsevier B.V.

Recent Discoveries and Future Challenges in Atmospheric Organic Chemistry.

PubMed

Glasius, Marianne; Goldstein, Allen H

2016-03-15

Earth's atmosphere contains a multitude of organic compounds, which differ by orders of magnitude regarding fundamental properties such as volatility, reactivity, and propensity to form cloud droplets, affecting their impact on global climate and human health. Despite recent major research efforts and advances, there are still substantial gaps in understanding of atmospheric organic chemistry, hampering efforts to understand, model, and mitigate environmental problems such as aerosol formation in both polluted urban and more pristine regions. The analytical toolbox available for chemists to study atmospheric organic components has expanded considerably during the past decade, opening new windows into speciation, time resolution and detection of reactive and semivolatile compounds at low concentrations. This has provided unprecedented opportunities, but also unveiled new scientific challenges. Specific groundbreaking examples include the role of epoxides in aerosol formation especially from isoprene, the importance of highly oxidized, reactive organics in air-surface processes (whether atmosphere-biosphere exchange or aerosols), as well as the extent of interactions of anthropogenic and biogenic emissions and the resulting impact on atmospheric organic chemistry.

Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, G.L.

1984-05-18

A method for preparing reactive metal surfaces, particularly uranium surfaces is disclosed, whereby the metal is immediately reactive to hydrogen gas at room temperature and low pressure. The metal surfaces are first pretreated by exposure to an acid which forms an adherent hydride-bearing composition on the metal surface. Subsequent heating of the pretreated metal at a temperature sufficient to decompose the hydride coating in vacuum or inert gas renders the metal surface instantaneously reactive to hydrogen gas at room temperature and low pressure.

Cold Pad-Batch dyeing method for cotton fabric dyeing with reactive dyes using ultrasonic energy.

PubMed

Khatri, Zeeshan; Memon, Muhammad Hanif; Khatri, Awais; Tanwari, Anwaruddin

2011-11-01

Reactive dyes are vastly used in dyeing and printing of cotton fibre. These dyes have a distinctive reactive nature due to active groups which form covalent bonds with -OH groups of cotton through substitution and/or addition mechanism. Among many methods used for dyeing cotton with reactive dyes, the Cold Pad Batch (CPB) method is relatively more environment friendly due to high dye fixation and non requirement of thermal energy. The dyed fabric production rate is low due to requirement of at least twelve hours batching time for dye fixation. The proposed CPB method for dyeing cotton involves ultrasonic energy resulting into a one third decrease in batching time. The dyeing of cotton fibre was carried out with CI reactive red 195 and CI reactive black 5 by conventional and ultrasonic (US) method. The study showed that the use of ultrasonic energy not only shortens the batching time but the alkalis concentrations can considerably be reduced. In this case, the colour strength (K/S) and dye fixation (%F) also enhances without any adverse effect on colour fastness of the dyed fabric. The appearance of dyed fibre surface using scanning electron microscope (SEM) showed relative straightening of fibre convolutions and significant swelling of the fibre upon ultrasonic application. The total colour difference values ΔE (CMC) for the proposed method, were found within close proximity to the conventionally dyed sample. Copyright © 2011 Elsevier B.V. All rights reserved.

Powder-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

2016-05-03

A powder-based adsorbent and a related method of manufacture are provided. The powder-based adsorbent includes polymer powder with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the powder-based adsorbent includes irradiating polymer powder, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Powder-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Foam-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

2015-06-02

Foam-based adsorbents and a related method of manufacture are provided. The foam-based adsorbents include polymer foam with grafted side chains and an increased surface area per unit weight to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. A method for forming the foam-based adsorbents includes irradiating polymer foam, grafting with polymerizable reactive monomers, reacting with hydroxylamine, and conditioning with an alkaline solution. Foam-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Lower catecholamine activity is associated with greater levels of anger in adults.

PubMed

Schwartz, Joseph A; Portnoy, Jill

2017-10-01

Previous research has revealed a consistent association between heart rate at rest and during stress and behavioral problems, potentially implicating autonomic nervous system (ANS) functioning in the etiological development of antisocial behavior. A complementary line of research has focused on the potential independent and interactive role of the two subsystems that comprise the ANS, the parasympathetic nervous system (PNS) and the sympathetic nervous system (SNS), on behavioral problems. The current study aims to contribute to the existing literature by examining the influence of heart rate (HR) reactivity, high-frequency heart rate variability (HF-HRV) reactivity, and catecholamine activity on a comprehensive measure of anger in a large, nationally-representative sample of adults from the United States. Results from a series of structural equation models (SEMs) revealed that catecholamine activity was most consistently linked to anger, while associations involving HR and HF-HRV reactivity were nonsignificant. Additional analyses revealed that HF-HRV did not significantly moderate the association between catecholamine activity and anger. These findings highlight the importance of SNS activity in the development of more reactive forms of aggression such as anger. Copyright © 2017 Elsevier B.V. All rights reserved.

Mineral transformation and biomass accumulation associated with uranium bioremediation at Rifle, Colorado

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

Li, L.; Steefel, C.I.; Williams, K.H.

2009-04-20

Injection of organic carbon into the subsurface as an electron donor for bioremediation of redox-sensitive contaminants like uranium often leads to mineral transformation and biomass accumulation, both of which can alter the flow field and potentially bioremediation efficacy. This work combines reactive transport modeling with a column experiment and field measurements to understand the biogeochemical processes and to quantify the biomass and mineral transformation/accumulation during a bioremediation experiment at a uranium contaminated site near Rifle, Colorado. We use the reactive transport model CrunchFlow to explicitly simulate microbial community dynamics of iron and sulfate reducers, and their impacts on reaction rates.more » The column experiment shows clear evidence of mineral precipitation, primarily in the form of calcite and iron monosulfide. At the field scale, reactive transport simulations suggest that the biogeochemical reactions occur mostly close to the injection wells where acetate concentrations are highest, with mineral precipitate and biomass accumulation reaching as high as 1.5% of the pore space. This work shows that reactive transport modeling coupled with field data can be an effective tool for quantitative estimation of mineral transformation and biomass accumulation, thus improving the design of bioremediation strategies.« less

Mineral transformation and biomass accumulation associated with uranium bioremediation at Rifle, Colorado.

PubMed

Li, Li; Steefel, Carl I; Williams, Kenneth H; Wilkins, Michael J; Hubbard, Susan S

2009-07-15

Injection of organic carbon into the subsurface as an electron donor for bioremediation of redox-sensitive contaminants like uranium often leads to mineral transformation and biomass accumulation, both of which can alter the flow field and potentially bioremediation efficacy. This work combines reactive transport modeling with a column experiment and field measurements to understand the biogeochemical processes and to quantify the biomass and mineral transformation/accumulation during a bioremediation experiment at a uranium contaminated site near Rifle, Colorado. We use the reactive transport model CrunchFlow to explicitly simulate microbial community dynamics of iron and sulfate reducers, and their impacts on reaction rates. The column experiment shows clear evidence of mineral precipitation, primarily in the form of calcite and iron monosulfide. At the field scale, reactive transport simulations suggest that the biogeochemical reactions occur mostly close to the injection wells where acetate concentrations are highest, with mineral precipitate and biomass accumulation reaching as high as 1.5% of the pore space. This work shows that reactive transport modeling coupled with field data can bean effective tool for quantitative estimation of mineral transformation and biomass accumulation, thus improving the design of bioremediation strategies.

Comparison of DNA-Reactive Metabolites from Nitrosamine and Styrene Using Voltammetric DNA/Microsomes Sensors

PubMed Central

Krishnan, Sadagopan; Bajrami, Besnik; Mani, Vigneshwaran; Pan, Shenmin; Rusling, James F.

2012-01-01

Voltammetric sensors made with films of polyions, double-stranded DNA and liver microsomes adsorbed layer-by-layer onto pyrolytic graphite electrodes were evaluated for reactive metabolite screening. This approach features simple, inexpensive screening without enzyme purification for applications in drug or environmental chemical development. Cytochrome P450 enzymes (CYPs) in the liver microsomes were activated by an NADPH regenerating system or by electrolysis to metabolize model carcinogenic compounds nitrosamine and styrene. Reactive metabolites formed in the films were trapped as adducts with nucleobases on DNA. The DNA damage was detected by square-wave voltammetry (SWV) using Ru(bpy)32+ as a DNA-oxidation catalyst. These sensors showed a larger rate of increase in signal vs. reaction time for a highly toxic nitrosamine than for the moderately toxic styrene due to more rapid reactive metabolite-DNA adduct formation. Results were consistent with reported in vivo TD50 data for the formation of liver tumors in rats. Analogous polyion/ liver microsome films prepared on 500 nm silica nanoparticles (nanoreactors) and reacted with nitrosamine or styrene, provided LC-MS or GC analyses of metabolite formation rates that correlated well with sensor response. PMID:23100998

Effect of oxide films on hydrogen permeability of candidate Stirling engine heater head tube alloys

NASA Technical Reports Server (NTRS)

Schuon, S. R.; Misencik, J. A.

1981-01-01

The effect of oxide films developed in situ from CO/CO2 doped hydrogen on high pressure hydrogen permeability at 820 C was studied on N-155, A-286, IN 800, 19-9DL, Nitronic 40, HS-188, and IN 718 tubing in a Stirling materials simulator. The hydrogen permeability decreased with increasing dopant levels of CO or CO2 and corresponding decreases in oxide porosity. Minor reactive alloying elements strongly influenced permeability. At high levels of CO or CO2, a liquid oxide formed on alloys with greater than 50 percent Fe. This caused increased permeability. The oxides formed on the inside tube walls were analyzed and their effective permeabilities were calculated.

Reactive polymer fused deposition manufacturing

DOEpatents

Kunc, Vlastimil; Rios, Orlando; Love, Lonnie J.; Duty, Chad E.; Johs, Alexander

2017-05-16

Methods and compositions for additive manufacturing that include reactive or thermosetting polymers, such as urethanes and epoxies. The polymers are melted, partially cross-linked prior to the depositing, deposited to form a component object, solidified, and fully cross-linked. These polymers form networks of chemical bonds that span the deposited layers. Application of a directional electromagnetic field can be applied to aromatic polymers after deposition to align the polymers for improved bonding between the deposited layers.

Meso-Scale Experimental & Numerical Studies for Predicting Macro-scale Performance of Advanced Reactive Materials (ARMs)

DTIC Science & Technology

2015-04-01

of impact-initiated reactions in Ti-Al-B based reactive materials in the form of compacts of powders of different sizes and morphologies . The major...More specifically, the influence of material-inherent elastic/plastic properties and reactant configuration (e.g., porosity, morphology , spacing...materials in the form of compacts of powders of different sizes and morphologies . The major goal is to delineate how processes of localized deformation and

Reactivity and reactions to regulatory transparency in medicine, psychotherapy and counselling.

PubMed

McGivern, Gerry; Fischer, Michael D

2012-02-01

We explore how doctors, psychotherapists and counsellors in the U.K. react to regulatory transparency, drawing on qualitative research involving 51 semi-structured interviews conducted during 2008-10. We use the concept of 'reactivity mechanisms' (Espeland & Sauder, 2007) to explain how regulatory transparency disrupts practices through simplifying and decontextualizing them, altering practitioners' reflexivity, leading to defensive forms of practice. We make an empirical contribution by exploring the impact of transparency on doctors compared with psychotherapists and counsellors, who represent an extreme case due to their uniquely complex practice, which is particularly affected by this form of regulation. We make a contribution to knowledge by developing a model of reactivity mechanisms, which explains how clinical professionals make sense of media and professional narratives about regulation in ways that produce emotional reactions and, in turn, defensive reactivity to transparency. Copyright © 2011 Elsevier Ltd. All rights reserved.

Oxidative transformation of tunichromes - Model studies with 1,2-dehydro-N-acetyldopamine and N-acetylcysteine.

PubMed

Kuang, Qun F; Abebe, Adal; Evans, Jason; Sugumaran, Manickam

2017-08-01

Tunichromes are 1,2-dehydrodopa containing bioactive peptidyl derivatives found in blood cells of several tunicates. They have been implicated in metal sequestering, tunic formation, wound healing and defense reaction. Earlier studies conducted on these compounds indicate their extreme liability, high reactivity and easy oxidative polymerization. Their reactions are also complicated by the presence of multiple dehydrodopyl units. Since they have been invoked in crosslinking and covalent binding, to understand the reactivities of these novel compounds, we have taken a simple model compound that possess the tunichrome reactive group viz., 1,2-dehydro-N-acetyldopamine (Dehydro NADA) and examined its reaction with N-acetylcysteine in presence of oxygen under both enzymatic and nonenzymatic conditions. Ultraviolet and visible spectral studies of reaction mixtures containing dehydro NADA and N-acetylcysteine in different molar ratios indicated the production of side chain and ring adducts of N-acetylcysteine to dehydro NADA. Liquid chromatography and mass spectral studies supported this contention and confirmed the production of several different products. Mass spectral analysis of these products show the potentials of dehydro NADA to form side chain adducts that can lead to polymeric products. This is the first report demonstrating the ability of dehydro dopyl units to form adducts and crosslinks with amino acid side chains. Copyright © 2017 Elsevier Inc. All rights reserved.

High hardness BaCb-(BxOy/BN) composites with 3D mesh-like fine grain-boundary structure by reactive spark plasma sintering.

PubMed

Vasylkiv, Oleg; Borodianska, Hanna; Badica, Petre; Grasso, Salvatore; Sakka, Yoshio; Tok, Alfred; Su, Liap Tat; Bosman, Michael; Ma, Jan

2012-02-01

Boron carbide B4C powders were subject to reactive spark plasma sintering (also known as field assisted sintering, pulsed current sintering or plasma assisted sintering) under nitrogen atmosphere. For an optimum hexagonal BN (h-BN) content estimated from X-ray diffraction measurements at approximately 0.4 wt%, the as-prepared BaCb-(BxOy/BN) ceramic shows values of Berkovich and Vickers hardness of 56.7 +/- 3.1 GPa and 39.3 +/- 7.6 GPa, respectively. These values are higher than for the vacuum SPS processed B4C pristine sample and the h-BN -mechanically-added samples. XRD and electronic microscopy data suggest that in the samples produced by reactive SPS in N2 atmosphere, and containing an estimated amount of 0.3-1.5% h-BN, the crystallite size of the boron carbide grains is decreasing with the increasing amount of N2, while for the newly formed lamellar h-BN the crystallite size is almost constant (approximately 30-50 nm). BN is located at the grain boundaries between the boron carbide grains and it is wrapped and intercalated by a thin layer of boron oxide. BxOy/BN forms a fine and continuous 3D mesh-like structure that is a possible reason for good mechanical properties.

Trifluoperazine inhibits acetaminophen-induced hepatotoxicity and hepatic reactive nitrogen formation in mice and in freshly isolated hepatocytes.

PubMed

Banerjee, Sudip; Melnyk, Stepan B; Krager, Kimberly J; Aykin-Burns, Nukhet; McCullough, Sandra S; James, Laura P; Hinson, Jack A

2017-01-01

The hepatotoxicity of acetaminophen (APAP) occurs by initial metabolism to N-acetyl-p-benzoquinone imine which depletes GSH and forms APAP-protein adducts. Subsequently, the reactive nitrogen species peroxynitrite is formed from nitric oxide (NO) and superoxide leading to 3-nitrotyrosine in proteins. Toxicity occurs with inhibited mitochondrial function. We previously reported that in hepatocytes the nNOS (NOS1) inhibitor NANT inhibited APAP toxicity, reactive nitrogen and oxygen species formation, and mitochondrial dysfunction. In this work we examined the effect of trifluoperazine (TFP), a calmodulin antagonist that inhibits calcium induced nNOS activation, on APAP hepatotoxicity and reactive nitrogen formation in murine hepatocytes and in vivo . In freshly isolated hepatocytes TFP inhibited APAP induced toxicity, reactive nitrogen formation (NO, GSNO, and 3-nitrotyrosine in protein), reactive oxygen formation (superoxide), loss of mitochondrial membrane potential, decreased ATP production, decreased oxygen consumption rate, and increased NADH accumulation. TFP did not alter APAP induced GSH depletion in the hepatocytes or the formation of APAP protein adducts which indicated that reactive metabolite formation was not inhibited. Since we previously reported that TFP inhibits the hepatotoxicity of APAP in mice without altering hepatic APAP-protein adduct formation, we examined the APAP treated mouse livers for evidence of reactive nitrogen formation. 3-Nitrotyrosine in hepatic proteins and GSNO were significantly increased in APAP treated mouse livers and decreased in the livers of mice treated with APAP plus TFP. These data are consistent with a hypothesis that APAP hepatotoxicity occurs with altered calcium metabolism, activation of nNOS leading to increased reactive nitrogen formation, and mitochondrial dysfunction.

On the potential for CO2 mineral storage in continental flood basalts – PHREEQC batch- and 1D diffusion–reaction simulations

PubMed Central

2012-01-01

Continental flood basalts (CFB) are considered as potential CO2 storage sites because of their high reactivity and abundant divalent metal ions that can potentially trap carbon for geological timescales. Moreover, laterally extensive CFB are found in many place in the world within reasonable distances from major CO2 point emission sources. Based on the mineral and glass composition of the Columbia River Basalt (CRB) we estimated the potential of CFB to store CO2 in secondary carbonates. We simulated the system using kinetic dependent dissolution of primary basalt-minerals (pyroxene, feldspar and glass) and the local equilibrium assumption for secondary phases (weathering products). The simulations were divided into closed-system batch simulations at a constant CO2 pressure of 100 bar with sensitivity studies of temperature and reactive surface area, an evaluation of the reactivity of H2O in scCO2, and finally 1D reactive diffusion simulations giving reactivity at CO2 pressures varying from 0 to 100 bar. Although the uncertainty in reactive surface area and corresponding reaction rates are large, we have estimated the potential for CO2 mineral storage and identified factors that control the maximum extent of carbonation. The simulations showed that formation of carbonates from basalt at 40 C may be limited to the formation of siderite and possibly FeMg carbonates. Calcium was largely consumed by zeolite and oxide instead of forming carbonates. At higher temperatures (60 – 100 C), magnesite is suggested to form together with siderite and ankerite. The maximum potential of CO2 stored as solid carbonates, if CO2 is supplied to the reactions unlimited, is shown to depend on the availability of pore space as the hydration and carbonation reactions increase the solid volume and clog the pore space. For systems such as in the scCO2 phase with limited amount of water, the total carbonation potential is limited by the amount of water present for hydration of basalt. PMID:22697910

A large OH sink in summertime surface air of the northern Indo-Gangetic plain revealed through in-situ total OH Reactivity measurements

NASA Astrophysics Data System (ADS)

Kumar, V.; Garg, S.; Chandra, P.; Sinha, V.

2013-12-01

The summertime surface air in the Northern Indo-Gangetic plain is characterized by high temperatures (up to 47 oC) and strong solar radiation (up to 765 Watt/m2), which together with large urban and agricultural emissions in the densely populated region, lead to intense photochemistry. The hydroxyl radical (OH) is the primary atmospheric oxidant responsible for oxidizing gaseous emissions and hence direct measurements of the total OH reactivity are necessary for understanding reactive emission budgets and constraining instantaneous ozone production regimes. Here, we present the first dataset of direct OH reactivity measurements from a regional surface site in the northern India-Gangetic plain (30.667°N, 76.729°E; 310 m above mean sea level). The measurements were performed in April-May 2013 using the comparative reactivity method [1]. A single PTRMS was used for sequential measurements of the total OH reactivity and circa 20 ambient VOCs. Nitrogen oxides (NO and NO2), sulphur dioxide, carbon monoxide, ozone and meteorological parameters were measured concomitantly using the IISER Mohali atmospheric chemistry facility. Air masses impacting the site arrived from rural and agricultural regions at high wind speeds of up to 24 m/s. A large variability was observed in the diel hourly averaged OH reactivity spanning an interquartile range of 36 s-1 - 120 s-1. The daily average and median total OH reactivity was 76 s-1 and 73 s-1, respectively corresponding to average and median OH chemical lifetimes of 13.1 milliseconds and 13.6 milliseconds, respectively. The five highest individual OH sinks measured were: acetaldehyde > isoprene+furan > NO2 > trimethyl benzene > CO. The measured OH reactivity did not show a pronounced diel cycle but remarkably the highest missing OH reactivity fraction (> 50 %) was observed during afternoon hours (12-16 local time) on very sunny days with low RH. This suggests that a significant fraction of secondary oxidation products formed due to photochemical oxidation reactions remain unmeasured. Likely compounds that could help explain the missing OH reactivity but were not covered by the measurement suite during the study period will be discussed in the presentation. Employing the ratio of the measured OH reactivity due to VOCs and due to NOx respectively [2], the peak ozone production at the site currently appears to be limited by the availability of NOx. References 1. V. Sinha et al., The Comparative Reactivity Method - a new tool to measure total OH Reactivity in ambient air. Atmos. Chem. Phys, 2008: p. 2213-2227. 2. V. Sinha,et al., Constraints on instantaneous ozone production rates and regimes during DOMINO derived using in-situ OH reactivity measurements, Atmos. Chem. Phys., 12, 7269-7283, doi:10.5194/acp-12-7269-2012, 2012. Acknowledgements: We acknowledge financial support from MHRD, India, and IISER Mohali-MPI-DST partner group and thank Chinmoy Sarkar.

Probing ‘Spin-Forbidden’ Oxygen Atom Transfer: Gas-Phase Reactions of Chromium-Porphyrin Complexes

PubMed Central

Fornarini, Simonetta; Lanucara, Francesco; Warren, Jeffrey J.

2010-01-01

Oxygen-atom transfer reactions of metalloporphyrin species play an important role in biochemical and synthetic oxidation reactions. An emerging theme in this chemistry is that spin-state changes can play important roles, and a ‘two-state’ reactivity model has been extensively applied especially in iron-porphyrin systems. Herein we explore the gas phase oxygen-atom transfer chemistry of meso-tetrakis(pentafluorophenyl)porphyrin (TPFPP) chromium complexes, as well as some other tetradentate macrocyclic ligands. Electrospray ionization in concert with Fourier transform ion cyclotron resonance (FT-ICR) spectrometry has been used to characterize and observe reactivity of the ionic species [(TPFPP)CrIII]+ (1) and [(TPFPP)CrVO]+ (2). These are an attractive system to examine the effects of spin state change on oxygen atom transfer because the d1 CrV species are doublets while the CrIII complexes have quartet ground states with high-lying doublet excited states. In the gas phase, [(TPFPP)CrIII]+ forms adducts with a variety of neutral donors but O-atom transfer is only observed for NO2. Pyridine N-oxide adducts of 1 do yield 2 upon collision induced dissociation (CID), but the ethylene oxide, DMSO, and TEMPO analogs do not. [(TPFPP)CrVO]+ is shown by its reactivity and by CID experiments to be a terminal metal-oxo with a single vacant coordination site. It also displays limited reaction chemistry, being deoxygenated only by the very potent reductant P(OMe)3. In general, [(TPFPP)CrVO]+ species are much less reactive than the Fe and Mn analogs. Thermochemical analysis of the reactions points towards the involvement of spin issues in the lower observed reactivity of the chromium complexes. PMID:20218631

Carbon Nanotube Spaceframes for Low-Density Aerospace Materials

DTIC Science & Technology

2012-01-26

different types of oxidative etching chemistries have been reported in the literature, with acidic conditions such as nitric acid etching and piranha...and reduce the production of adhered fulvic acid species.1 A range of RCA type different etching conditions were investigated involving different...carboxylic and hydroxyl type sites together by first using a dicarboxylic acid (preferably in a highly reactive form such as oxalic chloride or succinic

High-temperature compatibility study of iridium (DOP-26 alloy) with graphite and plutonia

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

Axler, K.M.; Eash, D.T.

1987-12-01

This report outlines the materials compatibility tests conducted on DOP-26 iridium alloy and carbon. The carbon used was in the form of woven graphite as present in the impact shell used to encase plutonia in nuclear heat sources. In addition, compatibility tests of the DOP-26 alloy with plutonia are described. The reactivity observed in both systems is discussed. 4 refs., 6 figs.

Thermodynamic Constraints in Using AuM (M = Fe, Co, Ni, and Mo) Alloys as N₂ Dissociation Catalysts: Functionalizing a Plasmon-Active Metal.

PubMed

Martirez, John Mark P; Carter, Emily A

2016-02-23

The Haber-Bosch process for NH3 synthesis is arguably one of the greatest inventions of the 20th century, with a massive footprint in agriculture and, historically, warfare. Current catalysts for this reaction use Fe for N2 activation, conducted at high temperatures and pressures to improve conversion rate and efficiency. A recent finding shows that plasmonic metal nanoparticles can either generate highly reactive electrons and holes or induce resonant surface excitations through plasmonic decay, which catalyze dissociation and redox reactions under mild conditions. It is therefore appealing to consider AuM (M = Fe, Co, Ni, and Mo) alloys to combine the strongly plasmonic nature of Au and the catalytic nature of M metals toward N2 dissociation, which together might facilitate ammonia production. To this end, through density functional theory, we (i) explore the feasibility of forming these surface alloys, (ii) find a pathway that may stabilize/deactivate surface M substituents during fabrication, and (iii) define a complementary route to reactivate them under operational conditions. Finally, we evaluate their reactivity toward N2, as well as their ability to support a pathway for N2 dissociation with a low thermodynamic barrier. We find that AuFe possesses similar appealing qualities, including relative stability with respect to phase separation, reversibility of Fe oxidation and reduction, and reactivity toward N2. While AuMo achieves the best affinity toward N2, its strong propensity toward oxidation could greatly limit its use.

Various cross-reactivity of the grass pollen group 4 allergens: crystallographic study of the Bermuda grass isoallergen Cyn d 4.

PubMed

Huang, Tse-Hao; Peng, Ho-Jen; Su, Song-Nan; Liaw, Shwu-Huey

2012-10-01

The structure of Cyn d 4, the group 4 allergen from Bermuda grass, is reported at 2.15 Å resolution and is the first crystal structure of a naturally isolated pollen allergen. A conserved N-terminal segment that is only present in the large isoallergens forms extensive interactions with surrounding residues and hence greatly enhances the structural stability of the protein. Cyn d 4 contains an FAD cofactor that is covalently linked to His88 and Cys152. To date, all identified bicovalent flavoproteins are oxidases and their substrates are either sugars or secondary metabolites. A deep large hydrophobic substrate-binding cleft is present. Thus, Cyn d 4 may be an oxidase that is involved in the biosynthesis of a pollen-specific metabolite. Cyn d 4 shares ~70% sequence identity with the Pooideae group 4 allergens. Various cross-reactivities between grass pollen group 4 allergens have previously been demonstrated using sera from allergic patients. The protein surface displays an unusually large number of positively charged clusters, reflecting the high pI of ~10. 38 decapeptides that cover the solvent-accessible sequences did not show any significant IgE-binding activity using sera with high Cyn d 4 reactivity from four patients, suggesting that the IgE epitopes of Cyn d 4 are predominantly conformational in nature. Several group 4 structures were then modelled and their potential cross-reactive and species-specific IgE epitopes were proposed.

High pressure chemistry of red phosphorus by photo-activated simple molecules

NASA Astrophysics Data System (ADS)

Ceppatelli, M.; Fanetti, S.; Bini, R.; Caporali, M.; Peruzzini, M.

2014-05-01

High pressure (HP) is very effective in reducing intermolecular distances and inducing unexpected chemical reactions. In addition the photo-activation of the reactants in HP conditions can lead to very efficient and selective processes. The chemistry of phosphorus is currently based on the white molecular form. The red polymeric allotrope, despite more stable and much less toxic, has not attracted much attention so far. However, switching from the white to the red form would benefit any industrial procedure, especially from an environmental point of view. On the other side, water and ethanol are renewable, environmental friendly and largely available molecules, usable as reactants and photo-activators in HP conditions. Here we report a study on the HP photo-induced reactivity of red phosphorus with water and ethanol, showing the possibility of very efficient and selective processes, leading to molecular hydrogen and valuable phosphorus compounds. The reactions have been studied by means of FTIR and Raman spectroscopy and pressure has been generated using membrane Diamond (DAC) and Sapphire (SAC) anvil cells. HP reactivity has been activated by the two-photon absorption of near-UV wavelengths and occurred in total absence of solvents, catalysts and radical initiators, at room T and mild pressure conditions (0.2-1.5 GPa).

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China

NASA Astrophysics Data System (ADS)

Cheng, Yafang; Zheng, Guangjie; Wei, Chao; Mu, Qing; Zheng, Bo; Wang, Zhibin; Gao, Meng; Zhang, Qiang; Wang, Kebin; Carmichael, Gregory; Pöschl, Ulrich; Su, Hang

2017-04-01

Fine-particle pollution associated with winter haze threatens the health of more than 400 million people in the North China Plain. Sulfate is a major component of fine haze particles. Record sulfate concentrations of up to 300 μg m-3 were observed during the January 2013 winter haze event in Beijing. State-of-the-art air quality models that rely on sulfate production mechanisms requiring photochemical oxidants cannot predict these high levels because of the weak photochemistry activity during haze events. We find that the missing source of sulfate and particulate matter can be explained by reactive nitrogen chemistry in aerosol water. The aerosol water serves as a reactor, where the alkaline aerosol components trap SO2, which is oxidized by NO2 to form sulfate, whereby high reaction rates are sustained by the high neutralizing capacity of the atmosphere in northern China. This mechanism is self-amplifying because higher aerosol mass concentration corresponds to higher aerosol water content, leading to faster sulfate production and more severe haze pollution. Reference: Cheng, Y., Zheng, G., Wei, C., Mu, Q., Zheng, B., Wang, Z., Gao, M., Zhang, Q., He, K., Carmichael, G., Pöschl, U., and Su, H.: Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China, Science Advances, 2, 10.1126/sciadv.1601530, 2016.

Comparison of Reactive and Non-Reactive Spark Plasma Sintering Routes for the Fabrication of Monolithic and Composite Ultra High Temperature Ceramics (UHTC) Materials

PubMed Central

Orrù, Roberto; Cao, Giacomo

2013-01-01

A wider utilization of ultra high temperature ceramics (UHTC) materials strongly depends on the availability of efficient techniques for their fabrication as dense bodies. Based on recent results reported in the literature, it is possible to state that Spark Plasma Sintering (SPS) technology offers a useful contribution in this direction. Along these lines, the use of two different SPS-based processing routes for the preparation of massive UHTCs is examined in this work. One method, the so-called reactive SPS (R-SPS), consists of the synthesis and densification of the material in a single step. Alternatively, the ceramic powders are first synthesized by Self-propagating High-temperature Synthesis (SHS) and then sintered by SPS. The obtained results evidenced that R-SPS method is preferable for the preparation of dense monolithic products, while the sintering of SHS powders requires relatively milder conditions when considering binary composites. The different kinetic mechanisms involved during R-SPS of the monolithic and composite systems, i.e., combustion-like or gradual solid-diffusion, respectively, provides a possible explanation. An important role is also played by the SHS process, particularly for the preparation of composite powders, since stronger interfaces are established between the ceramic constituents formed in situ, thus favoring diffusion processes during the subsequent SPS step. PMID:28809229

Reactive Nitrogen Chemistry in Aerosol Water as a Source of Sulfate during Haze Events in China

NASA Astrophysics Data System (ADS)

Su, H.; Zheng, G.; Wei, C.; Mu, Q.; Zheng, B.; Wang, Z.; Zhang, Q.; Gao, M.; He, K.; Carmichael, G. R.; Poeschl, U.; Cheng, Y.

2017-12-01

Fine particle pollution associated with winter haze threatens the health of over 400 million people in the North China Plain. Sulfate is a major component of fine haze particles. Record sulfate concentrations up to 300 μg m-3 were observed during the January 2013 winter haze event in Beijing. State-of-the-art air quality models relying on sulfate production mechanisms that require photochemical oxidants, cannot predict these high levels due to the weak photochemistry activity during haze events. We find that the missing source of sulfate and particulate matter can be explained by reactive nitrogen chemistry in aerosol water. The aerosol water serves as a reactor where the alkaline aerosol components trap SO2, which is oxidized by NO2 to form sulfate, whereby high reaction rates are sustained by the high neutralizing capacity of the atmosphere in northern China. This mechanism is self-amplifying because higher aerosol mass concentration corresponds to higher aerosol water content leading to faster sulfate production and more severe haze pollution. Reference: Cheng, Y., Zheng, G., Wei, C., Mu, Q., Zheng, B., Wang, Z., Gao, M., Zhang, Q., He, K., Carmichael, G., Pöschl, U., and Su, H.: Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China, Science Advances, 2, 10.1126/sciadv.1601530, 2016.

High level of reduced glutathione contributes to detoxification of lipid peroxide-derived reactive carbonyl species in transgenic Arabidopsis overexpressing glutathione reductase under aluminum stress.

PubMed

Yin, Lina; Mano, Jun'ichi; Tanaka, Kiyoshi; Wang, Shiwen; Zhang, Meijuan; Deng, Xiping; Zhang, Suiqi

2017-10-01

Lipid peroxide-derived reactive carbonyl species (RCS), generated downstream of reactive oxygen species (ROS), are critical damage-inducing species in plant aluminum (Al) toxicity. In mammals, RCS are scavenged primarily by glutathione (reduced form of glutathione, GSH), but in plant Al stress, contribution of GSH to RCS detoxification has not been evaluated. In this study, Arabidopsis plants overexpressing the gene AtGR1 (accession code At3g24170), encoding glutathione reductase (GR), were generated, and their performance under Al stress was examined. These transgenic plants (GR-OE plants) showed higher GSH levels and GSH/GSSG (oxidized form of GSH) ratio, and an improved Al tolerance as they suffered less inhibition of root growth than wild-type under Al stress. Exogenous application of 4-hydroxy-2-nonenal, an RCS responsible for Al toxicity in roots, markedly inhibited root growth in wild-type plants. GR-OE plants suffered significantly smaller inhibition, indicating that the enhanced GSH level increased the capacity of RCS detoxification. The generation of H 2 O 2 due to Al stress in GR-OE plants was lower by 26% than in wild-type. Levels of various RCS, such as malondialdehyde, butyraldehyde, phenylacetaldehyde, (E)-2-heptenal and n-octanal, were suppressed by more than 50%. These results indicate that high levels of GSH and GSH/GSSG ratio by GR overexpression contributed to the suppression of not only ROS, but also RCS. Thus, the maintenance of GSH level by overexpressing GR reinforces dual detoxification functions in plants and is an efficient approach to enhance Al tolerance. © 2017 Scandinavian Plant Physiology Society.

A Three-Step Atomic Layer Deposition Process for SiN x Using Si2Cl6, CH3NH2, and N2 Plasma.

PubMed

Ovanesyan, Rafaiel A; Hausmann, Dennis M; Agarwal, Sumit

2018-06-06

We report a novel three-step SiN x atomic layer deposition (ALD) process using Si 2 Cl 6 , CH 3 NH 2 , and N 2 plasma. In a two-step process, nonhydrogenated chlorosilanes such as Si 2 Cl 6 with N 2 plasmas lead to poor-quality SiN x films that oxidize rapidly. The intermediate CH 3 NH 2 step was therefore introduced in the ALD cycle to replace the NH 3 plasma step with a N 2 plasma, while using Si 2 Cl 6 as the Si precursor. This three-step process lowers the atomic H content and improves the film conformality on high-aspect-ratio nanostructures as Si-N-Si bonds are formed during a thermal CH 3 NH 2 step in addition to the N 2 plasma step. During ALD, the reactive surface sites were monitored using in situ surface infrared spectroscopy. Our infrared spectra show that, on the post-N 2 plasma-treated SiN x surface, Si 2 Cl 6 reacts primarily with the surface -NH 2 species to form surface -SiCl x ( x = 1, 2, or 3) bonds, which are the reactive sites during the CH 3 NH 2 cycle. In the N 2 plasma step, reactive -NH 2 surface species are created because of the surface H available from the -CH 3 groups. At 400 °C, the SiN x films have a growth per cycle of ∼0.9 Å with ∼12 atomic percent H. The films grown on high-aspect-ratio nanostructures have a conformality of ∼90%.

Factors Influencing the Stability of Au-Incorporated Metal-Oxide Supported Thin Films for Optical Gas Sensing

DOE PAGES

Baltrus, John P.; Holcomb, Gordon R.; Tylczak, Joseph H.; ...

2017-02-24

There is interest in using Au-nanoparticle incorporated oxide films as functional sensor layers for high-temperature applications in optical-based sensors for measurements in both highly-oxidizing and highly-reducing atmospheres at temperatures approaching 900°C-1000°C because of a relatively high melting temperature combined with the inert nature of Au nanoparticles. This study includes a systematic series of experiments and theoretical calculations targeted at further understanding stability of Au-nanoparticle incorporated TiO 2 films as archetype sensing materials. A combination of thermodynamic modeling and long-term exposure tests were utilized to unambiguously determine that gas stream composition-dependent reactive evaporation of Au (to form predominately Au(g) or AuH(g),more » depending upon the environment) at the surface of the nanoparticles is the dominant mechanism for mass loss of Au. Primary factors dictating the rate of reactive evaporation, and hence the associated film stability, were determined to be the gas stream temperature and the concentration of H 2, with the former playing a more significant role over the ranges of temperatures (700°C - 800°C) and H 2 concentrations (1% to 29% H 2 by volume) explored. The mitigation of Au-mass loss through reactive evaporation was also successfully demonstrated by depositing a SiO 2 overlayer on the Au-nanoparticle embedded films to prevent direct Au-nanoparticle/vapor-phase contact.« less

Factors Influencing the Stability of Au-Incorporated Metal-Oxide Supported Thin Films for Optical Gas Sensing

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

Baltrus, John P.; Holcomb, Gordon R.; Tylczak, Joseph H.

There is interest in using Au-nanoparticle incorporated oxide films as functional sensor layers for high-temperature applications in optical-based sensors for measurements in both highly-oxidizing and highly-reducing atmospheres at temperatures approaching 900°C-1000°C because of a relatively high melting temperature combined with the inert nature of Au nanoparticles. This study includes a systematic series of experiments and theoretical calculations targeted at further understanding stability of Au-nanoparticle incorporated TiO 2 films as archetype sensing materials. A combination of thermodynamic modeling and long-term exposure tests were utilized to unambiguously determine that gas stream composition-dependent reactive evaporation of Au (to form predominately Au(g) or AuH(g),more » depending upon the environment) at the surface of the nanoparticles is the dominant mechanism for mass loss of Au. Primary factors dictating the rate of reactive evaporation, and hence the associated film stability, were determined to be the gas stream temperature and the concentration of H 2, with the former playing a more significant role over the ranges of temperatures (700°C - 800°C) and H 2 concentrations (1% to 29% H 2 by volume) explored. The mitigation of Au-mass loss through reactive evaporation was also successfully demonstrated by depositing a SiO 2 overlayer on the Au-nanoparticle embedded films to prevent direct Au-nanoparticle/vapor-phase contact.« less

Gyrate erythema in the setting of tinea pedis.

PubMed

Myers, Kathryn; Terushkin, Vitaly; Meehan, Shane A; Cohen, David E

2016-12-15

Gyrate erythema, which also is known as erythemaannulare centrifugum (EAC), is a reactive dermatitisthat is thought to occur in response to an underlyingtrigger. The superficial form is characterized bythe typical, centrifugally-expanding, annular,erythematous patches or plaques with a distincttrailing scale. The deep form also is a centrifugallyexpanding,erythematous plaque but with induratedborders and absence of scale. These cutaneousfindings are thought to be reactive, most often inresponse to infections or drugs and, less likely, tounderlying malignant conditions.

In situ creation of reactive polymer nanoparticles and resulting polymer layers formed at the interfaces of liquid crystals (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kang, Shin-Woong; Kundu, Sudarshan; Park, Heung-Shik; Oh, Keun Chan; Lyu, Jae Jin

2017-02-01

We report the in situ creation of reactive polymer nanoparticles and resulting polymer networks formed at the interfaces of liquid crystals. It is known that polymerization-induced phase separation proceeds in two distinct regimes depending on the concentration of monomer. For a high monomer concentration, phase separation occurs mainly through the spinodal decomposition process, consequently resulting in interpenetrating polymer networks. For a dilute system, however, the phase separation mainly proceeds and completes in the binodal decomposition regime. The system resembles the aggregation process of colloidal particle. In this case, the reaction kinetics is limited by the reaction between in situ created polymer aggregates and hence the network morphologies are greatly influenced by the diffusion of reactive polymer particles. The thin polymer layers localized at the surface of substrate are inevitably observed and can be comprehended by the interfacial adsorption and further cross-linking reaction of reactive polymer aggregates at the interface. This process provides a direct perception on understanding polymer stabilized liquid crystals accomplished by the interfacial polymer layer. The detailed study has been performed for an extremely dilute condition (below 0.5 wt%) by employing systematic experimental approaches. Creation and growth of polymer nanoparticles have been measured by particle size analyzer. The interfacial localization of polymer aggregates and resulting interfacial layer formation with a tens of nanometer scale have been exploited at various interfaces such as liquid-solid, liquid-liquid, and liquid-gas interfaces. The resulting interfacial layers have been characterized by using fuorescent confocal microscope and field emission scanning electron microscope. The detailed processes of the polymer stabilized vertically aligned liquid crystals will be discussed in support of the reported study.

Composition and molecular scale structure of nanophases formed by precipitation of biotite weathering products

NASA Astrophysics Data System (ADS)

Tamrat, Wuhib Zewde; Rose, Jérôme; Grauby, Olivier; Doelsch, Emmanuel; Levard, Clément; Chaurand, Perrine; Basile-Doelsch, Isabelle

2018-05-01

Because of their large surface area and reactivity, nanometric-size soil mineral phases have a high potential for soil organic matter stabilization, contaminant sorption or soil aggregation. In the literature, Fe and Al phases have been the main targets of batch-synthesized nanomineral studies while nano-aluminosilicates (Al and Si phases) have been mainly studied in Andic soils. In the present work, we synthesized secondary nanophases of Fe, Al and Si. To simulate a system as close as possible to soil conditions, we conducted laboratory simulations of the processes of (1) biotite alteration in acidic conditions producing a Al Si Fe Mg K leachate solution and (2) the following neoformation of secondary nanophases by titrating the leachate solution to pH 4.2, 5 and 7. The morphology of the nanophases, their size, crystallinity and chemistry were characterized by TEM-EDX on single particles and their local atomic structure by EXAFS (Extended X-ray Absorption Fine Structure) at the Fe absorption K-edge. The main nanophases formed were amorphous particles 10-60 nm in size whose composition (dominated by Fe and Si) was strongly controlled by the pH conditions at the end of the titration. At pH 4.2 and pH 7, the structure of the nanophases was dominated by the polymerization of Fe, which was hindered by Al, Si, Mg and K. Conversely, at pH 5, the polymerization of Fe was counteracted by precipitation of high amounts of Si. The synthetized nanophases were estimated to be rather analogous to nanophases formed in natural biotite-bearing soils. Because of their small size and potential high surface reactivity, the adsorption capacities of these nanophases with respect to the OM should be revisited in the framework of soil C storage.

STEAM FORMING NEUTRONIC REACTOR AND METHOD OF OPERATING IT

DOEpatents

Untermyer, S.

1960-05-10

The heterogeneous reactor is liquid moderated and cooled by a steam forming coolant and is designed to produce steam from the coolant directly within the active portion of the reactor while avoiding the formation of bubbles in the liquid moderator. This reactor achieves inherent stability as a result of increased neutron leakage and increased neutron resonance absorption in the U/sup 238/ fuel with the formation of bubbles. The invention produces certain conditions under which the formation of vapor bubbles as a result of a neutron flux excursion from the injection of a reactivity increment into the reactor will operate to nullify the reactivity increment within a sufficiently short period of time to prevent unsafe reactor operating conditions from developing. This is obtained by disposing a plurality of fuel elements within a mass of steam forming coolant in the core with the ratio of the volume of steam forming coolant to the volume of fissionable isotopes being within the range yielding a multiplication factor greater than unity and a negative reactivity to core void coefficient at the boiling temperature of the coolant.

High temperature surface protection. [10 gas turbines

NASA Technical Reports Server (NTRS)

Levine, S. R.

1978-01-01

Alloys of the MCrAlX type are the basis for high temperature surface protection systems in gas turbines. M can be one or more of Ni, Co, or Fe and X denotes a reactive metal added to enhance oxide scale adherence. The selection and formation as well as the oxidation, hot corrosion and thermal fatigue performance of MCrAlX coatings are discussed. Coatings covered range from simple aluminides formed by pack cementation to the more advanced physical vapor deposition overlay coatings and developmental plasma spray deposited thermal barrier coatings.

Exploring Flow Procedures for Diazonium Formation.

PubMed

Hu, Te; Baxendale, Ian R; Baumann, Marcus

2016-07-14

The synthesis of diazonium salts is historically an important transformation extensively utilized in dye manufacture. However the highly reactive nature of the diazonium functionality has additionally led to the development of many new reactions including several carbon-carbon bond forming processes. It is therefore highly desirable to determine optimum conditions for the formation of diazonium compounds utilizing the latest processing tools such as flow chemistry to take advantage of the increased safety and continuous manufacturing capabilities. Herein we report a series of flow-based procedures to prepare diazonium salts for subsequent in-situ consumption.

Pilot Plant Makes Oxygen Difluoride

NASA Technical Reports Server (NTRS)

Humphrey, Marshall F.; Lawton, Emil A.

1989-01-01

Pilot plant makes oxygen difluoride highly-energetic, space-storable oxidizer not made commercially. Designed to handle reactants, product, and byproduct, most of which highly reactive, corrosive, and toxic. Oxygen difluoride evolves continuously from reactor containing potassium hydroxide in water at 10 degree C. Collection tanks alternated; one filled while other drained to storage cylinder. Excess OF2 and F2 dissipated in combustion of charcoal in burn barrel. Toxic byproduct, potassium fluoride, reacted with calcium hydroxide to form nontoxic calcium fluoride and to regenerate potassium hydroxide. Equipment processes toxic, difficult-to-make substance efficiently and safely.

Making mushy magma chambers in the lower continental crust: Cold storage and compositional bimodality

NASA Astrophysics Data System (ADS)

Jackson, Matthew; Blundy, Jon; Sparks, Steve

2017-04-01

Increasing geological and geophysical evidence suggests that crustal magma reservoirs are normally low melt fraction 'mushes' rather than high melt fraction 'magma chambers'. Yet high melt fractions must form within these mush reservoirs to explain the observed flow and eruption of low crystallinity magmas. In many models, crystallinity is linked directly to temperature, with higher temperature corresponding to lower crystallinity (higher melt fraction). However, increasing temperature yields less evolved (silicic) melt composition for a given starting material. If mobile, low crystallinity magmas require high temperature, it is difficult to explain how they can have evolved composition. Here we use numerical modelling to show that reactive melt flow in a porous and permeable mush reservoir formed by the intrusion of numerous basaltic sills into the lower continental crust produces magma in high melt fraction (> 0.5) layers akin to conventional magma chambers. These magma-chamber-like layers contain evolved (silicic) melt compositions and form at low (close to solidus) temperatures near the top of the mush reservoir. Evolved magma is therefore kept in 'cold storage' at low temperature, but also at low crystallinity so the magma is mobile and can leave the mush reservoir. Buoyancy-driven reactive flow and accumulation of melt in the mush reservoir controls the temperature and composition of magma that can leave the reservoir. The modelling also shows that processes in lower crustal mush reservoirs produce mobile magmas that contain melt of either silicic or mafic composition. Intermediate melt compositions are present but are not within mobile magmas. Silicic melt compositions are found at high melt fraction within the magma-chamber like layers near the top of the mush reservoir. Mafic melt compositions are found at high melt fraction within the cooling sills. Melt elsewhere in the reservoir has intermediate composition, but remains trapped in the reservoir because the local melt fraction is too low to form a mobile magma. The model results are consistent with geochemical data suggesting that lower crustal magma reservoirs supply silicic and mafic melts to arc volcanoes, but intermediate magmas are formed by mixing in shallower reservoirs. We suggest here that lower crustal magma chambers primarily form in response to changes in bulk composition caused by melt migration and chemical reaction in a mush reservoir. This process is different to the conventional and widely applied models of magma chamber formation. Similar processes are likely to operate in shallow mush reservoirs, but will likely be further complicated by the presence of volatile phases, and mixing of different melt compositions sourced from deeper mush reservoirs.

Vacuum Plasma Spray Forming of Tungsten Lorentz Force Accelerator Components

NASA Technical Reports Server (NTRS)

Zimmerman, Frank R.

2004-01-01

The Vacuum Plasma Spray (VPS) Laboratory at NASA's Marshall Space Flight Center, working with the Jet Propulsion Laboratory, has developed and demonstrated a fabrication technique using the VPS process to form anode and cathode sections for a Lorentz force accelerator made from tungsten. Lorentz force accelerators are an attractive form of electric propulsion that provides continuous, high-efficiency propulsion at useful power levels for such applications as orbit transfers or deep space missions. The VPS process is used to deposit refractory metals such as tungsten onto a graphite mandrel of the desired shape. Because tungsten is reactive at high temperatures, it is thermally sprayed in an inert environment where the plasma gun melts and deposits the molten metal powder onto a mandrel. A three-axis robot inside the chamber controls the motion of the plasma spray torch. A graphite mandrel acts as a male mold, forming the required contour and dimensions for the inside surface of the anode or cathode of the accelerator. This paper describes the processing techniques, design considerations, and process development associated with the VPS forming of Lorentz force accelerator components.

Hydrolysis of the quinone methide of butylated hydroxytoluene in aqueous solutions.

PubMed

Willcockson, Maren Gulsrud; Toteva, Maria M; Stella, Valentino J

2013-10-01

Butylated hydroxytoluene or BHT is an antioxidant commonly used in pharmaceutical formulations. BHT upon oxidation forms a quinone methide (QM). QM is a highly reactive electrophilic species that can undergo nucleophilic addition. Here, the kinetic reactivity of QM with water at various apparent pH values in a 50% (v/v) water-acetonitrile solution at constant ionic strength of I = 0.5 (NaCl)4 , was studied. The hydrolysis of QM in the presence of added acid, base, sodium chloride, and phosphate buffer resulted in the formation of only one product--the corresponding 3,5-di-tert-butyl-4-hydroxybenzyl alcohol (BA). The rate of BA formation was catalyzed by the addition of acid and base, but not chloride and phosphate species. Nucleophilic excipients, used in the pharmaceutical formulation, or nucleophilic groups on active pharmaceutical ingredient molecule may form adducts with QM, the immediate oxidative product of BHT degradation, thus having implications for drug product impurity profiles. Because of these considerations, BHT should be used with caution in formulations containing drugs or excipients capable of acting as nucleophiles. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Microstructure evolution of Al-doped zinc oxide films prepared by in-line reactive mid-frequency magnetron sputtering

NASA Astrophysics Data System (ADS)

Hong, R. J.; Jiang, X.

2006-07-01

Aluminium-doped zinc oxide (ZnO:Al or AZO) thin films were deposited on glass substrates by reactive mid-frequency (MF) magnetron sputtering from Zn/Al metallic targets. Strong (002) preferred orientation was detected by X-ray diffraction (XRD). It was observed by plan-view transmission electron microscopy (TEM) that an AZO film deposited at low substrate temperature was composed of irregular large grains; but the film prepared at high temperature was composed of moderate sized grains with a regular shape. A secondary phase of ZnO2 was also observed for the film deposited at low substrate temperature. The cross-sectional TEM study of the AZO film showed that prior to the well-aligned columnar growth an initial interfacial zone with nano crystallites were formed. The nano crystallites formed initially with a large tilt angle normal to the substrate surface and during the growth of the transition zone, the tilt angle decreased until it vanished. The evolution of the film structure is discussed in terms of evolutionary selection model and the dynamic deposition process.

Fullerene C60 and graphene photosensibiles for photodynamic virus inactivation

NASA Astrophysics Data System (ADS)

Belousova, I.; Hvorostovsky, A.; Kiselev, V.; Zarubaev, V.; Kiselev, O.; Piotrovsky, L.; Anfimov, P.; Krisko, T.; Muraviova, T.; Rylkov, V.; Starodubzev, A.; Sirotkin, A.; Grishkanich, A.; Kudashev, I.; Kancer, A.; Kustikova, M.; Bykovskaya, E.; Mayurova, A.; Stupnikov, A.; Ruzankina, J.; Afanasyev, M.; Lukyanov, N.; Redka, D.; Paklinov, N.

2018-02-01

A solid-phase photosensitizer based on aggregated C60 fullerene and graphene oxide for photodynamic inactivation of pathogens in biological fluids was studied. The most promising technologies of inactivation include the photodynamic effect, which consists in the inactivation of infectious agents by active oxygen forms (including singlet oxygen), formed when light is activated by the photosensitizer introduced into the plasma. Research shows features of solid-phase systems based on graphene and fullerene C60 oxide, which is a combination of an effective inactivating pathogens (for example, influenza viruses) reactive oxygen species formed upon irradiation of the photosensitizer in aqueous and biological fluids, a high photostability fullerene coatings and the possibility of full recovery photosensitizer from the biological environment after the photodynamic action.

S-ovalbumin, an ovalbumin conformer with properties analogous to those of loop-inserted serpins.

PubMed Central

Huntington, J. A.; Patston, P. A.; Gettins, P. G.

1995-01-01

Most serpins are inhibitors of serine proteinases and are thought to undergo a conformational change upon complex formation with proteinase that involves partial insertion of the reactive center loop into a beta-sheet of the inhibitor. Ovalbumin, although a serpin, is not an inhibitor of serine proteinases. It has been proposed that this deficiency arises from the presence of a charged residue, arginine, at a critical point (P14) in the reactive center region, which prevents loop insertion into the beta-sheet and thereby precludes inhibitory properties. To test whether loop insertion is prevented in ovalbumin we have examined the properties of two forms of ovalbumin: the native protein and S-ovalbumin, a form that forms spontaneously from native ovalbumin and has increased stability. Calorimetric measurements showed that S-ovalbumin was more stable than ovalbumin by about 3 kcal mol-1. CD spectra, which indicated that S-ovalbumin had less alpha-helix than native ovalbumin, and 1H NMR spectra, which indicated very similar overall structures, suggest limited conformational differences between the two forms. From comparison of the susceptibility of the reactive center region of each protein to proteolysis by porcine pancreatic elastase and by subtilisin Carlsberg, we concluded that the limited native-to-S conformational change specifically affected the reactive center region. These data are consistent with a structure for S-ovalbumin in which part of the reactive center loop has inserted into beta-sheet A to give a more stable structure, analogously to other serpins. However, the rate of loop insertion appears to be very much lower than for inhibitory serpins.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7613461

Dinitrophenyl-reactive immunoglobulins in the serum of normal bowfin, Amia calva

PubMed Central

Bradshaw, Claire; Sigel, M. M.

1972-01-01

The sera from unimmunized bowfin agglutinate a large variety of red cells. Although they precipitate DNP-BSA they manifest only slight agglutinating capacity for DNP-coated cells. 15S immunoglobulin isolated by DEAE-cellulose chromatography followed by Sephadex G-200 gel filtration possessed a high level of broad reactivity towards unmodified DNP-coated cells, whereas the 7S immunoglobulin isolated by this procedure was inactive. However, following precipitation of whole serum with DNP-BSA both molecules could be recovered in a form which demonstrated specificity for DNP, in that both precipitated DNP-BSA and agglutinated DNP-coated cells but not unmodified cells. The mechanism of activation of the 7S molecule is not known but the data suggest that this immunoglobulin is divalent. ImagesFIG. 3FIG. 4 PMID:4624342

Catalytic reactive separation system for energy-efficient production of cumene

DOEpatents

Buelna, Genoveva [Nuevo Laredo, MX; Nenoff, Tina M [Albuquerque, NM

2009-07-28

The present invention relates to an atmospheric pressure, reactive separation column packed with a solid acid zeolite catalyst for producing cumene from the reaction of benzene with propylene. Use of this un-pressurized column, where simultaneous reaction and partial separation occur during cumene production, allow separation of un-reacted, excess benzene from other products as they form. This high-yielding, energy-efficient system allows for one-step processing of cumene, with reduced need for product purification. Reacting propylene and benzene in the presence of beta zeolite catalysts generated a selectivity greater than 85% for catalytic separation reactions at a reaction temperature of 115 degrees C and at ambient pressure. Simultaneously, up to 76% of un-reacted benzene was separated from the product; which could be recycled back to the reactor for re-use.

Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron.

PubMed

Furukawa, Yoko; Kim, Jin-Wook; Watkins, Janet; Wilkin, Richard T

2002-12-15

Ferrihydrite, which is known to form in the presence of oxygen and to be stabilized by the adsorption of Si, PO4 and SO4, is ubiquitous in the fine-grained fractions of permeable reactive barrier (PRB) samples from the U.S. Coast Guard Support Center (Elizabeth City, NC) and the Denver Federal Center (Lakewood, CO) studied by high-resolution transmission electron microscopy and selected area electron diffraction. The concurrent energy-dispersive X-ray data indicate a strong association between ferrihydrite and metals such as Si, Ca, and Cr. Magnetite, green rust 1, aragonite, calcite, mackinawite, greigite and lepidocrocite were also present, indicative of a geochemical environment that is temporally and spatially heterogeneous. Whereas magnetite, which is known to form due to anaerobic Fe0 corrosion, passivates the Fe0 surface, ferrihydrite precipitation occurs away from the immediate Fe0 surface, forming small (<0.1 microm) discrete clusters. Consequently, Fe0-PRBs may remain effective for a longer period of time in slightly oxidized groundwater systems where ferrihydrite formation occurs compared to oxygen-depleted systems where magnetite passivation occurs. The ubiquitous presence of ferrihydrite suggests that the use of Fe0-PRBs may be extended to applications that require contaminant adsorption rather than, or in addition to, redox-promoted contaminant degradation.

Method and apparatus for depositing a coating on a tape carrier

DOEpatents

Storer, Jonathan; Matias, Vladimir

2010-06-15

A system and method for depositing ceramic materials, such as nitrides and oxides, including high temperature superconducting oxides on a tape substrate. The system includes a tape support assembly that comprises a rotatable drum. The rotatable drum supports at least one tape substrate axially disposed on the surface of the drum during the deposition of metals on the tape and subsequent oxidation to form the ceramic materials. The drum is located within a stator having a slot that is axially aligned with the drum. A space exists between the drum and stator. The space is filled with a predetermined partial pressure of a reactive gas. The drum, stator, and space are heated to a predetermined temperature. To form the ceramic material on the tape substrate, the drum is first rotated to align the tape substrate with the slot, and at least one metal is deposited on the substrate. The drum then continues to rotate, bringing the tape substrate into the space, where the metal deposited on the tape substrate reacts with the reactive gas to form the ceramic material. In one embodiment, the tape support system also includes a pay-out/take-up system that co-rotates with the drum and provides a continuous length of tape substrate.

Structural differences between the lignin-carbohydrate complexes present in wood and in chemical pulps.

PubMed

Lawoko, Martin; Henriksson, Gunnar; Gellerstedt, Göran

2005-01-01

Lignin-carbohydrate complexes (LCCs) were prepared in quantitative yield from spruce wood and from the corresponding kraft and oxygen-delignified pulps and were separated into different fractions on the basis of their carbohydrate composition. To obtain an understanding of the differences in lignin structure and reactivity within the various LCC fractions, thioacidolysis in combination with gas chromatography was used to quantify the content of beta-O-4 structures in the lignin. Periodate oxidation followed by determination of methanol was used to quantify the phenolic hydroxyl groups. Furthermore, size exclusion chromatography (SEC) of the thioacidolysis fractions was used to monitor any differences between the original molecular size distribution and that after the delignification processes. Characteristic differences between the various LCC fractions were observed, clearly indicating that two different forms of lignin are present in the wood fiber wall. These forms are linked to glucomannan and xylan, respectively. On pulping, the different LCCs have different reactivities. The xylan-linked lignin is to a large extent degraded, whereas the glucomannan-linked lignin undergoes a partial condensation to form more high molecular mass material. The latter seems to be rather unchanged during a subsequent oxygen-delignification stage. On the basis of these findings, a modified arrangement of the fiber wall polymers is suggested.

Detection and Characterization of Reactive Oxygen and Nitrogen Species in Biological Systems by Monitoring Species-Specific Products.

PubMed

Hardy, Micael; Zielonka, Jacek; Karoui, Hakim; Sikora, Adam; Michalski, Radosław; Podsiadły, Radosław; Lopez, Marcos; Vasquez-Vivar, Jeannette; Kalyanaraman, Balaraman; Ouari, Olivier

2018-05-20

Since the discovery of the superoxide dismutase enzyme, the generation and fate of short-lived oxidizing, nitrosating, nitrating, and halogenating species in biological systems has been of great interest. Despite the significance of reactive oxygen species (ROS) and reactive nitrogen species (RNS) in numerous diseases and intracellular signaling, the rigorous detection of ROS and RNS has remained a challenge. Recent Advances: Chemical characterization of the reactions of selected ROS and RNS with electron paramagnetic resonance (EPR) spin traps and fluorescent probes led to the establishment of species-specific products, which can be used for specific detection of several forms of ROS and RNS in cell-free systems and in cultured cells in vitro and in animals in vivo. Profiling oxidation products from the ROS and RNS probes provides a rigorous method for detection of those species in biological systems. Formation and detection of species-specific products from the probes enables accurate characterization of the oxidative environment in cells. Measurement of the total signal (fluorescence, chemiluminescence, etc.) intensity does not allow for identification of the ROS/RNS formed. It is critical to identify the products formed by using chromatographic or other rigorous techniques. Product analyses should be accompanied by monitoring of the intracellular probe level, another factor controlling the yield of the product(s) formed. More work is required to characterize the chemical reactivity of the ROS/RNS probes, and to develop new probes/detection approaches enabling real-time, selective monitoring of the specific products formed from the probes. Antioxid. Redox Signal. 28, 1416-1432.

REACTIVE MINERALS IN AQUIFERS: FORMATION PROCESSES AND QUANTITATIVE ANALYSIS

EPA Science Inventory

The presentation will focus on the occurrence, form, and characterization of reactive iron minerals in aquifers and soils. The potential for abiotic reductive transformations of contaminants at the mineral-water interface will be discussed along with available tools for site min...

Glycoconjugates and methods

DOEpatents

Bertozzi, Carolyn C [Albany, CA; Yarema, Kevin J [Albany, CA; Mahal, Lara K [Berkeley, CA

2008-04-01

Methods for making the functionalized glycoconjugates include (a) contacting a cell with a first monosaccharide, and (b) incubating the cell under conditions whereby the cell (i) internalizes the first monosaccharide, (ii) biochemically processes the first monosaccharide into a second saccharide, (iii) conjugates the saccharide to a carrier to form a glycoconjugate, and (iv) extracellularly expresses the glycoconjugate to form an extracellular glycoconjugate comprising a selectively reactive functional group. Methods for forming products at a cell further comprise contacting the functional group of the extracellularly expressed glycoconjugate with an agent which selectively reacts with the functional group to form a product. Subject compositions include cyto-compatible monosaccharides comprising a nitrogen or ether linked functional group selectively reactive at a cell surface and compositions and cells comprising such saccharides.

Global Profiling of Reactive Oxygen and Nitrogen Species in Biological Systems

PubMed Central

Zielonka, Jacek; Zielonka, Monika; Sikora, Adam; Adamus, Jan; Joseph, Joy; Hardy, Micael; Ouari, Olivier; Dranka, Brian P.; Kalyanaraman, Balaraman

2012-01-01

Herein we describe a high-throughput fluorescence and HPLC-based methodology for global profiling of reactive oxygen and nitrogen species (ROS/RNS) in biological systems. The combined use of HPLC and fluorescence detection is key to successful implementation and validation of this methodology. Included here are methods to specifically detect and quantitate the products formed from interaction between the ROS/RNS species and the fluorogenic probes, as follows: superoxide using hydroethidine, peroxynitrite using boronate-based probes, nitric oxide-derived nitrosating species with 4,5-diaminofluorescein, and hydrogen peroxide and other oxidants using 10-acetyl-3,7-dihydroxyphenoxazine (Amplex® Red) with and without horseradish peroxidase, respectively. In this study, we demonstrate real-time monitoring of ROS/RNS in activated macrophages using high-throughput fluorescence and HPLC methods. This global profiling approach, simultaneous detection of multiple ROS/RNS products of fluorescent probes, developed in this study will be useful in unraveling the complex role of ROS/RNS in redox regulation, cell signaling, and cellular oxidative processes and in high-throughput screening of anti-inflammatory antioxidants. PMID:22139901

Mineral Surface Rearrangement at High Temperatures: Implications for Extraterrestrial Mineral Grain Reactivity.

PubMed

King, Helen E; Plümper, Oliver; Putnis, Christine V; O'Neill, Hugh St C; Klemme, Stephan; Putnis, Andrew

2017-04-20

Mineral surfaces play a critical role in the solar nebula as a catalytic surface for chemical reactions and potentially acted as a source of water during Earth's accretion by the adsorption of water molecules to the surface of interplanetary dust particles. However, nothing is known about how mineral surfaces respond to short-lived thermal fluctuations that are below the melting temperature of the mineral. Here we show that mineral surfaces react and rearrange within minutes to changes in their local environment despite being far below their melting temperature. Polished surfaces of the rock and planetary dust-forming silicate mineral olivine ((Mg,Fe) 2 SiO 4 ) show significant surface reorganization textures upon rapid heating resulting in surface features up to 40 nm in height observed after annealing at 1200 °C. Thus, high-temperature fluctuations should provide new and highly reactive sites for chemical reactions on nebula mineral particles. Our results also may help to explain discrepancies between short and long diffusion profiles in experiments where diffusion length scales are of the order of 100 nm or less.

HU-331, a novel cannabinoid-based anticancer topoisomerase II inhibitor.

PubMed

Kogan, Natalya M; Schlesinger, Michael; Priel, Esther; Rabinowitz, Ruth; Berenshtein, Eduard; Chevion, Mordechai; Mechoulam, Raphael

2007-01-01

Anthracyclines, a large group of quinonoid compounds, are used to treat some forms of cancer. Although highly effective in cancer therapy, the mechanism of action of these compounds is not specific; they act on cancer and other cells by numerous mechanisms. A new anticancer quinone (HU-331) was synthesized from cannabidiol. It shows significant high efficacy against human cancer cell lines in vitro and against in vivo tumor grafts in nude mice. In this study, we investigated its mode of action and present evidence on its unique mechanism. HU-331 does not cause cancer cell cycle arrest, cell apoptosis, or caspase activation. HU-331-caused cell death of human cancer cell lines is not mediated by reactive oxygen intermediates/species, as exposure to HU-331 failed to elicit the generation of reactive oxygen species. HU-331 inhibits DNA topoisomerase II even at nanomolar concentrations but has only a slight nonsignificant effect on DNA topoisomerase I action. The cannabinoid quinone HU-331 is a highly specific inhibitor of topoisomerase II, compared with most known anticancer quinones. It might represent a new potent anticancer drug.

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China

PubMed Central

Cheng, Yafang; Zheng, Guangjie; Wei, Chao; Mu, Qing; Zheng, Bo; Wang, Zhibin; Gao, Meng; Zhang, Qiang; He, Kebin; Carmichael, Gregory; Pöschl, Ulrich; Su, Hang

2016-01-01

Fine-particle pollution associated with winter haze threatens the health of more than 400 million people in the North China Plain. Sulfate is a major component of fine haze particles. Record sulfate concentrations of up to ~300 μg m−3 were observed during the January 2013 winter haze event in Beijing. State-of-the-art air quality models that rely on sulfate production mechanisms requiring photochemical oxidants cannot predict these high levels because of the weak photochemistry activity during haze events. We find that the missing source of sulfate and particulate matter can be explained by reactive nitrogen chemistry in aerosol water. The aerosol water serves as a reactor, where the alkaline aerosol components trap SO2, which is oxidized by NO2 to form sulfate, whereby high reaction rates are sustained by the high neutralizing capacity of the atmosphere in northern China. This mechanism is self-amplifying because higher aerosol mass concentration corresponds to higher aerosol water content, leading to faster sulfate production and more severe haze pollution. PMID:28028539

Neutron Absorbing Alloys

DOEpatents

Zhong, Yuanzhen , Parikh, Hemant; Smith, Terry E.

2002-05-28

A process for making homogeneous copolymers of vinylpyrrolidone (VP) and vinyl acetate (VA) which form clear aqueous solutions and have high cloud points. The process involves precharging VP and VA monomers in a predetermined ratio, and then feeding VP and VA at a predetermined rate, the ratio of the components in the initial charge and the feeding rates for the monomer being selected in accordance with the reactivity rates of the monomers towards copolymerization as opposed to homopolymerization.

Properties of Reactive Atomic Species Generated at High Temperatures and Their Low Temperature Reactions to Form Novel Substances

DTIC Science & Technology

1979-01-01

product is magnesium pinacolate, minor but important are the magnesium enolate of acetone and isopropoxide in 1:1 ratio. The double ketyl is a...tungsten, molybdenum and titanium were either unknown or had been made in very poor yield. Our vaporization techniques make these compounds readily...excess cyclooctatetraene. Mono and binuclear complexes of titanium have been isolated; the latter, triscyclooctatetraenedititanium was shown to be a

MOLTEN FLUORIDE NUCLEAR REACTOR FUEL

DOEpatents

Barton, C.J.; Grimes, W.R.

1960-01-01

Molten-salt reactor fuel compositions consisting of mixtures of fluoride salts are reported. In its broadest form, the composition contains an alkali fluoride such as sodium fluoride, zirconium tetrafluoride, and a uranium fluoride, the latter being the tetrafluoride or trifluoride or a mixture of the two. An outstanding property of these fuel compositions is a high coeffieient of thermal expansion which provides a negative temperature coefficient of reactivity in reactors in which they are used.

High salt-induced excess reactive oxygen species production resulted in heart tube malformation during gastrulation.

PubMed

Gao, Lin-Rui; Wang, Guang; Zhang, Jing; Li, Shuai; Chuai, Manli; Bao, Yongping; Hocher, Berthold; Yang, Xuesong

2018-09-01

An association has been proved between high salt consumption and cardiovascular mortality. In vertebrates, the heart is the first functional organ to be formed. However, it is not clear whether high-salt exposure has an adverse impact on cardiogenesis. Here we report high-salt exposure inhibited basement membrane breakdown by affecting RhoA, thus disturbing the expression of Slug/E-cadherin/N-cadherin/Laminin and interfering with mesoderm formation during the epithelial-mesenchymal transition(EMT). Furthermore, the DiI + cell migration trajectory in vivo and scratch wound assays in vitro indicated that high-salt exposure restricted cell migration of cardiac progenitors, which was caused by the weaker cytoskeleton structure and unaltered corresponding adhesion junctions at HH7. Besides, down-regulation of GATA4/5/6, Nkx2.5, TBX5, and Mef2c and up-regulation of Wnt3a/β-catenin caused aberrant cardiomyocyte differentiation at HH7 and HH10. High-salt exposure also inhibited cell proliferation and promoted apoptosis. Most importantly, our study revealed that excessive reactive oxygen species(ROS)generated by high salt disturbed the expression of cardiac-related genes, detrimentally affecting the above process including EMT, cell migration, differentiation, cell proliferation and apoptosis, which is the major cause of malformation of heart tubes. © 2018 Wiley Periodicals, Inc.

High pressure liquid and gaseous oxygen impact sensitivity evaluation of materials for use at Kennedy Space Center

NASA Technical Reports Server (NTRS)

Bryan, C. J.

1976-01-01

The sensitivity of materials in contact with gaseous oxygen (GOX) or liquid oxygen (LOX) was examined. Specifically, the reactivity of materials when in contact with GOX or LOX if subjected to such stimuli as mechanical impact, adiabatic compression (pneumatic impact), or an electrical discharge in the form of a spark were examined. Generally, materials are more sensitive in gaseous oxygen than in liquid oxygen and impact sensitivity is known to increase with increasing pressure. Materials presently being used or considered for use in oxygen systems at KSC were evaluated. Results are given in tabular form.

Lipid oxidation in minced beef meat with added Krebs cycle substrates to stabilise colour.

PubMed

Yi, G; Grabež, V; Bjelanovic, M; Slinde, E; Olsen, K; Langsrud, O; Phung, V T; Haug, A; Oostindjer, M; Egelandsdal, B

2015-11-15

Krebs cycle substrates (KCS) can stabilise the colour of packaged meat by oxygen reduction. This study tested whether this reduction releases reactive oxygen species that may lead to lipid oxidation in minced meat under two different storage conditions. KCS combinations of succinate and glutamate increased peroxide forming potential (PFP, 1.18-1.32 mmol peroxides/kg mince) and thiobarbituric acid reactive substances (TBARS, 0.30-0.38 mg malondialdehyde (MDA) equivalents/kg mince) under low oxygen storage conditions. Both succinate and glutamate were metabolised. Moreover, under high oxygen (75%) storage conditions, KCS combinations of glutamate, citrate and malate increased PFP (from 1.22 to 1.29 mmol peroxides/kg) and TBARS (from 0.37 to 0.40 mg MDA equivalents/kg mince). Only glutamate was metabolised. The KCS combinations that were added to stabilise colour were metabolised during storage, and acted as pro-oxidants that promoted lipid oxidation in both high and low oxygen conditions. Copyright © 2015. Published by Elsevier Ltd.

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Mahne, Nika; Schafzahl, Bettina; Leypold, Christian; Leypold, Mario; Grumm, Sandra; Leitgeb, Anita; Strohmeier, Gernot A.; Wilkening, Martin; Fontaine, Olivier; Kramer, Denis; Slugovc, Christian; Borisov, Sergey M.; Freunberger, Stefan A.

2017-03-01

Non-aqueous metal-oxygen batteries depend critically on the reversible formation/decomposition of metal oxides on cycling. Irreversible parasitic reactions cause poor rechargeability, efficiency, and cycle life, and have predominantly been ascribed to the reactivity of reduced oxygen species with cell components. These species, however, cannot fully explain the side reactions. Here we show that singlet oxygen forms at the cathode of a lithium-oxygen cell during discharge and from the onset of charge, and accounts for the majority of parasitic reaction products. The amount increases during discharge, early stages of charge, and charging at higher voltages, and is enhanced by the presence of trace water. Superoxide and peroxide appear to be involved in singlet oxygen generation. Singlet oxygen traps and quenchers can reduce parasitic reactions effectively. Awareness of the highly reactive singlet oxygen in non-aqueous metal-oxygen batteries gives a rationale for future research towards achieving highly reversible cell operation.

Boron deactivation in heavily boron-doped Czochralski silicon during rapid thermal anneal: Atomic level understanding

NASA Astrophysics Data System (ADS)

Gao, Chao; Lu, Yunhao; Dong, Peng; Yi, Jun; Ma, Xiangyang; Yang, Deren

2014-01-01

The changes in hole concentration of heavily boron (B)-doped Czochralski silicon subjected to high temperature rapid thermal anneal (RTA) and following conventional furnace anneal (CFA) have been investigated. It is found that decrease in hole concentration, namely, B deactivation, is observed starting from 1050 °C and increases with RTA temperature. The following CFA at 300-500 °C leads to further B deactivation, while that at 600-800 °C results in B reactivation. It is supposed that the interaction between B atoms and silicon interstitials (I) thus forming BI pairs leads to the B deactivation during the high temperature RTA, and, moreover, the formation of extended B2I complexes results in further B deactivation in the following CFA at 300-500 °C. On the contrary, the dissociation of BI pairs during the following CFA at 600-800 °C enables the B reactivation. Importantly, the first-principles calculation results can soundly account for the above-mentioned supposition.

The discovery of a conjugate system of faults in the Wharton Basin intraplate deformation zone

PubMed Central

Singh, Satish C.; Hananto, Nugroho; Qin, Yanfang; Leclerc, Frederique; Avianto, Praditya; Tapponnier, Paul E.; Carton, Helene; Wei, Shengji; Nugroho, Adam B.; Gemilang, Wishnu A.; Sieh, Kerry; Barbot, Sylvain

2017-01-01

The deformation at well-defined, narrow plate boundaries depends on the relative plate motion, but how the deformation takes place within a distributed plate boundary zone remains a conundrum. This was confirmed by the seismological analyses of the 2012 great Wharton Basin earthquakes [moment magnitude (Mw) 8.6], which suggested the rupture of several faults at high angles to one another. Using high-resolution bathymetry and seismic reflection data, we report the discovery of new N294°E-striking shear zones, oblique to the plate fabric. These shear zones are expressed by sets of normal faults striking at N335°E, defining the direction of the principal compressional stress in the region. Also, we have imaged left-lateral strike-slip faults along reactivated N7°E-oriented oceanic fracture zones. The shear zones and the reactivated fracture zones form a conjugate system of faults, which accommodate present-day intraplate deformation in the Wharton Basin. PMID:28070561

Decidualized Human Endometrial Stromal Cells Mediate Hemostasis, Angiogenesis, and Abnormal Uterine Bleeding

PubMed Central

Lockwood, Charles J.; Krikun, Graciela; Hickey, Martha; Huang, S. Joseph; Schatz, Frederick

2011-01-01

Factor VII binds trans-membrane tissue factor to initiate hemostasis by forming thrombin. Tissue factor expression is enhanced in decidualized human endometrial stromal cells during the luteal phase. Long-term progestin only contraceptives elicit: 1) abnormal uterine bleeding from fragile vessels at focal bleeding sites, 2) paradoxically high tissue factor expression at bleeding sites; 3) reduced endometrial blood flow promoting local hypoxia and enhancing reactive oxygen species levels; and 4) aberrant angiogenesis reflecting increased stromal cell-expressed vascular endothelial growth factor, decreased Angiopoietin-1 and increased endothelial cell-expressed Angiopoietin-2. Aberrantly high local vascular permeability enhances circulating factor VII to decidualized stromal cell-expressed tissue factor to generate excess thrombin. Hypoxia-thrombin interactions augment expression of vascular endothelial growth factor and interleukin-8 by stromal cells. Thrombin, vascular endothelial growth factor and interlerukin-8 synergis-tically augment angiogenesis in a milieu of reactive oxygen species-induced endothelial cell activation. The resulting enhanced vessel fragility promotes abnormal uterine bleeding. PMID:19208784

Experimental laboratory measurement of thermophysical properties of selected coal types

NASA Technical Reports Server (NTRS)

Lloyd, W. G.

1979-01-01

A number of bituminous coals of moderate to high plasticity were examined, along with portions of their extrudates from the JPL 1.5-inch 850 F screw extruder. Portions of the condensed pyrolysis liquids released during extrusion, and of the gaseous products formed during extrusion were also analyzed. In addition to the traditional determinations, the coals and extrudates were examined in terms of microstructure (especially extractable fractions), thermal analysis (especially that associated with the plastic state), and reactivity towards thermal and catalyzed hydroliquefaction. The process of extrusion increases the fixed carbon content of coals by about 5% and tends to increase the surface area. Coals contaning 25% or more DMF-extractable material show an increase in extractables as a result of extrusion; those initially containing less than 20% extractables show a decrease as a result of extrusion. Both the raw and extruded samples of Kentucky #9 coal are highly reactive towards hydroliquefaction, undergoing conversions of 75 to 80% in 15 min and 85-94% in 60 min in a stirred clave.

The discovery of a conjugate system of faults in the Wharton Basin intraplate deformation zone.

PubMed

Singh, Satish C; Hananto, Nugroho; Qin, Yanfang; Leclerc, Frederique; Avianto, Praditya; Tapponnier, Paul E; Carton, Helene; Wei, Shengji; Nugroho, Adam B; Gemilang, Wishnu A; Sieh, Kerry; Barbot, Sylvain

2017-01-01

The deformation at well-defined, narrow plate boundaries depends on the relative plate motion, but how the deformation takes place within a distributed plate boundary zone remains a conundrum. This was confirmed by the seismological analyses of the 2012 great Wharton Basin earthquakes [moment magnitude ( M w ) 8.6], which suggested the rupture of several faults at high angles to one another. Using high-resolution bathymetry and seismic reflection data, we report the discovery of new N294°E-striking shear zones, oblique to the plate fabric. These shear zones are expressed by sets of normal faults striking at N335°E, defining the direction of the principal compressional stress in the region. Also, we have imaged left-lateral strike-slip faults along reactivated N7°E-oriented oceanic fracture zones. The shear zones and the reactivated fracture zones form a conjugate system of faults, which accommodate present-day intraplate deformation in the Wharton Basin.

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

Explosive Compations of Intermetallic-Forming Powder Mixtures for Fabricating Structural Energetic Materials

NASA Astrophysics Data System (ADS)

Du, S. W.; Aydelotte, B.; Fondse, D.; Wei, C.-T.; Jiang, F.; Herbold, E.; Vecchio, K.; Meyers, M. A.; Thadhani, N. N.

2009-12-01

A double-tube implosion geometry is used to explosively shock consolidate intermetallic-forming Ni-Al, Ta-Al, Nb-Al, Mo-Al and W-Al powder mixtures for fabricating bulk structural energetic materials, with mechanical strength and ability to undergo impact-initiated exothermic reactions. The compacts are characterized based on uniformity of micro structure and degree of densification. Mechanical properties of the compacts are characterized over the strain-rate range of 10-3 to 104 s-1. The impact reactivity is determined using rod-on-anvil experiments, in which disk-shaped compacts mounted on a copper projectile, are impacted against a steel anvil in using a 7.62 mm gas gun. The impact reactivity of the various explosively-consolidated reactive powder mixture compacts is correlated with overall kinetic energy and impact stress to determine their influence on threshold for reaction initiation. The characteristics of the various compacts, their mechanical properties and impact-initiated chemical reactivity will be described in this paper.

Detection of reactive metabolites using isotope-labeled glutathione trapping and simultaneous neutral loss and precursor ion scanning with ultra-high-pressure liquid chromatography triple quadruple mass spectrometry.

PubMed

Huang, Ke; Huang, Lingyi; van Breemen, Richard B

2015-04-07

Metabolic activation of drugs to electrophilic species is responsible for over 60% of black box warnings and drug withdrawals from the market place in the United States. Reactive metabolite trapping using glutathione (GSH) and analysis using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) or HPLC with high resolution mass spectrometry (mass defect filtering) have enabled screening for metabolic activation to become routine during drug development. However, current MS-based approaches cannot detect all GSH conjugates present in complex mixtures, especially those present in extracts of botanical dietary supplements. To overcome these limitations, a fast triple quadrupole mass spectrometer-based approach was developed that can detect positively and negatively charged GSH conjugates in a single analysis without the need for advanced knowledge of the elemental compositions of potential conjugates and while avoiding false positives. This approach utilized UHPLC instead of HPLC to shorten separation time and enhance sensitivity, incorporated stable-isotope labeled GSH to avoid false positives, and used fast polarity switching electrospray MS/MS to detect GSH conjugates that form positive and/or negative ions. The general new method was then used to test the licorice dietary supplement Glycyrrhiza glabra, which was found to form multiple GSH conjugates upon metabolic activation. Among the GSH conjugates found in the licorice assay were conjugates with isoliquiritigenin and glabridin, which is an irreversible inhibitor of cytochrome P450 enzymes.

Evaluation of the chemical reactivity in lignin precursors using the Fukui function.

PubMed

Martinez, Carmen; Rivera, José L; Herrera, Rafael; Rico, José L; Flores, Nelly; Rutiaga, José G; López, Pablo

2008-02-01

The hydroxycinnamyl alcohols: p-coumarol, coniferol and sinapol are considered the basic units and precursors of lignins models. In this work, the specific reactivity of these molecules was studied. We investigate their intrinsic chemical reactivity in terms of the Fukui function, applying the principle of hard and soft acids and bases (HSAB) in the framework of the density functional theory (DFT). Comparisons of their nucleophilic, electrophilic and free radical reactivity show their most probably sites to form linkages among them. It is found that the most reactive sites, for reactions involving free radicals, are the carbons at the beta-position in the p-coumarol and sinapol molecules, whilst the regions around the carbon-oxygen bond of the phenoxyl group are the most reactive in coniferol.

Analytical solutions for sequentially coupled one-dimensional reactive transport problems Part I: Mathematical derivations

NASA Astrophysics Data System (ADS)

Srinivasan, V.; Clement, T. P.

2008-02-01

Multi-species reactive transport equations coupled through sorption and sequential first-order reactions are commonly used to model sites contaminated with radioactive wastes, chlorinated solvents and nitrogenous species. Although researchers have been attempting to solve various forms of these reactive transport equations for over 50 years, a general closed-form analytical solution to this problem is not available in the published literature. In Part I of this two-part article, we derive a closed-form analytical solution to this problem for spatially-varying initial conditions. The proposed solution procedure employs a combination of Laplace and linear transform methods to uncouple and solve the system of partial differential equations. Two distinct solutions are derived for Dirichlet and Cauchy boundary conditions each with Bateman-type source terms. We organize and present the final solutions in a common format that represents the solutions to both boundary conditions. In addition, we provide the mathematical concepts for deriving the solution within a generic framework that can be used for solving similar transport problems.

Nanoporous Gold for Enzyme Immobilization.

PubMed

Stine, Keith J; Jefferson, Kenise; Shulga, Olga V

2017-01-01

Nanoporous gold (NPG) is a material of emerging interest for immobilization of biomolecules, especially enzymes. The material provides a high surface area form of gold that is suitable for physisorption or for covalent modification by self-assembled monolayers. The material can be used as a high surface area electrode and with immobilized enzymes can be used for amperometric detection schemes. NPG can be prepared in a variety of formats from alloys containing between 20 and 50 % atomic composition of gold and less noble element(s) by dealloying procedures. Materials resembling NPG can be prepared by hydrothermal and electrodeposition methods. Related high surface area gold structures have been prepared using templating approaches. Covalent enzyme immobilization can be achieved by first forming a self-assembled monolayer on NPG bearing a terminal reactive functional group followed by conjugation to the enzyme through amide linkages to lysine residues. Enzymes can also be entrapped by physisorption or immobilized by electrostatic interactions.

Mitigation of NADPH Oxidase 2 Activity as a Strategy to Inhibit Peroxynitrite Formation*

PubMed Central

Zielonka, Jacek; Zielonka, Monika; VerPlank, Lynn; Cheng, Gang; Hardy, Micael; Ouari, Olivier; Ayhan, Mehmet Menaf; Podsiadły, Radosław; Sikora, Adam; Lambeth, J. David; Kalyanaraman, Balaraman

2016-01-01

Using high throughput screening-compatible assays for superoxide and hydrogen peroxide, we identified potential inhibitors of the NADPH oxidase (Nox2) isoform from a small library of bioactive compounds. By using multiple probes (hydroethidine, hydropropidine, Amplex Red, and coumarin boronate) with well defined redox chemistry that form highly diagnostic marker products upon reaction with superoxide (O2˙̄), hydrogen peroxide (H2O2), and peroxynitrite (ONOO−), the number of false positives was greatly decreased. Selected hits for Nox2 were further screened for their ability to inhibit ONOO− formation in activated macrophages. A new diagnostic marker product for ONOO− is reported. We conclude that the newly developed high throughput screening/reactive oxygen species assays could also be used to identify potential inhibitors of ONOO− formed from Nox2-derived O2˙̄ and nitric oxide synthase-derived nitric oxide. PMID:26839313

Biomimetic catalytic transformation of toxic α-oxoaldehydes to high-value chiral α-hydroxythioesters using artificial glyoxalase I

NASA Astrophysics Data System (ADS)

Park, Sang Yeon; Hwang, In-Soo; Lee, Hyun-Ju; Song, Choong Eui

2017-04-01

Glyoxalase I plays a critical role in the enzymatic defence against glycation by catalysing the isomerization of hemithioacetal, formed spontaneously from cytotoxic α-oxoaldehydes and glutathione, to (S)-α-hydroxyacylglutathione derivatives. Upon the hydrolysis of the thioesters catalysed by glyoxalase II, inert (S)-α-hydroxy acids, that is, lactic acid, are then produced. Herein, we demonstrate highly enantioselective glyoxalase I mimic catalytic isomerization of in-situ-generated hemithioacetals, providing facile access to both enantiomers of α-hydroxy thioesters. Owing to the flexibility of thioesters, a family of optically pure α-hydroxyamides, which are highly important drug candidates in the pharmaceutical industry, were prepared without any coupling reagents. Similar to real enzymes, the enforced proximity of the catalyst and substrates by the chiral cage in situ formed by the incorporation of potassium salt can enhance the reactivity and efficiently transfer the stereochemical information.

Potassium ferrate [Fe(VI)] does not mediate self-sterilization of a surrogate Mars soil.

PubMed

Crawford, Ronald L; Paszczynski, Andrzej; Allenbach, Lisa

2003-03-06

Martian soil is thought to be enriched with strong oxidants such as peroxides and/or iron in high oxidation states that might destroy biological materials. There is also a high flux of ultraviolet radiation at the surface of Mars. Thus, Mars may be inhospitable to life as we know it on Earth. We examined the hypothesis that if the soil of Mars contains ferrates [Fe(VI)], the strongest of the proposed oxidizing species, and also is exposed to high fluxes of UV radiation, it will be self-sterilizing. Under ambient conditions (25 degrees C, oxygen and water present) K2FeO4 mixed into sand mineralized some reactive organic molecules to CO2, while less reactive compounds were not degraded. Dried endospores of Bacillus subtilis incubated in a Mars surrogate soil comprised of dry silica sand containing 20% by weight K2FeO4 and under conditions similar to those now on Mars (extreme desiccation, cold, and a CO2-dominated atmosphere) were resistant to killing by the ferrate-enriched sand. Similar results were observed with permanganate. Spores in oxidant-enriched sand exposed to high fluxes of UV light were protected from the sporocidal activity of the radiation below about 5 mm depths. Based on our data and previously published descriptions of ancient but dormant life forms on Earth, we suggest that if entities resembling bacterial endospores were produced at some point by life forms on Mars, they might still be present and viable, given appropriate germination conditions. Endospores delivered to Mars on spacecraft would possibly survive and potentially compromise life detection experiments.

The immunogenicity of Echinococcus granulosus antigen 5 is determined by its post-translational modifications.

PubMed

Lorenzo, C; Last, J A; González-Sapienza, G G

2005-11-01

Since its early introduction as a marker for the immunodiagnosis of hydatid disease, antigen 5 (Ag5) has been regarded as one of the more relevant antigens of Echinococcus granulosus, and it is still widely used in different confirmation techniques. In this work we prepared 2 recombinant forms of the antigen, namely, rAg5 (corresponding to the unprocessed polypeptide chain of the antigen) and rAg5-38s (corresponding to its 38 kDa subunit). Their antigenicities were compared to that of the native antigen using a human serum collection. There was a major drop in the reactivity of the sera, particularly against rAg5-38s, which was confirmed by analysis of the cross-reactivity of 2 panels of monoclonal antibodies specific for rAg5-38s and the native antigen. Using the chemically deglycosylated native antigen, we demonstrated that the reduced antigenicity of the recombinants is due to the loss of the sugar determinants, and not to their misfolding. Inhibition experiments using phosphorylcholine confirmed that this moiety also contributes to the reactivity of the antigen, but to a much lesser extent. The presence of immunodominant highly cross-reactive glycan moieties in the Ag5 molecule may involve a parasite evasion mechanism.

Response surface optimization of electro-oxidation process for the treatment of C.I. Reactive Yellow 186 dye: reaction pathways

NASA Astrophysics Data System (ADS)

Rajkumar, K.; Muthukumar, M.

2017-05-01

In this study, central composite design at five levels (- β, -1, 0, +1, + β) combined with response surface methodology has been applied to optimize C.I. Reactive Yellow 186 using electro-oxidation process with graphite electrodes in a batch reactor. The variables considered were the pH ( X 1), NaCl concentration (M) ( X 2), and electrolysis time (min) ( X 3) on C.I. Reactive Yellow 186 were studied. A second-order empirical relationship between the response and independent variables was derived. Analysis of variance showed a high coefficient of determination value ( R 2 = 0.9556 and 0.9416 for color and COD, respectively). The optimized condition of the electro-oxidation of Reactive Yellow 186 is as follows: pH 3.9; NaCl concentration 0.11 M; and electrolysis time 18 min. Under this condition, the maximal decolorization efficiency of 99 % and COD removal 73 % was achieved. Detailed physico-chemical analysis of electrode and residues of the electro-oxidation process has also been carried out UV-Visible and Fourier transform infrared spectroscopy. The intermediate compounds formed during the oxidation were identified using a gas chromatography coupled with mass spectrometry. According to these results, response surface methodology could be useful for reducing the time to treat effluent wastewater.

Influence of Gas Atmosphere Dew Point on the Selective Oxidation and the Reactive Wetting During Hot Dip Galvanizing of CMnSi TRIP Steel

NASA Astrophysics Data System (ADS)

Cho, Lawrence; Lee, Seok Jae; Kim, Myung Soo; Kim, Young Ha; De Cooman, Bruno C.

2013-01-01

The selective oxidation and reactive wetting of intercritically annealed Si-bearing CMnSi transformation-induced plasticity steels were investigated by high-resolution transmission electron microscopy. In a N2 + 10 pct H2 gas atmosphere with a dew point (DP) ranging from 213 K to 278 K (-60 °C to 5 °C), a continuous layer of selective oxides was formed on the surface. Annealing in a higher DP gas atmosphere resulted in a thinner layer of external oxidation and a greater depth of internal oxidation. The hot dipping was carried out in a Zn bath containing 0.22 mass pct Al, and the bath temperature was 733 K (460 °C). Coarse and discontinuous Fe2Al5- x Zn x grains and Fe-Zn intermetallics (ζ and δ) were observed at the steel/coating interface after the hot dip galvanizing (HDG) of panels were annealed in a low DP atmosphere 213 K (-60 °C). The Fe-Zn intermetallics were formed both in areas where the Fe2Al5- x Zn x inhibition layer had not been formed and on top of non-stoichiometric Fe-Al-Zn crystals. Poor wetting was observed on panels annealed in a low DP atmosphere because of the formation of thick film-type oxides on the surface. After annealing in higher DP gas atmospheres, i.e., 263 K and 278 K (-10 °C and 5 °C), a continuous and fine-grained Fe2Al5- x Zn x layer was formed. No Fe-Zn intermetallics were formed. The small grain size of the inhibition layer was attributed to the nucleation of the Fe2Al5- x Zn x grains on small ferrite sub-surface grains and the presence of granular surface oxides. A high DP atmosphere can therefore significantly contribute to the decrease of Zn-coating defects on CMnSi TRIP steels processed in HDG lines.

High-Frequency Heart Rate Variability Reactivity and Trait Worry Interact to Predict the Development of Sleep Disturbances in Response to a Naturalistic Stressor.

PubMed

MacNeil, Sasha; Deschênes, Sonya S; Caldwell, Warren; Brouillard, Melanie; Dang-Vu, Thien-Thanh; Gouin, Jean-Philippe

2017-12-01

High-frequency heart rate variability (HF-HRV) reactivity was proposed as a vulnerability factor for stress-induced sleep disturbances. Its effect may be amplified among individuals with high trait worry or sleep reactivity. This study evaluated whether HF-HRV reactivity to a worry induction, sleep reactivity, and trait worry predict increases in sleep disturbances in response to academic stress, a naturalistic stressor. A longitudinal study following 102 undergraduate students during an academic semester with well-defined periods of lower and higher academic stress was conducted. HF-HRV reactivity to a worry induction, trait worry using the Penn State Worry Questionnaire, and sleep reactivity using the Ford Insomnia Stress Reactivity Test were measured during the low stress period. Sleep disturbances using the Pittsburgh Sleep Quality Index were assessed twice during the lower stress period and three times during the higher stress period. Greater reductions in HF-HRV in response to the worry induction predicted increases in sleep disturbances from the lower to the higher academic stress period. Trait worry moderated this association: individuals with both higher trait worry and greater HF-HRV reactivity to worry had larger increases in stress-related sleep disturbances over time, compared to participants with lower trait worry and HF-HRV reactivity. A similar, but marginally significant effect was found for sleep reactivity. This study supports the role of HF-HRV reactivity as a vulnerability factor for stress-induced sleep disturbances. The combination of high trait worry and high HF-HRV reactivity to worry might identify a subgroup of individuals most vulnerable to stress-related sleep disturbances.

Evidence that the reactivity of the martian soil is due to superoxide ions

NASA Technical Reports Server (NTRS)

Yen, A. S.; Kim, S. S.; Hecht, M. H.; Frant, M. S.; Murray, B.

2000-01-01

The Viking Landers were unable to detect evidence of life on Mars but, instead, found a chemically reactive soil capable of decomposing organic molecules. This reactivity was attributed to the presence of one or more as-yet-unidentified inorganic superoxides or peroxides in the martian soil. Using electron paramagnetic resonance spectroscopy, we show that superoxide radical ions (O2-) form directly on Mars-analog mineral surfaces exposed to ultraviolet radiation under a simulated martian atmosphere. These oxygen radicals can explain the reactive nature of the soil and the apparent absence of organic material at the martian surface.

EEG classification of emotions using emotion-specific brain functional network.

PubMed

Gonuguntla, V; Shafiq, G; Wang, Y; Veluvolu, K C

2015-08-01

The brain functional network perspective forms the basis to relate mechanisms of brain functions. This work analyzes the network mechanisms related to human emotion based on synchronization measure - phase-locking value in EEG to formulate the emotion specific brain functional network. Based on network dissimilarities between emotion and rest tasks, most reactive channel pairs and the reactive band corresponding to emotions are identified. With the identified most reactive pairs, the subject-specific functional network is formed. The identified subject-specific and emotion-specific dynamic network pattern show significant synchrony variation in line with the experiment protocol. The same network pattern are then employed for classification of emotions. With the study conducted on the 4 subjects, an average classification accuracy of 62 % was obtained with the proposed technique.

Phenylethynyl Containing Reactive Additives

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Smith, Joseph G., Jr. (Inventor); Hergenrother, Paul M. (Inventor)

2002-01-01

Phenylethynyl containing reactive additives were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynylphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pyrrolidi none to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.

Phenylethynyl Containing Reactive Additives

NASA Technical Reports Server (NTRS)

Connell, John W. (Inventor); Smith, Joseph G., Jr. (Inventor); Hergenrother, Paul M. (Inventor)

2002-01-01

Phenylethynyl containing reactive additives were prepared from aromatic diamine, containing phenylethvnvl groups and various ratios of phthalic anhydride and 4-phenylethynviphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pvrrolidinone to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.

Fatal outcome after reactivation of inherited chromosomally integrated HHV-6A (iciHHV-6A) transmitted through liver transplantation.

PubMed

Bonnafous, P; Marlet, J; Bouvet, D; Salamé, E; Tellier, A-C; Guyetant, S; Goudeau, A; Agut, H; Gautheret-Dejean, A; Gaudy-Graffin, C

2018-06-01

HHV-6A and HHV-6B are found as inherited and chromosomally integrated forms (iciHHV-6A and -6B) into all germinal and somatic cells and vertically transmitted in a Mendelian manner in about 1% of the population. They were occasionally shown to be horizontally transmitted through hematopoietic stem cell transplantation. Here, we present a clinical case of horizontal transmission of iciHHV-6A from donor to recipient through liver transplantation. Molecular analysis performed on three viral genes (7.2 kb) in the recipient and donor samples supports transmission of iciHHV-6A from the graft. Transmission was followed by reactivation, with high viral loads in several compartments. The infection was uncontrollable, leading to severe disease and death, despite antiviral treatments and the absence of resistance mutations. This case highlights the fact that physicians should be aware of the possible horizontal transmission of iciHHV-6 and its consequences in case of reactivation in immunocompromised patients. © 2018 The American Society of Transplantation and the American Society of Transplant Surgeons.

A selfish genetic element influencing longevity correlates with reactive behavioural traits in female house mice (Mus domesticus).

PubMed

Auclair, Yannick; König, Barbara; Lindholm, Anna K

2013-01-01

According to theory in life-history and animal personality, individuals with high fitness expectations should be risk-averse, while individuals with low fitness expectations should be more bold. In female house mice, a selfish genetic element, the t haplotype, is associated with increased longevity under natural conditions, representing an appropriate case study to investigate this recent theory empirically. Following theory, females heterozygous for the t haplotype (+/t) are hypothesised to express more reactive personality traits and be more shy, less explorative and less active compared to the shorter-lived homozygous wildtype females (+/+). As males of different haplotype do not differ in survival, no similar pattern is expected. We tested these predictions by quantifying boldness, exploration, activity, and energetic intake in both +/t and +/+ mice. +/t females, unlike +/+ ones, expressed some reactive-like personality traits: +/t females were less active, less prone to form an exploratory routine and tended to ingest less food. Taken together these results suggest that differences in animal personality may contribute to the survival advantage observed in +/t females but fail to provide full empirical support for recent theory.

Fe/Si(001) Ferromagnetic Layers: Reactivity, Local Atomic Structure and Magnetism

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

Lungu, G. A.; Costescu, R. M.; Husanu, M. A.

2011-10-03

Ultrathin ferromagnetic Fe layers on Si(001) have recently been synthesized using the molecular beam epitaxy (MBE) technique, and their structural and magnetic properties, as well as their interface reactivity have been investigated. The study was undertaken as function of the amount of Fe deposited and of substrate temperature. The interface reactivity was characterized by Auger electron spectroscopy (AES). The surface structure was characterized by low-energy electron diffraction (LEED). The magnetism was investigated by magneto-optical Kerr effect (MOKE). A higher deposition temperature stabilizes a better surface ordering, but it also enhances Fe and Si interdiffusion and it therefore decreases the magnetism.more » Despite the rapid disappearance of the long range order with Fe deposition at room temperature, the material exhibits a significant uniaxial in-plane magnetic anisotropy. For the Fe deposition performed at high temperature (500 deg. C), a weak ferromagnetism is still observed, with saturation magnetization of about 10% of the value obtained previously. MOKE studies allowed inferring the main properties of the distinct formed layers.« less

Plasma-Functionalized Solution: A Potent Antimicrobial Agent for Biomedical Applications from Antibacterial Therapeutics to Biomaterial Surface Engineering.

PubMed

Park, Joo Young; Park, Sanghoo; Choe, Wonho; Yong, Hae In; Jo, Cheorun; Kim, Kijung

2017-12-20

Deadly diseases caused by pathogenic bacteria and viruses have increasingly victimized humans; thus, the importance of disinfection has increased in medical settings as well as in food and agricultural industries. Plasma contains multiple bactericidal agents, including reactive species, charged particles, and photons, which can have synergistic effects. In particular, the chemicals formed in aqueous solution during plasma exposure have the potential for high antibacterial activity against various bacterial infections. Here, we report the antibiotic potency of plasma-treated water (PTW). To illustrate the applicability of PTW for disinfecting biological substances, an Escherichia coli biofilm was used. We sought to identify the chemical species in PTW and investigate their separate effects on biofilm removal. Dielectric barrier discharge in ambient air was used to prepare the PTW and treat the biofilm directly. Hydrogen peroxide, ozone, and nitrites were identified as the long-lived reactive species in the PTW, whereas hydroxyl radicals and superoxide anions were identified as the short-lived reactive species in the PTW; all these species showed an ability to disinfect in biofilm removal.

A reactive distillation process for the treatment of LiCl-KCl eutectic waste salt containing rare earth chlorides

NASA Astrophysics Data System (ADS)

Eun, H. C.; Choi, J. H.; Kim, N. Y.; Lee, T. K.; Han, S. Y.; Lee, K. R.; Park, H. S.; Ahn, D. H.

2016-11-01

The pyrochemical process, which recovers useful resources (U/TRU metals) from used nuclear fuel using an electrochemical method, generates LiCl-KCl eutectic waste salt containing radioactive rare earth chlorides (RECl3). It is necessary to develop a simple process for the treatment of LiCl-KCl eutectic waste salt in a hot-cell facility. For this reason, a reactive distillation process using a chemical agent was achieved as a method to separate rare earths from the LiCl-KCl waste salt. Before conducting the reactive distillation, thermodynamic equilibrium behaviors of the reactions between rare earth (Nd, La, Ce, Pr) chlorides and the chemical agent (K2CO3) were predicted using software. The addition of the chemical agent was determined to separate the rare earth chlorides into an oxide form using these equilibrium results. In the reactive distillation test, the rare earth chlorides in LiCl-KCl eutectic salt were decontaminated at a decontamination factor (DF) of more than 5000, and were mainly converted into oxide (Nd2O3, CeO2, La2O3, Pr2O3) or oxychloride (LaOCl, PrOCl) forms. The LiCl-KCl was purified into a form with a very low concentration (<1 ppm) for the rare earth chlorides.

Impact of Microcystis aeruginosa Exudate on the Formation and Reactivity of Iron Oxide Particles Following Fe(II) and Fe(III) Addition.

PubMed

Garg, Shikha; Wang, Kai; Waite, T David

2017-05-16

Impact of the organic exudate secreted by a toxic strain of Microcystis aeruginosa on the formation, aggregation, and reactivity of iron oxides that are formed on addition of Fe(II) and Fe(III) salts to a solution of the exudate is investigated in this study. The exudate has a stabilizing effect on the particles formed with decreased aggregation rate and increased critical coagulant concentration required for diffusion-limited aggregation to occur. These results suggest that the presence of algal exudates from Microcystis aeruginosa may significantly influence particle aggregation both in natural water bodies where Fe(II) oxidation results in oxide formation and in water treatment where Fe(III) salts are commonly added to aid particle growth and contaminant capture. The exudate also affects the reactivity of iron oxide particles formed with exudate coated particles undergoing faster dissolution than bare iron oxide particles. This has implications to iron availability, especially where algae procure iron via dissolution of iron oxide particles as a result of either reaction with reducing moieties, light-mediated ligand to metal charge transfer and/or reaction with siderophores. The increased reactivity of exudate coated particles is attributed, for the most part, to the smaller size of these particles, higher surface area and increased accessibility of surface sites.

Polyamines are traps for reactive intermediates in furan metabolism

PubMed Central

Peterson, Lisa A.; Phillips, Martin B.; Lu, Ding; Sullivan, Mathilde M.

2011-01-01

Furan is toxic and carcinogenic in rodents. Because of the large potential for human exposure, furan is classified as a possible human carcinogen. The detailed mechanism by which furan causes toxicity and cancer is not yet known. Since furan toxicity requires cytochrome P450-catalyzed oxidation of furan, we have characterized the urinary and hepatocyte metabolites of furan to gain insight into the chemical nature of the reactive intermediate. Previous studies in hepatocytes indicated that furan is oxidized to the reactive α,β-unsaturated dialdehyde, cis-2-butene-1,4-dial (BDA), which reacts with glutathione (GSH) to form 2-(S-glutathionyl)-succinaldehyde (GSH-BDA). This intermediate forms pyrrole cross-links with cellular amines such as lysine and glutamine. In this report, we demonstrate that GSH-BDA also forms cross-links with ornithine, putrescine and spermidine when furan is incubated with rat hepatocytes. The relative levels of these metabolites are not completely explained by hepatocellular levels of the amines or by their reactivity with GSH-BDA. Mercapturic acid derivatives of the spermidine cross-links were detected in the urine of furan-treated rats, which indicates that this metabolic pathway occurs in vivo. Their detection in furan-treated hepatocytes and in urine from furan-treated rats indicates that polyamines may play an important role in the toxicity of furan PMID:21842885

Hemodynamic Profiles of Functional and Dysfunctional Forms of Repetitive Thinking.

PubMed

Ottaviani, Cristina; Brosschot, Jos F; Lonigro, Antonia; Medea, Barbara; Van Diest, Ilse; Thayer, Julian F

2017-04-01

The ability of the human brain to escape the here and now (mind wandering) can take functional (problem solving) and dysfunctional (perseverative cognition) routes. Although it has been proposed that only the latter may act as a mediator of the relationship between stress and cardiovascular disease, both functional and dysfunctional forms of repetitive thinking have been associated with blood pressure (BP) reactivity of the same magnitude. However, a similar BP reactivity may be caused by different physiological determinants, which may differ in their risk for cardiovascular pathology. To examine the way (hemodynamic profile) and the extent (compensation deficit) to which total peripheral resistance and cardiac output compensate for each other in determining BP reactivity during functional and dysfunctional types of repetitive thinking. Fifty-six healthy participants randomly underwent a perseverative cognition, a mind wandering, and a problem solving induction, each followed by a 5-min recovery period while their cardiovascular parameters were continuously monitored. Perseverative cognition and problem solving (but not mind wandering) elicited BP increases of similar magnitude. However, perseverative cognition was characterized by a more vascular (versus myocardial) profile compared to mind wandering and problem solving. As a consequence, BP recovery was impaired after perseverative cognition compared to the other two conditions. Given that high vascular resistance and delayed recovery are the hallmarks of hypertension the results suggest a potential mechanism through which perseverative cognition may act as a mediator in the relationship between stress and risk for developing precursors to cardiovascular disease.

Carbonate Mineralization of Volcanic Province Basalts

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

Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

2010-03-31

Flood basalts are receiving increasing attention as possible host formations for geologic sequestration of anthropogenic CO2, with studies underway in the United States, India, Iceland, and Canada. As an extension of our previous experiments with Columbia River basalt, basalts from the eastern United States, India, and South Africa were reacted with aqueous dissolved CO2 and aqueous dissolved CO2-H2S mixtures under supercritical CO2 (scCO2) conditions to study the geochemical reactions resulting from injection of CO2 in such formations. The results of these studies are consistent with cation release behavior measured in our previous experiments (in press) for basalt samples tested inmore » single pass flow through dissolution experiments under dilute solution and mildly acidic conditions. Despite the basalt samples having similar bulk chemistry, mineralogy and apparent dissolution kinetics, long-term static experiments show significant differences in rates of mineralization as well as compositions and morphologies of precipitates that form when the basalts are reacted with CO2-saturated water. For example, basalt from the Newark Basin in the United States was by far the most reactive of any basalt tested to date. Carbonate reaction products for the Newark Basin basalt were globular in form and contained significantly more Fe than the secondary carbonates that precipitated on the other basalt samples. In comparison, the post-reacted samples associated with the Columbia River basalts from the United States contained calcite grains with classic dogtooth spar morphology and trace cation substitution (Mg and Mn). Carbonation of the other basalts produced precipitates with compositions that varied chemically throughout the entire testing period. Examination of polished cross sections of the reacted grains by scanning electron microscopy and energy dispersive x-ray spectroscopy show precipitate overgrowths with varying chemical compositions. Compositional differences in the precipitates suggest changes in fluid chemistry unique to the dissolution behavior of each basalt sample reacted with CO2-saturated water. The Karoo basalt from South Africa appeared the least reactive, with very limited mineralization occurring during the testing with CO2-saturated water. The relative reactivity of different basalt samples were unexpectedly different in the experiments conducted using aqueous dissolved CO2-H2S mixtures versus those reacted with aqueous dissolved CO2 mixtures. For example, the Karoo basalt was highly reactive in the presence of aqueous dissolved CO2-H2S, as evident by small nodules of carbonate coating the basalt grains after 181 days of testing. However the most reactive basalt in CO2-H2O, Newark Basin, formed limited amounts of carbonate precipitates in the presence of aqueous dissolved CO2-H2S mixture. Basalt reactivity in CO2-H2O mixtures appears to be controlled by the composition of the glassy mesostasis, which is the most reactive component in the basalt rock. With the addition of H2S to the CO2-H2O system, basalt reactivity appears to be controlled by precipitation of coatings of insoluble Fe sulfides.« less

Thiol trapping and metabolic redistribution of sulfur metabolites enable cells to overcome cysteine overload

PubMed Central

Deshpande, Anup Arunrao; Bhatia, Muskan; Laxman, Sunil; Bachhawat, Anand Kumar

2017-01-01

Cysteine is an essential requirement in living organisms. However, due to its reactive thiol side chain, elevated levels of intracellular cysteine can be toxic and therefore need to be rapidly eliminated from the cellular milieu. In mammals and many other organisms, excess cysteine is believed to be primarily eliminated by the cysteine dioxygenase dependent oxidative degradation of cysteine, followed by the removal of the oxidative products. However, other mechanisms of tackling excess cysteine are also likely to exist, but have not thus far been explored. In this study, we use Saccharomyces cerevisiae, which naturally lacks a cysteine dioxygenase, to investigate mechanisms for tackling cysteine overload. Overexpressing the high affinity cysteine transporter, YCT1, enabled yeast cells to rapidly accumulate high levels of intracellular cysteine. Using targeted metabolite analysis, we observe that cysteine is initially rapidly interconverted to non-reactive cystine in vivo. A time course revealed that cells systematically convert excess cysteine to inert thiol forms; initially to cystine, and subsequently to cystathionine, S-Adenosyl-L-homocysteine (SAH) and S-Adenosyl L-methionine (SAM), in addition to eventually accumulating glutathione (GSH) and polyamines. Microarray based gene expression studies revealed the upregulation of arginine/ornithine biosynthesis a few hours after the cysteine overload, and suggest that the non-toxic, non-reactive thiol based metabolic products are eventually utilized for amino acid and polyamine biogenesis, thereby enabling cell growth. Thus, cells can handle potentially toxic amounts of cysteine by a combination of thiol trapping, metabolic redistribution to non-reactive thiols and subsequent consumption for anabolism. PMID:28435838

Characterization and device applications of ZnO films deposited by high power impulse magnetron sputtering (HiPIMS)

NASA Astrophysics Data System (ADS)

Partridge, J. G.; Mayes, E. L. H.; McDougall, N. L.; Bilek, M. M. M.; McCulloch, D. G.

2013-04-01

ZnO films have been reactively deposited on sapphire substrates at 300 °C using a high impulse power magnetron sputtering deposition system and characterized structurally, optically and electronically. The unintentionally doped n-type ZnO films exhibit high transparency, moderate carrier concentration (˜5 × 1018 cm-3) and a Hall mobility of 8.0 cm2 V-1 s-1, making them suitable for electronic device applications. Pt/ZnO Schottky diodes formed on the HiPIMS deposited ZnO exhibited rectification ratios up to 104 at ±2 V and sensitivity to UV light.

Distilling Heterogeneity among Children with Disruptive Behavior: Associations between Symptom Patterns and Social Functioning.

PubMed

Aitken, Madison; Henry, Shanelle; Andrade, Brendan F

2017-10-16

Children with disruptive behavior (DB) are a heterogeneous group who exhibit several characteristics that may contribute to poor social functioning. The present study identified profiles of reactive aggression, proactive aggression, callous-unemotional (CU) traits, and prosocial behavior in a sample of children with DB. Associations with social functioning (social interaction, social status) were then examined, along with sex differences in profile membership. Parent ratings of 304 clinic-referred children ages 6-12 years with DB were analyzed using latent profile analysis. Five profiles were identified: 1) Moderate prosocial behavior, reactive aggression, and CU, and low proactive aggression (labelled Moderate); 2) Relatively high prosocial behavior and low reactive and proactive aggression and CU traits (Prosocial); 3) High prosocial behavior and reactive aggression, moderate proactive aggression, and low-moderate CU (Reactive-Prosocial); 4) Low prosocial behavior, high CU, high-moderate reactive aggression, and low-moderate proactive aggression (Reactive-CU); and 5) Low prosocial behavior and high reactive and proactive aggression and CU (Aggressive-CU). Profiles characterized by CU traits, reactive aggression, and low prosocial behavior were associated with the most problematic parent-rated social interaction and social status. The results highlight the need to differentiate profiles of psychopathology in children with DB to better address factors most associated with social functioning.

Regioselective Aziridination of Silyl Allenes and Application for the Synthesis of New Heterocycles

NASA Astrophysics Data System (ADS)

Burke, Eileen Grace

Rhodium catalyzed aziridination of homoallenic sulfamates has proven to be a successful first step in the synthesis of a diverse array of complex nitrogenated motifs. Previously, however, the resultant methyleneaziridine was limited to the exocyclic isomer. In this work, a reliable direction strategy for the formation of the endocyclic isomer was identified. Placement of a silicon group on the allene so that its C - Si bond is co-planar to the distal pi-bond allowed for stabilization of the developing positive charge during aziridination, and therefore selective activation to form the endocyclic methyleneaziridine. This strategy proved robust, and endocyclic methyleneaziridines were formed in high yields with exclusive formation of the desired isomer regardless of the substitution of the allene. With the endocyclic isomer now readily available, its reactivity could be explored. First, the endocyclic methyleneaziridine was applied to the synthesis of densely functionalized, nitrogen containing motifs. In comparison with their exocyclic counterparts, the endocyclic methyleneaziridines were found to have differing reactivity. The olefin could be epoxidized using meta-chloroperoxybenzoic acid (mCPBA), and the resulting spirocyclic intermediate rapidly rearranged to an azetidin-3-one. This synthesis of the highly substituted fourmembered heterocycle represented a novel approach to these motifs, and was found to be both flexible, and to selectively form a single diastereomer. Additional derivatization of these scaffolds gave a diverse array of complex products. Further use of the endocyclic methyleneaziridine focused not on the complexity of the product motif but rather on its utility. The remaining silyl group could be eliminated upon reaction with a fluoride source, triggering the formation of an alkyne and resultant opening of the aziridine. This strained heterocyclic alkyne and its synthesis represent a new addition to the field of strained alkyne synthesis. Uniquely, the arrangement of heteroatoms activated the alkyne without allowing for detrimental relaxation of ring strain, giving a strained alkyne that balanced reactivity and stability. These alkynes were applied to post-polymerization modification, wherein their unique capability of opening the strain inducing ring after reaction of the alkyne was successfully demonstrated.

Infant negative reactivity defines the effects of parent-child synchrony on physiological and behavioral regulation of social stress.

PubMed

Pratt, Maayan; Singer, Magi; Kanat-Maymon, Yaniv; Feldman, Ruth

2015-11-01

How infants shape their own development has puzzled developmentalists for decades. Recent models suggest that infant dispositions, particularly negative reactivity and regulation, affect outcome by determining the extent of parental effects. Here, we used a microanalytic experimental approach and proposed that infants with varying levels of negative reactivity will be differentially impacted by parent-infant synchrony in predicting physiological and behavioral regulation of increasing social stress during an experimental paradigm. One hundred and twenty-two mother-infant dyads (4-6 months) were observed in the face-to-face still face (SF) paradigm and randomly assigned to three experimental conditions: SF with touch, standard SF, and SF with arms' restraint. Mother-infant synchrony and infant negative reactivity were observed at baseline, and three mechanisms of behavior regulation were microcoded; distress, disengagement, and social regulation. Respiratory sinus arrhythmia baseline, reactivity, and recovery were quantified. Structural equation modeling provided support for our hypothesis. For physiological regulation, infants high in negative reactivity receiving high mother-infant synchrony showed greater vagal withdrawal, which in turn predicted comparable levels of vagal recovery to that of nonreactive infants. In behavioral regulation, only infants low in negative reactivity who received high synchrony were able to regulate stress by employing social engagement cues during the SF phase. Distress was reduced only among calm infants to highly synchronous mothers, and disengagement was lowest among highly reactive infants experiencing high mother-infant synchrony. Findings chart two pathways by which synchrony may bolster regulation in infants of high and low reactivity. Among low reactive infants, synchrony builds a social repertoire for handling interpersonal stress, whereas in highly reactive infants, it constructs a platform for repeated reparation of momentary interactive "failures" and reduces the natural tendency of stressed infants to disengage from source of distress. Implications for the construction of synchrony-focused interventions targeting infants of varying dispositions are discussed.

Relational victimization, friendship, and adolescents' hypothalamic-pituitary-adrenal axis responses to an in vivo social stressor.

PubMed

Calhoun, Casey D; Helms, Sarah W; Heilbron, Nicole; Rudolph, Karen D; Hastings, Paul D; Prinstein, Mitchell J

2014-08-01

Adolescents' peer experiences may have significant associations with biological stress-response systems, adding to or reducing allostatic load. This study examined relational victimization as a unique contributor to reactive hypothalamic-pituitary-adrenal (HPA) axis responses as well as friendship quality and behavior as factors that may promote HPA recovery following a stressor. A total of 62 adolescents (ages 12-16; 73% female) presenting with a wide range of life stressors and adjustment difficulties completed survey measures of peer victimization and friendship quality. Cortisol samples were collected before and after a lab-based interpersonally themed social stressor task to provide measures of HPA baseline, reactivity, and recovery. Following the stressor task, adolescents discussed their performance with a close friend; observational coding yielded measures of friends' responsiveness. Adolescents also reported positive and negative friendship qualities. Results suggested that higher levels of adolescents' relational victimization were associated with blunted cortisol reactivity, even after controlling for physical forms of victimization and other known predictors of HPA functioning (i.e., life stress or depressive symptoms). Friendship qualities (i.e., low negative qualities) and specific friendship behaviors (i.e., high levels of responsiveness) contributed to greater HPA regulation; however, consistent with theories of rumination, high friend responsiveness in the context of high levels of positive friendship quality contributed to less cortisol recovery. Findings extend prior work on the importance of relational victimization and dyadic peer relations as unique and salient correlates of adaptation in adolescence.

Relational victimization, friendship, and adolescents’ hypothalamic–pituitary–adrenal axis responses to an in vivo social stressor

PubMed Central

CALHOUN, CASEY D.; HELMS, SARAH W.; HEILBRON, NICOLE; RUDOLPH, KAREN D.; HASTINGS, PAUL D.; PRINSTEIN, MITCHELL J.

2014-01-01

Adolescents’ peer experiences may have significant associations with biological stress-response systems, adding to or reducing allostatic load. This study examined relational victimization as a unique contributor to reactive hypothalamic–pituitary–adrenal (HPA) axis responses as well as friendship quality and behavior as factors that may promote HPA recovery following a stressor. A total of 62 adolescents (ages 12–16; 73% female) presenting with a wide range of life stressors and adjustment difficulties completed survey measures of peer victimization and friendship quality. Cortisol samples were collected before and after a lab-based interpersonally themed social stressor task to provide measures of HPA baseline, reactivity, and recovery. Following the stressor task, adolescents discussed their performance with a close friend; observational coding yielded measures of friends’ responsiveness. Adolescents also reported positive and negative friendship qualities. Results suggested that higher levels of adolescents’ relational victimization were associated with blunted cortisol reactivity, even after controlling for physical forms of victimization and other known predictors of HPA functioning (i.e., life stress or depressive symptoms). Friendship qualities (i.e., low negative qualities) and specific friendship behaviors (i.e., high levels of responsiveness) contributed to greater HPA regulation; however, consistent with theories of rumination, high friend responsiveness in the context of high levels of positive friendship quality contributed to less cortisol recovery. Findings extend prior work on the importance of relational victimization and dyadic peer relations as unique and salient correlates of adaptation in adolescence. PMID:25047287

Trait aggressiveness modulates neurophysiological correlates of laboratory-induced reactive aggression in humans.

PubMed

Krämer, Ulrike M; Büttner, Sarah; Roth, Gerhard; Münte, Thomas F

2008-08-01

Reactive aggression following provocation is a frequent form of human social behavior. The neural basis of reactive aggression, especially its control, remains poorly understood, however. We conducted an event-related potential (ERP) study using a competitive reaction time task that elicits aggression through provocation. Participants were selected from a larger sample because of extreme scores in trait aggressiveness, yielding high and low trait aggressive groups. As each trial in the task is separated into a decision phase, during which the punishment level for the opponent is set, and an outcome phase, during which the punishment is applied or received, we were able to disentangle provocation-related and evaluation-related modulations of the ERPs during the aggressive interaction. Specifically, we observed an enhanced frontal negativity during the decision phase under high provocation that was positively correlated with the participants' ability to refrain from retaliation. This held true for high trait aggressive participants only, pointing to a higher need for inhibitory and control processes in these people when provoked. During the outcome phase, we detected a mediofrontal negativity in loss compared to win trials, resembling previous ERP findings to negative feedback stimuli, which have been linked to the evaluation of an outcome's valence. This mediofrontal negativity was differentially pronounced in aggressive and nonaggressive participants: Nonaggressive participants showed only a slightly smaller mediofrontal negativity in win than in loss trials, suggesting that for them punishing the opponent had a similar negative valence as being punished.

Development of the Use of Alternative Cements for the Treatment of Intermediate Level Waste

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

Hayes, M.; Godfrey, I.H.

2007-07-01

This paper describes initial development studies undertaken to investigate the potential use of alternative, non ordinary Portland cement (OPC) based encapsulation matrices to treat historic legacy wastes within the UK's Intermediate Level Waste (ILW) inventory. Currently these wastes are encapsulated in composite OPC cement systems based on high replacement with blast furnace slag of pulverised fuel ash. However, the high alkalinity of these cements can lead to high corrosion rates with reactive metals found in some wastes releasing hydrogen and forming expansive corrosion products. This paper therefore details preliminary results from studies on two commercial products, calcium sulfo-aluminate (CSA) andmore » magnesium phosphate (MP) cement which react with a different hydration chemistry, and which may allow wastes containing these metals to be encapsulated with lower reactivity. The results indicate that grouts can be formulated from both cements over a range of water contents and reactant ratios that have significantly improved fluidity in comparison to typical OPC cements. All designed mixes set in 24 hours with zero bleed and the pH values in the plastic state were in the range 10-11 for CSA and 5-7 for MP cements. In addition, a marked reduction in aluminium corrosion rate has been observed in both types of cements compared to a composite OPC system. These results therefore provide encouragement that both cement types can provide a possible alternative to OPC in the immobilisation of reactive wastes, however further investigation is needed. (authors)« less

Gestational diabetes mellitus alters maternal and neonatal circulating endothelial progenitor cell subsets.

PubMed

Acosta, Juan C; Haas, David M; Saha, Chandan K; Dimeglio, Linda A; Ingram, David A; Haneline, Laura S

2011-03-01

The purpose of this study was to examine whether women with gestational diabetes mellitus (GDM) and their offspring have reduced endothelial progenitor cell subsets and vascular reactivity. Women with GDM, healthy control subjects, and their infants participated. Maternal blood and cord blood were assessed for colony-forming unit-endothelial cells and endothelial progenitor cell subsets with the use of polychromatic flow cytometry. Cord blood endothelial colony-forming cells were enumerated. Vascular reactivity was tested by laser Doppler imaging. Women with GDM had fewer CD34, CD133, CD45, and CD31 cells (circulating progenitor cells [CPCs]) at 24-32 weeks' gestation and 1-2 days after delivery, compared with control subjects. No differences were detected in colony-forming unit-endothelial cells or colony-forming unit-endothelial cells. In control subjects, CPCs were higher in the third trimester, compared with the postpartum period. Cord blood from GDM pregnancies had reduced CPCs. Vascular reactivity was not different between GDM and control subjects. The normal physiologic increase in CPCs during pregnancy is impaired in women with GDM, which may contribute to endothelial dysfunction and GDM-associated morbidities. Copyright © 2011 Mosby, Inc. All rights reserved.

Efficient MgO-based mesoporous CO2 trapper and its performance at high temperature.

PubMed

Han, Kun Kun; Zhou, Yu; Chun, Yuan; Zhu, Jian Hua

2012-02-15

A novel MgO-based porous adsorbent has been synthesized in a facile co-precipitation method for the first time, in order to provide a candidate for trapping CO(2) in flue gas at high temperature. The resulting composite exhibits a mesoporous structure with a wide pore size distribution, due to the even dispersion and distribution of microcrystalline MgO in the framework of alumina to form a concrete-like structure. These sorbents can capture CO(2) at high temperature (150-400°C), possessing high reactivity and stability in cyclic adsorption-desorption processes, providing competitive candidates to control CO(2) emission. Copyright © 2011 Elsevier B.V. All rights reserved.

Mechano-chemical pathways to H2O and CO2 splitting

NASA Astrophysics Data System (ADS)

Vedadi, Mohammad H.; Haas, Stephan

2011-10-01

The shock-induced collapse of CO2-filled nanobubbles is investigated using molecular dynamics simulations based on a reactive force field. The energetic nanojet and high-pressure water hammer shock formed during and after collapse of the nanobubble trigger mechano-chemical H2O-CO2 reactions, some of which lead to splitting of water and formation of O2 molecules. The dominant pathways through which splitting of water molecules occur are identified.

reaxFF Reactive Force Field for Disulfide Mechanochemistry, Fitted to Multireference ab Initio Data.

PubMed

Müller, Julian; Hartke, Bernd

2016-08-09

Mechanochemistry, in particular in the form of single-molecule atomic force microscopy experiments, is difficult to model theoretically, for two reasons: Covalent bond breaking is not captured accurately by single-determinant, single-reference quantum chemistry methods, and experimental times of milliseconds or longer are hard to simulate with any approach. Reactive force fields have the potential to alleviate both problems, as demonstrated in this work: Using nondeterministic global parameter optimization by evolutionary algorithms, we have fitted a reaxFF force field to high-level multireference ab initio data for disulfides. The resulting force field can be used to reliably model large, multifunctional mechanochemistry units with disulfide bonds as designed breaking points. Explorative calculations show that a significant part of the time scale gap between AFM experiments and dynamical simulations can be bridged with this approach.

Synthesis of Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} through a reactive flux method and its visible-light photocatalytic performances

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

Zhu, Xianglin; Wang, Zeyan, E-mail: wangzeyan@sdu.edu.cn, E-mail: bbhuang@sdu.edu.cn; Huang, Baibiao, E-mail: wangzeyan@sdu.edu.cn, E-mail: bbhuang@sdu.edu.cn

2015-10-01

Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} was prepared by a reactive flux method. The structures, morphologies, and light absorption properties were investigated. Owing to the polar crystal structure, an internal electric field can be formed inside the material, which can facilitate the photogenerated charge separation during the photocatalytic process. Based on both the wide light absorption spectra and high charge separation efficiency originated from the polarized internal electric field, Ag{sub 9}(SiO{sub 4}){sub 2}NO{sub 3} exhibit higher efficiency over Ag{sub 3}PO{sub 4} during the degradation of organic dyes under visible light irradiation, which is expected to be a potential material for solarmore » energy harvest and conversion.« less

Solid-state structure of a Li/F carbenoid: pentafluoroethyllithium.

PubMed

Waerder, Benedikt; Steinhauer, Simon; Neumann, Beate; Stammler, Hans-Georg; Mix, Andreas; Vishnevskiy, Yury V; Hoge, Berthold; Mitzel, Norbert W

2014-10-20

Lithium carbenoids are versatile compounds for synthesis owing to their intriguing ambiphilic behavior. Although this class of compounds has been known for several years, few solid-state structures exist because of their high reactivity and often low thermal stability. Using cryo X-ray techniques, we were now able to elucidate the first solid-state structure of a Li/F alkyl carbenoid, pentafluoroethyllithium (LiC2F5), finally yielding a prototype for investigating structure-reactivity relationships for this class of molecules. The compound forms a diethyl ether-solvated dimer bridged by a rare C-F-Li link. Complementary NMR spectroscopy studies in solution show dynamic processes and indicate rapid exchange of starting material and product. Theoretical investigations help to understand the formation of the observed unusual structural motif. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of Lipid Peroxidation-Derived α, β-Unsaturated Aldehydes in Vascular Dysfunction

PubMed Central

Lee, Seung Eun; Park, Yong Seek

2013-01-01

Vascular diseases are the most prominent cause of death, and inflammation and vascular dysfunction are key initiators of the pathophysiology of vascular disease. Lipid peroxidation products, such as acrolein and other α, β-unsaturated aldehydes, have been implicated as mediators of inflammation and vascular dysfunction. α, β-Unsaturated aldehydes are toxic because of their high reactivity with nucleophiles and their ability to form protein and DNA adducts without prior metabolic activation. This strong reactivity leads to electrophilic stress that disrupts normal cellular function. Furthermore, α, β-unsaturated aldehydes are reported to cause endothelial dysfunction by induction of oxidative stress, redox-sensitive mechanisms, and inflammatory changes such as induction of cyclooxygenase-2 and cytokines. This review provides an overview of the effects of lipid peroxidation products, α, β-unsaturated aldehydes, on inflammation and vascular dysfunction. PMID:23819013

Reactive N emissions from beef cattle feedlots

USDA-ARS?s Scientific Manuscript database

Large amounts of nitrogen (N) are fed to meet the nutritional needs of beef cattle in feedlots. However, only from 10 to 15% of fed N is retained in animals. Most N is excreted. Chemical and biological processes transform manure N into ammonia, nitrous oxide and nitrate. These reactive forms of ...

Rheological properties of reactive extrusion modified waxy starch and waxy starch-polyacrylamide copolymer gels

USDA-ARS?s Scientific Manuscript database

The rheological properties of modified waxy starch and waxy starch-polyacrylamide graft copolymers prepared by reactive extrusion were investigated. Both materials can absorb huge amount of water and form gels. The modified waxy starch and waxy starch-polyacrylamide graft copolymer gels all exhibite...

DEVELOPMENT AND CHARACTERIZATION OF AN ANNULAR DENUDER METHODOLOGY FOR THE MEASUREMENT OF DIVALENT INORGANIC REACTIVE GASEOUS MERCURY IN AMBIENT AIR

EPA Science Inventory

Atmospheric mercury is predominantly present in the gaseous elemental form (Hg0). However, anthropogenic emissions (e.g. incineration, fossil fuel combustion) emit and natural processes create particulate-phase mercury (Hg(p)) and divalent reactive gas-phase mercury (RGM). RG...

Co-processing of agricultural plastic waste and switchgrass via tail gas reactive pyrolysis

USDA-ARS?s Scientific Manuscript database

Mixtures of agricultural plastic waste in the form of polyethylene hay bale covers (PE) (4-37%) and switchgrass were investigated using the US Department of Agriculture’s tail gas reactive pyrolysis (TGRP) at different temperatures (400-570 deg C). TGRP of switchgrass and plastic mixtures significan...

Characterizing Emotional Dysfunction in Borderline Personality, Major Depression, and their Co-occurrence

PubMed Central

Dixon-Gordon, Katherine L.; Weiss, Nicole H.; Tull, Matthew T.; DiLillo, David; Messman-Moore, Terri; Gratz, Kim L.

2015-01-01

This research aimed to characterize patterns of emotional reactivity and dysregulation in borderline personality, depression, and their co-occurrence. In Study 1, 488 young adult women from the community were categorized into four groups based on self-reported major depressive disorder (MDD) and borderline personality disorder (BPD) symptoms (Low BPD/Low MDD; Low BPD/High MDD; High BPD/Low MDD; High BPD/High MDD). Immediate and prolonged subjective emotional reactivity to a laboratory stressor were assessed, and participants completed self-report and behavioral measures of emotion dysregulation. Study 2 extended these findings, examining emotional reactivity and dysregulation in a clinical population of 176 substance dependent patients with diagnoses of BPD and MDD and including a biological index of emotional reactivity. Results revealed greater prolonged fear reactivity in the High BPD/High MDD (vs. Low BPD/Low MDD) group in Study 1, and greater prolonged anxiety and negative affect reactivity in both High BPD groups (vs. Low BPD/Low MDD and Low BPD/High MDD groups) in Study 2 (but no differences in cortisol reactivity). Results also demonstrated greater subjective (but not behavioral) emotion dysregulation in the High BPD/High MDD (vs. Low BPD/Low MDD) group in Study 1 and both High BPD groups (vs. both Low BPD groups) in Study 2. Finally, the High BPD/High MDD group reported greater difficulties controlling impulsive behaviors compared with all other groups in Study 1 and the Low BPD groups in Study 2. Findings suggest that BPD pathology (but not MDD pathology alone) is characterized by greater prolonged emotional (especially anxiety/fear-related) reactivity and heightened emotion dysregulation. PMID:26343484

Stratospheric ClO and ozone from the Microwave Limb Sounder on the Upper Atmosphere Research Satellite

NASA Technical Reports Server (NTRS)

Waters, J. W.; Froidevaux, L.; Read, W. G.; Manney, G. L.; Elson, L. S.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.

1993-01-01

Concentrations of atmospheric ozone and of ClO (the predominant form of reactive chlorine responsible for stratospheric ozone depletion) are reported for both the Arctic and Antarctic winters of the past 18 months. Chlorine in the lower stratosphere was almost completely converted to chemically reactive forms in both the northern and southern polar winter vortices. This occurred in the south long before the development of the Antarctic ozone hole, suggesting that ozone loss can be masked by influx of ozone-rich air.

Reactive multilayer synthesis of hard ceramic foils and films

DOEpatents

Makowiecki, Daniel M.; Holt, Joseph B.

1996-01-01

A method for synthesizing hard ceramic materials such as carbides, borides nd aluminides, particularly in the form of coatings provided on another material so as to improve the wear and abrasion performance of machine tools, for example. The method involves the sputter deposition of alternating layers of reactive metals with layers of carbon, boron, or aluminum and the subsequent reaction of the multilayered structure to produce a dense crystalline ceramic. The material can be coated on a substrate or formed as a foil which can be coild as a tape for later use.

Cardiovascular Reactivity in Patients With Major Depressive Disorder With High- or Low-Level Depressive Symptoms: A Cross-Sectional Comparison of Cardiovascular Reactivity to Laboratory-Induced Mental Stress.

PubMed

Wang, Mei-Yeh; Chiu, Chen-Huan; Lee, Hsin-Chien; Su, Chien-Tien; Tsai, Pei-Shan

2016-03-01

Depression increases the risk of adverse cardiac events. Cardiovascular reactivity is defined as the pattern of cardiovascular responses to mental stress. An altered pattern of cardiovascular reactivity is an indicator of subsequent cardiovascular disease. Because depression and adverse cardiac events may have a dose-dependent association, this study examined the differences in cardiovascular reactivity to mental stress between patients with major depressive disorder (MDD) with high depression levels and those with low depression levels. Moreover, autonomic nervous system regulation is a highly plausible biological mechanism for the pattern of cardiovascular reactivity to mental stress. The association between cardiovascular reactivity and parameters of heart rate variability (HRV), an index for quantifying autonomic nervous system activity modulation, was thus examined. This study included 88 patients with MDD. HRV was measured before stress induction. The Stroop Color and Word Test and mirror star-tracing task were used to induce mental stress. We observed no significant association between depressive symptom level and any of the cardiovascular reactivity parameters. Cardiovascular reactivity to mental stress was comparable between patients with MDD with high-level depressive symptoms and those with low-level depressive symptoms. After adjusting for confounding variables, the high-frequency domain of HRV was found to be an independent predictor of the magnitude of heart rate reactivity (β = -.33, p = .002). In conclusion, the magnitude of cardiovascular reactivity may be independent of depression severity in patients with MDD. The autonomic regulation of cardiovascular responses to mental stress primarily influences heart rate reactivity in patients with MDD. © The Author(s) 2015.

Reactivity-based drug discovery using vitamin B(6)-derived pharmacophores.

PubMed

Wondrak, Georg T

2008-05-01

Endogenous reactive intermediates including photoexcited states of tissue chromophores, reactive oxygen species (ROS), reactive carbonyl species (RCS), transition metal ions, and Schiff bases have been implicated in the initiation and progression of diverse human pathologies including tumorigenesis, atherosclerosis, diabetes, and neurodegenerative disease. In contrast to structure-based approaches that target macromolecules by selective ligands, reactivity-based drug discovery uses chemical reagents as therapeutics that target reactive chemical species involved in human pathology. Reactivity-based design of prototype agents that effectively antagonize, modulate, and potentially even reverse the chemistry underlying tissue damage from oxidative and carbonyl stress therefore holds great promise in delivering significant therapeutic benefit. Apart from its established role as an essential cofactor for numerous enzymes, a large body of evidence suggests that B(6)-vitamers contain reactive pharmacophores that mediate therapeutically useful non-vitamin drug actions as potent antioxidants, metal chelators, carbonyl scavengers, Schiff base forming agents, and photosensitizers. Based on the fascinating chemical versatility of B(6)-derived pharmacophores, B(6)-vitamers are therefore promising lead compounds for reactivity-based drug design.

Synthesis and processing of nanostructured BN and BN/Ti composites

NASA Astrophysics Data System (ADS)

Horvath, Robert Steven

Superhard materials, such as cubic-BN, are widely used in machine tools, grinding wheels, and abrasives. Low density combined with high hardness makes c-BN and its composites attractive candidate materials for personnel and vehicular armor. However, improvements in toughness, and ballistic-impact performance, are needed to meet anticipated performance requirements. To achieve such improvements, we have targeted for development nanostructured c-BN, and its composites with Ti. Current research utilizes an experimental high pressure/high temperature (HPHT) method to produce these materials on a laboratory scale. Results from this work should transfer well into the industrial arena, utilizing high-tonnage presses used in the production of synthetic diamond and c-BN. Progress has been made in: (1) HPHT synthesis of cBN powder using Mg as catalyst; (2) HPHT consolidation of cBN powder to produce nanostructured cBN; (3) reactive-HPHT consolidation of mixed cBN/Ti powder to produce nanostructured Ti- or TiB2/TiN-bonded cBN; and (4) reactive-HPHT consolidation of mixed hBN/Ti powder to produce nanostructured Ti-bonded TiB2/TiN or TiB2/TiN. Even so, much remains to be done to lay a firm scientific foundation to enable the reproducible fabrication of large-area panels for armor applications. To this end, Rutgers has formed a partnership with a major producer of hard and superhard materials. The ability to produce hard and superhard nanostructured composites by reacting cBN or hBN with Ti under high pressure also enables multi-layered structures to be developed. Such structures may be designed to satisfy impedance-mismatch requirements for high performance armor, and possibly provide a multi-hit capability. A demonstration has been made of reactive-HPHT processing of multi-layered composites, consisting of alternating layers of superhard Ti-bonded cBN and tough Ti. It is noteworthy that the pressure requirements for processing Ti-bonded cBN, Ti-bonded TiB2/TiN, and their corresponding multi-layered structures are in the 0.1-1.0 GPa range, well within the capabilities of today's hot-pressing technologies; thus scaling this new reactive-HPHT processing technology seems assured. Future research will focus on establishing mechanisms and kinetics of the various phase transformations observed during reactive-HPHT processing, with the objective of being able to optimize processing parameters to generate nanostructured cBN-based and TiB2/TiN-based composites that display superior mechanical properties, particularly under high-strain-rate conditions.

Birth weight, current anthropometric markers, and high sensitivity C-reactive protein in Brazilian school children.

PubMed

Boscaini, Camile; Pellanda, Lucia Campos

2015-01-01

Studies have shown associations of birth weight with increased concentrations of high sensitivity C-reactive protein. This study assessed the relationship between birth weight, anthropometric and metabolic parameters during childhood, and high sensitivity C-reactive protein. A total of 612 Brazilian school children aged 5-13 years were included in the study. High sensitivity C-reactive protein was measured by particle-enhanced immunonephelometry. Nutritional status was assessed by body mass index, waist circumference, and skinfolds. Total cholesterol and fractions, triglycerides, and glucose were measured by enzymatic methods. Insulin sensitivity was determined by the homeostasis model assessment method. Statistical analysis included chi-square test, General Linear Model, and General Linear Model for Gamma Distribution. Body mass index, waist circumference, and skinfolds were directly associated with birth weight (P < 0.001, P = 0.001, and P = 0.015, resp.). Large for gestational age children showed higher high sensitivity C-reactive protein levels (P < 0.001) than small for gestational age. High birth weight is associated with higher levels of high sensitivity C-reactive protein, body mass index, waist circumference, and skinfolds. Large for gestational age altered high sensitivity C-reactive protein and promoted additional risk factor for atherosclerosis in these school children, independent of current nutritional status.

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

Coker, Eric Nicholas; Miller, James E.

A thermal oxidation-reduction cycle is disclosed that uses iron titanium oxide as the reactive material. The cycle may be used for the thermal splitting of water and/or carbon dioxide to form hydrogen and/or carbon monoxide. The formed compounds may be used as syngas precursors to form fuels.

Daily life stress reactivity in remitted versus non-remitted depressed individuals.

PubMed

van Winkel, M; Nicolson, N A; Wichers, M; Viechtbauer, W; Myin-Germeys, I; Peeters, F

2015-06-01

Little is known about how daily life mood reactivity to minor stressors (stress reactivity) might change following major depressive disorder (MDD) treatment. We investigate whether (i) mood states and appraisals of daily stressors change after treatment; (ii) stress reactivity to event, activity, or social stress differs; (iii) stress reactivity depends on severity of residual depressive symptoms; and (iv) stress reactivity in individuals with remitted or non-remitted depression differ from that of never-depressed individuals. Thirty depressed individuals participated in an experience sampling study before and after a treatment period of 18 months; 39 healthy individuals formed a comparison group. Reactivity of positive affect (PA) and negative affect (NA) to daily stressors were measured. More residual symptoms were associated with larger NA responses to stress. Compared to healthy controls, participants with non-remitted MDD showed higher NA-reactivity to all stressors. In contrast, stress reactivity to event and activity stressors was normalized in remitted patients. However, they still showed heightened NA-reactivity to social stress. Greater stress reactivity to event and activity stress appears to be state-dependent. The heightened social stress reactivity in remitted patients suggests that sensitivity to social stress may reflect an underlying vulnerability in MDD. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Processing and mechanical properties of metal-ceramic composites with controlled microstructure formed by reactive metal penetration

NASA Astrophysics Data System (ADS)

Ellerby, Donald Thomas

1999-12-01

Compared to monolithic ceramics, metal-reinforced ceramic composites offer the potential for improved toughness and reliability in ceramic materials. As such, there is significant scientific and commercial interest in the microstructure and properties of metal-ceramic composites. Considerable work has been conducted on modeling the toughening behavior of metal reinforcements in ceramics; however, there has been limited application and testing of these concepts on real systems. Composites formed by newly developed reactive processes now offer the flexibility to systematically control metal-ceramic composite microstructure, and to test some of the property models that have been proposed for these materials. In this work, the effects of metal-ceramic composite microstructure on resistance curve (R-curve) behavior, strength, and reliability were systematically investigated. Al/Al2O3 composites were formed by reactive metal penetration (RMP) of aluminum metal into aluminosilicate ceramic preforms. Processing techniques were developed to control the metal content, metal composition, and metal ligament size in the resultant composite microstructure. Quantitative stereology and microscopy were used to characterize the composite microstructures, and then the influence of microstructure on strength, toughness, R-curve behavior, and reliability, was investigated. To identify the strength limiting flaws in the composite microstructure, fractography was used to determine the failure origins. Additionally, the crack bridging tractions produced by the metal ligaments in metal-ceramic composites formed by the RMP process were modeled. Due to relatively large flaws and low bridging stresses in RMP composites, no dependence of reliability on R-curve behavior was observed. The inherent flaws formed during reactive processing appear to limit the strength and reliability of composites formed by the RMP process. This investigation has established a clear relationship between processing, microstructure, and properties in metal-ceramic composites formed by the RMP process. RMP composite properties are determined by the metal-ceramic composite microstructure (e.g., metal content and ligament size), which can be systematically varied by processing. Furthermore, relative to the ceramic preforms used to make the composites, metal-ceramic composites formed by RMP generally have improved properties and combinations of properties that make them more desirable for advanced engineering applications.

Biological Sensitivity to Context: The Interactive Effects of Stress Reactivity and Family Adversity on Socio-Emotional Behavior and School Readiness

PubMed Central

Obradović, Jelena; Bush, Nicole R.; Stamperdahl, Juliet; Adler, Nancy E.; Boyce, W. Thomas

2009-01-01

This study examined the direct and interactive effects of stress reactivity and family adversity on socio-emotional and cognitive development in 338 five-to-six-year-old children. Neurobiological stress reactivity was measured as respiratory sinus arrhythmia and salivary cortisol responses to social, cognitive, sensory, and emotional challenges. Adaptation was assessed using child, parent, and teacher reports of externalizing symptoms, prosocial behaviors, school engagement, and academic competence. Results revealed significant interactions between reactivity and adversity. High stress reactivity was associated with more maladaptive outcomes in the context of high adversity but with better adaption in the context of low adversity. The findings corroborate a reconceptualization of stress reactivity as biological sensitivity to context by showing that high reactivity can both hinder and promote adaptive functioning. PMID:20331667

Mothers' depressive symptoms predict both increased and reduced negative reactivity: aversion sensitivity and the regulation of emotion.

PubMed

Dix, Theodore; Moed, Anat; Anderson, Edward R

2014-07-01

This study examined whether, as mothers' depressive symptoms increase, their expressions of negative emotion to children increasingly reflect aversion sensitivity and motivation to minimize ongoing stress or discomfort. In multiple interactions over 2 years, negative affect expressed by 319 mothers and their children was observed across variations in mothers' depressive symptoms, the aversiveness of children's immediate behavior, and observed differences in children's general negative reactivity. As expected, depressive symptoms predicted reduced maternal negative reactivity when child behavior was low in aversiveness, particularly with children who were high in negative reactivity. Depressive symptoms predicted high negative reactivity and steep increases in negative reactivity as the aversiveness of child behavior increased, particularly when high and continued aversiveness from the child was expected (i.e., children were high in negative reactivity). The findings are consistent with the proposal that deficits in parenting competence as depressive symptoms increase reflect aversion sensitivity and motivation to avoid conflict and suppress children's aversive behavior. © The Author(s) 2014.

Computational-Experimental Processing of Boride/Carbide Composites by Reactive Infusion of Hf Alloy Melts into B4C

DTIC Science & Technology

2015-09-16

AFRL-AFOSR-VA-TR-2015-0314 Computational -Experimental Processing of Boride /Carbide Composites by Reactive Infusion of Hf Alloy Melts into B4C...Computational -Experimental Processing of Boride /Carbide Composites by Reactive Infusion of Hf Alloy Melts into B4C 5a.  CONTRACT NUMBER 5b.  GRANT...with a packed bed of B4C to form boride - carbide precipitates. Although the ultimate goal of the research endeavor is to enhance significantly the

Studies on the reactive melt infiltration of silicon and silicon-molybdenum alloys in porous carbon

NASA Technical Reports Server (NTRS)

Singh, M.; Behrendt, D. R.

1992-01-01

Investigations on the reactive melt infiltration of silicon and silicon-1.7 and 3.2 at percent molybdenum alloys into porous carbon preforms have been carried out by process modeling, differential thermal analysis (DTA) and melt infiltration experiments. These results indicate that the initial pore volume fraction of the porous carbon preform is a critical parameter in determining the final composition of the raction-formed silicon carbide and other residual phases. The pore size of the carbon preform is very detrimental to the exotherm temperatures due to liquid silicon-carbon reactions encountered during the reactive melt infiltration process. A possible mechanism for the liquid silicon-porous (glassy) carbon reaction has been proposed. The composition and microstructure of the reaction-formed silicon carbide has been discussed in terms of carbon preform microstructures, infiltration materials, and temperatures.

Effects of periodontal therapy on C-reactive protein and HDL in serum of subjects with periodontitis.

PubMed

Leite, Anne Carolina Eleutério; Carneiro, Valéria Martins de Araújo; Guimarães, Maria do Carmo Machado

2014-01-01

To investigate the effects of nonsurgical periodontal therapy on levels of high-sensitivity C-reactive protein in the sera and its association with body mass index and high density lipoprotein in subjects with severe periodontitis. Sera from 28 subjects (mean age: 34.36±6.24; 32% men) with severe periodontitis and 27 healthy controls (mean age: 33.18±6.42; 33% men) were collected prior to periodontal therapy. Blood samples were obtained from 23 subjects who completed therapy (9-12 months). Oral and systemic parameters such as the number of blood cells, glucose examination, lipid profile, and high-sensitivity C-reactive protein levels accessed by high-sensitivity immunonephelometry assay, were included. Before therapy, in the periodontitis group, the ratio of subjects with high-sensitivity C-reactive protein <0.3 mg/dL was statistically lower than in the control group (P<0.0216). After therapy, the ratio of subjects with high-sensitivity C-reactive protein <0.3 mg/dL was significantly higher (65.22%) (P<0.0339). The mean value for body mass index was statistically lower in subjects with high-sensitivity C-reactive protein <0.3 mg/dL (24.63±4.19), compared with those with high-sensitivity C-reactive protein >0.3 mg/dL (28.91±6.03) (P<0.0411). High density lipoprotein presented a mean value statistically higher after therapy (P<0.0027). In systemically healthy subjects with periodontitis, periodontal therapy was associated with decreased levels of circulating high-sensitivity C-reactive protein and increase of high density lipoprotein in serum. The clinical trial was registered at http://www.clinicaltrials.gov.br/, No. RBR-24T799.

In situ visualisation and characterisation of the capacity of highly reactive minerals to preserve soil organic matter (SOM) in colloids at submicron scale.

PubMed

Xiao, Jian; Wen, Yongli; Li, Huan; Hao, Jialong; Shen, Qirong; Ran, Wei; Mei, Xinlan; He, Xinhua; Yu, Guanghui

2015-11-01

Mineral-organo associations (MOAs) are a mixture of identifiable biopolymers associated with highly reactive minerals and microorganisms. However, the in situ characterization and correlation between soil organic matter (SOM) and highly reactive Al and Fe minerals are still unclear for the lack of technologies, particularly in the long-term agricultural soil colloids at submicron scale. We combined several novel techniques, including nano-scale secondary ion mass spectrometry (NanoSIMS), X-ray absorption near edge structure (XANES) and confocal laser scanning microscopy (CLSM) to characterise the capacity of highly reactive Al and Fe minerals to preserve SOM in Ferralic Cambisol in south China. Our results demonstrated that: (1) highly reactive minerals were strongly related to SOM preservation, while SOM had a more significant line correlation with the highly reactive Al minerals than the highly reactive Fe minerals, according to the regions of interest correlation analyses using NanoSIMS; (2) allophane and ferrihydrite were the potential mineral species to determine the SOM preservation capability, which was evaluated by the X-ray photoelectron spectroscopy (XPS) and Fe K-edge XANES spectroscopy techniques; and (3) soil organic biopolymers with dominant compounds, such as proteins, polysaccharides and lipids, were distributed at the rough and clustered surface of MOAs with high chemical and spatial heterogeneity according to the CLSM observation. Our results also promoted the understanding of the roles played by the highly reactive Al and Fe minerals in the spatial distribution of soil organic biopolymers and SOM sequestration. Copyright © 2015 Elsevier Ltd. All rights reserved.

Gasification Characteristics of Coal/Biomass Mixed Fuels

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

Mitchell, Reginald

2014-09-01

A research project was undertaken that had the overall objective of developing the models needed to accurately predict conversion rates of coal/biomass mixtures to synthesis gas under conditions relevant to a commercially-available coal gasification system configured to co-produce electric power as well as chemicals and liquid fuels. In our efforts to accomplish this goal, experiments were performed in an entrained flow reactor in order to produce coal and biomass chars at high heating rates and temperatures, typical of the heating rates and temperatures fuel particles experience in real systems. Mixed chars derived from coal/biomass mixtures containing up to 50% biomassmore » and the chars of the pure coal and biomass components were subjected to a matrix of reactivity tests in a pressurized thermogravimetric analyzer (TGA) in order to obtain data on mass loss rates as functions of gas temperature, pressure and composition as well as to obtain information on the variations in mass specific surface area during char conversion under kinetically-limited conditions. The experimental data were used as targets when determining the unknown parameters in the chemical reactivity and specific surface area models developed. These parameters included rate coefficients for the reactions in the reaction mechanism, enthalpies of formation and absolute entropies of adsorbed species formed on the carbonaceous surfaces, and pore structure coefficients in the model used to describe how the mass specific surface area of the char varies with conversion. So that the reactivity models can be used at high temperatures when mass transport processes impact char conversion rates, Thiele modulus – effectiveness factor relations were also derived for the reaction mechanisms developed. In addition, the reactivity model and a mode of conversion model were combined in a char-particle gasification model that includes the effects of chemical reaction and diffusion of reactive gases through particle pores and energy exchange between the particle and its environment. This char-particle gasification model is capable of predicting the average mass loss rates, sizes, apparent densities, specific surface areas, and temperatures of the char particles produced when co-firing coal and biomass to the type environments established in entrained flow gasifiers operating at high temperatures and elevated pressures.« less

Generic method for the absolute quantification of glutathione S-conjugates: Application to the conjugates of acetaminophen, clozapine and diclofenac.

PubMed

den Braver, Michiel W; Vermeulen, Nico P E; Commandeur, Jan N M

2017-03-01

Modification of cellular macromolecules by reactive drug metabolites is considered to play an important role in the initiation of tissue injury by many drugs. Detection and identification of reactive intermediates is often performed by analyzing the conjugates formed after trapping by glutathione (GSH). Although sensitivity of modern mass spectrometrical methods is extremely high, absolute quantification of GSH-conjugates is critically dependent on the availability of authentic references. Although 1 H NMR is currently the method of choice for quantification of metabolites formed biosynthetically, its intrinsically low sensitivity can be a limiting factor in quantification of GSH-conjugates which generally are formed at low levels. In the present study, a simple but sensitive and generic method for absolute quantification of GSH-conjugates is presented. The method is based on quantitative alkaline hydrolysis of GSH-conjugates and subsequent quantification of glutamic acid and glycine by HPLC after precolumn derivatization with o-phthaldialdehyde/N-acetylcysteine (OPA/NAC). Because of the lower stability of the glycine OPA/NAC-derivate, quantification of the glutamic acid OPA/NAC-derivate appeared most suitable for quantification of GSH-conjugates. The novel method was used to quantify the concentrations of GSH-conjugates of diclofenac, clozapine and acetaminophen and quantification was consistent with 1 H NMR, but with a more than 100-fold lower detection limit for absolute quantification. Copyright © 2017. Published by Elsevier B.V.

Nanoalloying and phase transformations during thermal treatment of physical mixtures of Pd and Cu nanoparticles

PubMed Central

Mukundan, Vineetha; Yin, Jun; Joseph, Pharrah; Luo, Jin; Shan, Shiyao; Zakharov, Dmitri N; Zhong, Chuan-Jian; Malis, Oana

2014-01-01

Nanoscale alloying and phase transformations in physical mixtures of Pd and Cu ultrafine nanoparticles are investigated in real time with in situ synchrotron-based x-ray diffraction complemented by ex situ high-resolution transmission electron microscopy. The combination of metal–support interaction and reactive/non-reactive environment was found to determine the thermal evolution and ultimate structure of this binary system. At 300 °C, the nanoparticles supported on silica and carbon black intermix to form a chemically ordered CsCl-type (B2) alloy phase. The B2 phase transforms into a disordered fcc alloy at higher temperature (> 450 °C). The alloy nanoparticles supported on silica and carbon black are homogeneous in volume, but evidence was found of Pd surface enrichment. In sharp contrast, when supported on alumina, the two metals segregated at 300 °C to produce almost pure fcc Cu and Pd phases. Upon further annealing of the mixture on alumina above 600 °C, the two metals interdiffused, forming two distinct disordered alloys of compositions 30% and 90% Pd. The annealing atmosphere also plays a major role in the structural evolution of these bimetallic nanoparticles. The nanoparticles annealed in forming gas are larger than the nanoparticles annealing in helium due to reduction of the surface oxides that promotes coalescence and sintering. PMID:27877663

Environmental Effects on Zirconium Hydroxide Nanoparticles and Chemical Warfare Agent Decomposition: Implications of Atmospheric Water and Carbon Dioxide.

PubMed

Balow, Robert B; Lundin, Jeffrey G; Daniels, Grant C; Gordon, Wesley O; McEntee, Monica; Peterson, Gregory W; Wynne, James H; Pehrsson, Pehr E

2017-11-15

Zirconium hydroxide (Zr(OH) 4 ) has excellent sorption properties and wide-ranging reactivity toward numerous types of chemical warfare agents (CWAs) and toxic industrial chemicals. Under pristine laboratory conditions, the effectiveness of Zr(OH) 4 has been attributed to a combination of diverse surface hydroxyl species and defects; however, atmospheric components (e.g., CO 2 , H 2 O, etc.) and trace contaminants can form adsorbates with potentially detrimental impact to the chemical reactivity of Zr(OH) 4 . Here, we report the hydrolysis of a CWA simulant, dimethyl methylphosphonate (DMMP) on Zr(OH) 4 determined by gas chromatography-mass spectrometry and in situ attenuated total reflectance Fourier transform infrared spectroscopy under ambient conditions. DMMP dosing on Zr(OH) 4 formed methyl methylphosphonate and methoxy degradation products on free bridging and terminal hydroxyl sites of Zr(OH) 4 under all evaluated environmental conditions. CO 2 dosing on Zr(OH) 4 formed adsorbed (bi)carbonates and interfacial carbonate complexes with relative stability dependent on CO 2 and H 2 O partial pressures. High concentrations of CO 2 reduced DMMP decomposition kinetics by occupying Zr(OH) 4 active sites with carbonaceous adsorbates. Elevated humidity promoted hydrolysis of adsorbed DMMP on Zr(OH) 4 to produce methanol and regenerated free hydroxyl species. Hydrolysis of DMMP by Zr(OH) 4 occurred under all conditions evaluated, demonstrating promise for chemical decontamination under diverse, real-world conditions.

Synthesis, characterization, and reactivity of arylpalladium cyanoalkyl complexes: selection of catalysts for the alpha-arylation of nitriles.

PubMed

Culkin, Darcy A; Hartwig, John F

2002-08-14

A new coupling process, the palladium-catalyzed alpha-arylation of nitriles, was developed by exploring the structure and reactivity of arylpalladium cyanoalkyl complexes. Complexes of 1,2-bis(diphenylphosphino)benzene (DPPBz), 1,1'-bis(di-i-propylphosphino)ferrocene (D(i)()PrPF), racemic-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), and diphenylethylphosphine (PPh(2)Et) were prepared. Coordination to palladium through the alpha-carbon was observed for DPPBz-ligated complexes and for complexes of primary and benzylic nitrile anions. However, the anion of isobutyronitrile was coordinated to palladium through the cyano-nitrogen when the complex was ligated by D(i)()PrPF. The isobutyronitrile anion displaced a phosphine ligand to form a C,N-bridged dimer when generated from PPh(2)Et-ligated palladium. These results suggest that the nitrile anion preferentially coordinates to palladium through the carbon atom in the absence of steric effects. Thermolysis of the arylpalladium cyanoalkyl complexes led to reductive elimination that formed alpha-aryl nitriles. The high yields and short reaction times observed for BINAP-ligated complexes suggested that BINAP-ligated palladium catalysts might be appropriate for the arylation of nitriles. Initial results on a palladium-catalyzed process for the direct coupling of aryl bromides and primary, benzylic, and secondary nitrile anions to form alpha-aryl nitriles in good yields are reported.

Using stable isotopes to monitor forms of sulfur during desulfurization processes: A quick screening method

USGS Publications Warehouse

Liu, Chao-Li; Hackley, Keith C.; Coleman, D.D.; Kruse, C.W.

1987-01-01

A method using stable isotope ratio analysis to monitor the reactivity of sulfur forms in coal during thermal and chemical desulfurization processes has been developed at the Illinois State Geological Survey. The method is based upon the fact that a significant difference exists in some coals between the 34S/32S ratios of the pyritic and organic sulfur. A screening method for determining the suitability of coal samples for use in isotope ratio analysis is described. Making these special coals available from coal sample programs would assist research groups in sorting out the complex sulfur chemistry which accompanies thermal and chemical processing of high sulfur coals. ?? 1987.

A novel aldo-keto reductase from Jatropha curcas L. (JcAKR) plays a crucial role in the detoxification of methylglyoxal, a potent electrophile.

PubMed

Mudalkar, Shalini; Sreeharsha, Rachapudi Venkata; Reddy, Attipalli Ramachandra

2016-05-20

Abiotic stress leads to the generation of reactive oxygen species (ROS) which further results in the production of reactive carbonyls (RCs) including methylglyoxal (MG). MG, an α, β-dicarbonyl aldehyde, is highly toxic to plants and the mechanism behind its detoxification is not well understood. Aldo-keto reductases (AKRs) play a role in detoxification of reactive aldehydes and ketones. In the present study, we cloned and characterised a putative AKR from Jatropha curcas (JcAKR). Phylogenetically, it forms a small clade with AKRs of Glycine max and Rauwolfia serpentina. JcAKR was heterologously expressed in Escherichia coli BL-21(DE3) cells and the identity of the purified protein was confirmed through MALDI-TOF analysis. The recombinant protein had high enzyme activity and catalytic efficiency in assays containing MG as the substrate. Protein modelling and docking studies revealed MG was efficiently bound to JcAKR. Under progressive drought and salinity stress, the enzyme and transcript levels of JcAKR were higher in leaves compared to roots. Further, the bacterial and yeast cells expressing JcAKR showed more tolerance towards PEG (5%), NaCl (200mM) and MG (5mM) treatments compared to controls. In conclusion, our results project JcAKR as a possible and potential target in crop improvement for abiotic stress tolerance. Copyright © 2016 Elsevier GmbH. All rights reserved.

Antigen-specific TIL therapy for melanoma: A flexible platform for personalized cancer immunotherapy.

PubMed

Kelderman, Sander; Heemskerk, Bianca; Fanchi, Lorenzo; Philips, Daisy; Toebes, Mireille; Kvistborg, Pia; van Buuren, Marit M; van Rooij, Nienke; Michels, Samira; Germeroth, Lothar; Haanen, John B A G; Schumacher, N M

2016-06-01

Tumor infiltrating lymphocyte (TIL) therapy has shown objective clinical response rates of 50% in stage IV melanoma patients in a number of clinical trials. Nevertheless, the majority of patients progress either directly upon therapy or after an initial period of tumor control. Recent data have shown that most TIL products that are used for therapy contain only low frequencies of T cells reactive against known melanoma-associated epitopes. Because of this, the development of a technology to create T-cell products that are enriched for reactivity against defined melanoma-associated antigens would seem valuable, both to evaluate the tumoricidal potential of T cells directed against different antigen classes and to potentially increase response rates. Here, we developed and validated a conditional MHC streptamer-based platform for the creation of TIL products with defined antigen reactivities. We have used this platform to successfully enrich both high-frequency (≥1%) and low-frequency (<1%) tumor-specific CD8(+) T-cell populations, and thereby created T-cell products with enhanced tumor recognition potential. Collectively, these data demonstrate that selection of antigen-specific T-cell populations can be used to create defined T-cell products for clinical use. This strategy thus forms a highly flexible platform for the development of antigen-specific cell products for personalized cancer immunotherapy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical Energy Release in Several Recently Discovered Detonation and Deflagration Flows

NASA Astrophysics Data System (ADS)

Tarver, Craig M.

2010-10-01

Several recent experiments on complex detonation and deflagration flows are analyzed in terms of the chemical energy release required to sustain these flows. The observed double cellular structures in detonating gaseous nitromethane-oxygen and NO2-fuel (H2, CH4, and C2H6) mixtures are explained by the amplification of two distinct pressure wave frequencies by two exothermic reactions, the faster reaction forming vibrationally excited NO* and the slower reaction forming highly vibrationally excited N2**. The establishment of a Chapman-Jouguet (C-J) deflagration behind a weak shock wave, the C-J detonation established after a head-on collision with a shock front, and the C-J detonation conditions established in reactive supersonic flows are quantitatively calculated using the chemical energy release of a H2 + Cl2 mixture. For these three reactive flows, these calculations illustrate that different fractions of the exothermic chemical energy are used to sustain steady-state propagation. C-J detonation calculations on the various initial states using the CHEETAH chemical equilibrium code are shown to be in good agreement with experimental detonation velocity measurements for the head-on collision and supersonic flow detonations.

Hole hopping through tyrosine/tryptophan chains protects proteins from oxidative damage

PubMed Central

Gray, Harry B.; Winkler, Jay R.

2015-01-01

Living organisms have adapted to atmospheric dioxygen by exploiting its oxidizing power while protecting themselves against toxic side effects. Reactive oxygen and nitrogen species formed during oxidative stress, as well as high-potential reactive intermediates formed during enzymatic catalysis, could rapidly and irreversibly damage polypeptides were protective mechanisms not available. Chains of redox-active tyrosine and tryptophan residues can transport potentially damaging oxidizing equivalents (holes) away from fragile active sites and toward protein surfaces where they can be scavenged by cellular reductants. Precise positioning of these chains is required to provide effective protection without inhibiting normal function. A search of the structural database reveals that about one third of all proteins contain Tyr/Trp chains composed of three or more residues. Although these chains are distributed among all enzyme classes, they appear with greatest frequency in the oxidoreductases and hydrolases. Consistent with a redox-protective role, approximately half of the dioxygen-using oxidoreductases have Tyr/Trp chain lengths ≥3 residues. Among the hydrolases, long Tyr/Trp chains appear almost exclusively in the glycoside hydrolases. These chains likely are important for substrate binding and positioning, but a secondary redox role also is a possibility. PMID:26195784

Crosslinking reactions of 4-amino-6-oxo-2-vinylpyrimidine with guanine derivatives and structural analysis of the adducts

PubMed Central

Kusano, Shuhei; Ishiyama, Shogo; Lam, Sik Lok; Mashima, Tsukasa; Katahira, Masato; Miyamoto, Kengo; Aida, Misako; Nagatsugi, Fumi

2015-01-01

DNA interstrand crosslinks (ICLs) are the primary mechanism for the cytotoxic activity of many clinical anticancer drugs, and numerous strategies for forming ICLs have been developed. One such method is using crosslink-forming oligonucleotides (CFOs). In this study, we designed a 4-amino-6-oxo-2-vinylpyrimidine (AOVP) derivative with an acyclic spacer to react selectively with guanine. The AOVP CFO exhibited selective crosslinking reactivity with guanine and thymine in DNA, and with guanine in RNA. These crosslinking reactions with guanine were accelerated in the presence of CoCl2, NiCl2, ZnCl2 and MnCl2. In addition, we demonstrated that the AOVP CFO was reactive toward 8-oxoguanine opposite AOVP in the duplex DNA. The structural analysis of each guanine and 8-oxoguanine adduct in the duplex DNA was investigated by high-resolution NMR. The results suggested that AOVP reacts at the N2 amine in guanine and at the N1 or N2 amines in 8-oxoguanine in the duplex DNA. This study demonstrated the first direct determination of the adduct structure in duplex DNA without enzyme digestion. PMID:26245348

78 FR 72673 - Zero Rate Reactive Power Rate Schedules; Notice of Staff Workshop

Federal Register 2010, 2011, 2012, 2013, 2014

2013-12-03

... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Docket No. AD14-1-000] Zero Rate Reactive Power Rate Schedules; Notice of Staff Workshop This notice establishes the location and date for... located at: https://www.ferc.gov/whats-new/registration/zero-rate-12-11-13-form.asp . The workshop will...

Herbivore derived fatty acid-amides elicit reactive oxygen species burst in plants

USDA-ARS?s Scientific Manuscript database

The formation of a reactive oxygen species (ROS) burst is a central response of plants to many forms of stress including pathogen attack, several abiotic stresses, damage and insect infestation. These ROS act as a direct defense as well as signaling and regulatory molecules. Perception of microbe or...

Reactivation of Memory by Hypnosis and Suggestion. Final Report.

ERIC Educational Resources Information Center

London, Perry; Cooper, Leslie M.

This study tested the hypothesis that the memory of meaningful material can be reactivated without relearning by means of hypnotic suggestion. Very susceptible (T) and non-susceptible (UT) subjects were sought from among those who volunteered for the experiment. Two forms of a memory test for connected meaningful material were developed. Each form…

Toward Greater Specificity in Identifying Associations among Interparental Aggression, Child Emotional Reactivity to Conflict, and Child Problems

ERIC Educational Resources Information Center

Davies, Patrick T.; Cicchetti, Dante; Martin, Meredith J.

2012-01-01

This study examined specific forms of emotional reactivity to conflict and temperamental emotionality as explanatory mechanisms in pathways among interparental aggression and child psychological problems. Participants of the multimethod, longitudinal study included 201 two-year-old children and their mothers who had experienced elevated violence…

Analysis and design of a calcium-based sulfur sorbent for applications in integrated gasification combined cycle energy systems

NASA Astrophysics Data System (ADS)

Hasler, David Johann Ludwig

The reactivity of various Ca-based sorbent materials in pelletized form with H2S or CO2 was investigated at high temperatures (750--880°C). An extensive study was conducted to compare the performance of sorbent pellets derived from plaster of Paris and limestone. Multicycle absorption and regeneration tests showed that plaster-based pellets out performed the limestone-based pellets primarily due to a higher surface area and mesoporosity. The effect of pore-modifiers on the reactivity of limestone with H 2S was investigated by incorporating additives such as cornstarch, graphite and polyvinylalcohol (PVA) in the sorbent. Multicycle sulfidation and regeneration tests of the modified sorbent showed that starch did not improve the reactivity of the limestone, graphite reduced the reactivity, while PVA improved it. The effect of the chemical additives MgO and SrO on the performance of CaO-based sorbent pellets was investigated. The effect of MgO was tested by starting with materials that contained MgCO3 in a natural form, such as dolomite. The effect of SrO was tested by starting with SrCO 3 either co-precipitated with CaCO3 or by wet-mixing SrCO 3 with limestone in slurry form. The MgO was found to improve the thermal stability of the CaO-based sorbent but lowered the overall absorption capacity of the material when reacted with CO2 or H2S, while SrO decreased the thermal stability of the sorbent when it was reacted with CO2; no absorption tests were run with H2S. A study of the performance of pelletized CaO-based cores coated with a refractory material such as alumina and limestone or alumina and kaolin was conducted. The reactivity of the core and shell pellets with H2S was determined. The strength and durability of the pellets were determined by using crushing strength analysis and abrasion resistance tests. Pellets coated with either alumina and limestone or alumina and kaolin proved to be strong and adequate for use in industrial reactors. A semi-empirical mathematical model was developed to represent the reaction of H2S with a sorbent pellet. The model was based on the well-known shrinking core model and it was applied successfully for the analysis of both pellet cores and core and shell pellets reacting with H2S.

The Lunar Environment: Determining the Health Effects of Exposure to Moon Dusts

NASA Technical Reports Server (NTRS)

Khan-Mayberry, Noreen

2007-01-01

The Earth s moon presents a hostile environment in which to live and work. There is no atmosphere to protect its surface from the ravages of solar wind and micrometeorite impacts. As a result, the moon s surface is covered with a thin layer of fine, charged, reactive dust capable of entering habitats and vehicle compartments, where it can result in crewmember health problems. During the Apollo missions, lunar dusts were introduced into the crew vehicle, resulting in direct exposure and occasional reports of respiratory, dermal and ocular irritation. In order to study the toxicological effects of lunar dust, NASA formed the Lunar Airborne Dust Toxicity Advisory Group (LADTAG). This interdisciplinary group is comprised of leading experts in space toxicology, lunar geology, space medicine and biomedical research. LADTAG has demonstrated that lunar soil contains several types of reactive dusts, including an extremely fine respirable component. These dusts have highly reactive surfaces in the lunar environment; the grains contain surface coatings which are generated by vapor phases formed by hypervelocity impact of micrometeorites. This unique class of dusts has surface properties that are unlike any Earth based analog. These distinctive properties are why lunar dusts are of great toxicological interest. Understanding how these reactive components behave "biochemically" in a moisture-rich pulmonary environment will aid in determining how toxic these particles are to humans. The data obtained from toxicological examination of lunar dusts will determine the human risk criteria for lunar dust exposure and produce a lunar health standard. LADTAG s analysis of lunar dusts and lunar dust simulants will include detailed lunar particle characterizations, determining the properties of particle activation, reactivation of lunar dust, the process of dust passivation and discerning the pathology of lunar dust exposure via inhalation, intratracheal instillation, cell culture exposure, dermal exposure and ocular exposure. The resulting health standard will be time-based and will vary by the duration and type of exposure. It may also be necessary to set multiple standards for different types of lunar dust, as well as for dust in its activated form vs. aged & passivated dust. This standard, set to protect the health of our robust astronaut crews, will not only impact NASA medical operations, but engineering designs as well. The data from our multidisciplinary research are vital in developing remediation devices and environmental monitors. Ultimately, the engineering and safety groups will design and develop countermeasures for space vehicles, suits, rovers and habitats that will be sustained within the limits of the health standard.

Reactivation of Chromosomally Integrated Human Herpesvirus-6 by Telomeric Circle Formation

PubMed Central

Prusty, Bhupesh K.; Krohne, George; Rudel, Thomas

2013-01-01

More than 95% of the human population is infected with human herpesvirus-6 (HHV-6) during early childhood and maintains latent HHV-6 genomes either in an extra-chromosomal form or as a chromosomally integrated HHV-6 (ciHHV-6). In addition, approximately 1% of humans are born with an inheritable form of ciHHV-6 integrated into the telomeres of chromosomes. Immunosuppression and stress conditions can reactivate latent HHV-6 replication, which is associated with clinical complications and even death. We have previously shown that Chlamydia trachomatis infection reactivates ciHHV-6 and induces the formation of extra-chromosomal viral DNA in ciHHV-6 cells. Here, we propose a model and provide experimental evidence for the mechanism of ciHHV-6 reactivation. Infection with Chlamydia induced a transient shortening of telomeric ends, which subsequently led to increased telomeric circle (t-circle) formation and incomplete reconstitution of circular viral genomes containing single viral direct repeat (DR). Correspondingly, short t-circles containing parts of the HHV-6 DR were detected in cells from individuals with genetically inherited ciHHV-6. Furthermore, telomere shortening induced in the absence of Chlamydia infection also caused circularization of ciHHV-6, supporting a t-circle based mechanism for ciHHV-6 reactivation. PMID:24367281

Performance of two differently designed permeable reactive barriers with sulfate and zinc solutions.

PubMed

Pérez, Norma; Schwarz, Alex O; Barahona, Esteban; Sanhueza, Pamela; Diaz, Isabel; Urrutia, Homero

2018-06-18

For the first time, this laboratory-scale study evaluates the feasibility of incorporating diffusive exchange in permeable reactive barriers. In order to do this, the performance of two permeable reactive barriers (PRB) with different internal substrate arrangements were compared during the administration of a sulfate solution without metals (for 163 days) and with metals (for 60 days), simulating groundwater contaminated with acid mine drainage (AMD). In order to simulate a traditional PRB, a homogeneous distribution was implemented in the first reactor and the other PRB reactor utilized diffusion-active technology (DAPRB). In the DAPRB, the distribution of the reactive material was interspersed with the conductive material. The measurements in the internal ports showed that transverse gradients of sulfide formed in the DAPRB, causing the diffusion of sulfide from the substrate toward the layer interface, which is where the sulfide reacts by forming complexes with the metal. The DAPRB prevents the microorganisms from direct contact with AMD. This protection caused greater activity (sulfide production). Copyright © 2018 Elsevier B.V. All rights reserved.

Trans-3,4-dideoxyglucone-3-ene (trans-3,4-DGE), a most reactive glucose degradation product in freshly heat sterilized glucose solutions.

PubMed

Chen, Ke; Prabel, Jason; Dutton, Johanna; Gotoda, Masaharu; Asai, Yumi; Grobin, Adam

2015-12-11

In our study, one or more glucose degradation products (GDPs) in freshly heat sterilized dextrose 5% in water (D5W) were found to react with a drug candidate having a β-keto amide group (Compound A) to form several drug related compounds with the same molecular weight. However the previously identified GDPs did not react with Compound A to produce the observed adducts, indicating that unidentified GDP(s) reacted with Compound A to form these adducts. Our investigation by reaction-directed fractionation of the reactive D5W with HPLC led to the identification of the reactive GDP, trans-3,4-dideoxyglucosone-3-ene (trans-3,4-DGE), responsible for producing these reaction products. The trans-3,4-DGE was identified from its derivatives of dinitrophenylhydrazine (DNPH) and acetoacetanilide and confirmed by (1) admixing Compound A with authentic trans-3,4-DGE to produce the identical impurities as admixing with freshly heat sterilized D5W, and (2) NMR analysis of the reactive fraction of glucose solutions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetic and mechanistic reactivity. Isoprene impact on ozone levels in an urban area near Tijuca Forest, Rio de Janeiro.

PubMed

da Silva, Cleyton Martins; da Silva, Luane Lima; Corrêa, Sergio Machado; Arbilla, Graciela

2016-12-01

Volatile organic compounds (VOCs) play a central role in atmospheric chemistry. In this work, the kinetic and mechanistic reactivities of VOCs are analyzed, and the contribution of the organic compounds emitted by anthropogenic and natural sources is estimated. VOCs react with hydroxyl radicals and other photochemical oxidants, such as ozone and nitrate radicals, which cause the conversion of NO to NO 2 in various potential reaction paths, including photolysis, to form oxygen atoms, which generate ozone. The kinetic reactivity was evaluated based on the reaction coefficients for hydroxyl radicals with VOCs. The mechanistic reactivity was estimated using a detailed mechanism and the incremental reactivity scale that Carter proposed. Different scenarios were proposed and discussed, and a minimum set of compounds, which may describe the tropospheric reactivity in the studied area, was determined. The role of isoprene was analyzed in terms of its contribution to ozone formation.

Emotional Reactivity and Internalizing Symptoms: Moderating Role of Emotion Regulation

PubMed Central

Shapero, Benjamin G.; Abramson, Lyn Y.; Alloy, Lauren B.

2015-01-01

Emotion dysregulation has been associated with increases in many forms of psychopathology in adolescents and adults. The development of effective emotion regulation skills is important during adolescence, especially as stressful life events increase during this time. The current study examined two emotion regulation strategies, cognitive reappraisal and affective suppression, in interaction with self-report and biological measures of emotional reactivity as predictors of internalizing symptoms. A community sample of adolescents (n = 127), at an age of risk for depression and anxiety, completed self-report measures of emotional reactivity and internalizing symptoms. In addition, they completed a modified social stress task and were assessed on biological measures of reactivity and regulation. Findings suggested that the trait tendency to reappraise was associated with a reduced impact of emotional reactivity on depressive, but not anxiety symptoms. Implications for shared and specific aspects of emotional reactivity and regulation are discussed. PMID:27231404

Analysis of MHC class I folding: novel insights into intermediate forms

PubMed Central

Simone, Laura C.; Tuli, Amit; Simone, Peter D.; Wang, Xiaojian; Solheim, Joyce C.

2012-01-01

Folding around a peptide ligand is integral to the antigen presentation function of major histocompatibility complex (MHC) class I molecules. Several lines of evidence indicate that the broadly cross-reactive 34-1-2 antibody is sensitive to folding of the MHC class I peptide-binding groove. Here, we show that peptide-loading complex proteins associated with the murine MHC class I molecule Kd are found primarily in association with the 34-1-2+ form. This led us to hypothesize that the 34-1-2 antibody may recognize intermediately, as well as fully, folded MHC class I molecules. In order to further characterize the form(s) of MHC class I molecules recognized by 34-1-2, we took advantage of its cross-reactivity with Ld. Recognition of the open and folded forms of Ld by the 64-3-7 and 30-5-7 antibodies, respectively, has been extensively characterized, providing us with parameters against which to compare 34-1-2 reactivity. We found that the 34-1-2+ Ld molecules displayed characteristics indicative of incomplete folding, including increased tapasin association, endoplasmic reticulum retention, and instability at the cell surface. Moreover, we demonstrate that an Ld-specific peptide induced folding of the 34-1-2+ Ld intermediate. Altogether, these results yield novel insights into the nature of MHC class I molecules recognized by the 34-1-2 antibody. PMID:22329842

The toxicity of textile reactive azo dyes after hydrolysis and decolourisation.

PubMed

Gottlieb, Anna; Shaw, Chris; Smith, Alan; Wheatley, Andrew; Forsythe, Stephen

2003-02-27

The toxicity of C.I. Reactive Black 5 and three Procion dyes, as found in textile effluents, was determined using the bioluminescent bacterium Vibrio fischeri. Hydrolysed Reactive Black had a slightly greater toxicity than the parent form (EC(50) 11.4+/-3.68 and 27.5+/-4.01 mg l(-1), respectively). A baffled bioreactor with anaerobic and aerobic compartments was used to decolourise hydrolysed Reactive Black 5 in a synthetic effluent. Decolourisation of hydrolysed Reactive Black resulted in an increased toxicity (EC(50) 0.2+/-0.03 mg l(-1)). Toxicity was not detectable when decolourised Reactive Black 5 was metabolised under aerobic conditions. No genotoxicity was detected after the decolourisation of either the parent or the hydrolysed reactive dyes, either in vitro or in the bioreactor. The toxicity and genotoxicity of decolourised C.I. Acid Orange 7 was due to the production of 1-amino-2-naphthol (EC(50) 0.1+/-0.03 mg l(-1)).

Durable zinc oxide-containing sorbents for coal gas desulfurization

DOEpatents

Siriwardane, Ranjani V.

1996-01-01

Durable zinc-oxide containing sorbent pellets for removing hydrogen sulfide from a gas stream at an elevated temperature are made up to contain titania as a diluent, high-surface-area silica gel, and a binder. These materials are mixed, moistened, and formed into pellets, which are then dried and calcined. The resulting pellets undergo repeated cycles of sulfidation and regeneration without loss of reactivity and without mechanical degradation. Regeneration of the pellets is carried out by contacting the bed with an oxidizing gas mixture.

Horizontal and vertical structure of reactive bromine events probed by bromine monoxide MAX-DOAS

NASA Astrophysics Data System (ADS)

Simpson, William R.; Peterson, Peter K.; Frieß, Udo; Sihler, Holger; Lampel, Johannes; Platt, Ulrich; Moore, Chris; Pratt, Kerri; Shepson, Paul; Halfacre, John; Nghiem, Son V.

2017-08-01

Heterogeneous photochemistry converts bromide (Br-) to reactive bromine species (Br atoms and bromine monoxide, BrO) that dominate Arctic springtime chemistry. This phenomenon has many impacts such as boundary-layer ozone depletion, mercury oxidation and deposition, and modification of the fate of hydrocarbon species. To study environmental controls on reactive bromine events, the BRomine, Ozone, and Mercury EXperiment (BROMEX) was carried out from early March to mid-April 2012 near Barrow (Utqiaġvik), Alaska. We measured horizontal and vertical gradients in BrO with multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instrumentation at three sites, two mobile and one fixed. During the campaign, a large crack in the sea ice (an open lead) formed pushing one instrument package ˜ 250 km downwind from Barrow (Utqiaġvik). Convection associated with the open lead converted the BrO vertical structure from a surface-based event to a lofted event downwind of the lead influence. The column abundance of BrO downwind of the re-freezing lead was comparable to upwind amounts, indicating direct reactions on frost flowers or open seawater was not a major reactive bromine source. When these three sites were separated by ˜ 30 km length scales of unbroken sea ice, the BrO amount and vertical distributions were highly correlated for most of the time, indicating the horizontal length scales of BrO events were typically larger than ˜ 30 km in the absence of sea ice features. Although BrO amount and vertical distribution were similar between sites most of the time, rapid changes in BrO with edges significantly smaller than this ˜ 30 km length scale episodically transported between the sites, indicating BrO events were large but with sharp edge contrasts. BrO was often found in shallow layers that recycled reactive bromine via heterogeneous reactions on snowpack. Episodically, these surface-based events propagated aloft when aerosol extinction was higher (> 0.1 km-1); however, the presence of aerosol particles aloft was not sufficient to produce BrO aloft. Highly depleted ozone (< 1 nmol mol-1) repartitioned reactive bromine away from BrO and drove BrO events aloft in cases. This work demonstrates the interplay between atmospheric mixing and heterogeneous chemistry that affects the vertical structure and horizontal extent of reactive bromine events.

Potassium ferrate [Fe(VI)] does not mediate self-sterilization of a surrogate mars soil

PubMed Central

Crawford, Ronald L; Paszczynski, Andrzej; Allenbach, Lisa

2003-01-01

Background Martian soil is thought to be enriched with strong oxidants such as peroxides and/or iron in high oxidation states that might destroy biological materials. There is also a high flux of ultraviolet radiation at the surface of Mars. Thus, Mars may be inhospitable to life as we know it on Earth. We examined the hypothesis that if the soil of Mars contains ferrates [Fe(VI)], the strongest of the proposed oxidizing species, and also is exposed to high fluxes of UV radiation, it will be self-sterilizing. Results Under ambient conditions (25°C, oxygen and water present) K2FeO4 mixed into sand mineralized some reactive organic molecules to CO2, while less reactive compounds were not degraded. Dried endospores of Bacillus subtilis incubated in a Mars surrogate soil comprised of dry silica sand containing 20% by weight K2FeO4 and under conditions similar to those now on Mars (extreme desiccation, cold, and a CO2-dominated atmosphere) were resistant to killing by the ferrate-enriched sand. Similar results were observed with permanganate. Spores in oxidant-enriched sand exposed to high fluxes of UV light were protected from the sporocidal activity of the radiation below about 5 mm depths. Conclusion Based on our data and previously published descriptions of ancient but dormant life forms on Earth, we suggest that if entities resembling bacterial endospores were produced at some point by life forms on Mars, they might still be present and viable, given appropriate germination conditions. Endospores delivered to Mars on spacecraft would possibly survive and potentially compromise life detection experiments. PMID:12694634

Metallic interconnects for SOFC: Characterisation of corrosion resistance and conductivity evaluation at operating temperature of differently coated alloys

NASA Astrophysics Data System (ADS)

Fontana, S.; Amendola, R.; Chevalier, S.; Piccardo, P.; Caboche, G.; Viviani, M.; Molins, R.; Sennour, M.

One of challenges in improving the performance and cost-effectiveness of solid oxide fuel cells (SOFCs) is the development of suitable interconnect materials. Recent researches have enabled to decrease the operating temperature of the SOFC from 1000 to 800 °C. Chromia forming alloys are then among the best candidates for interconnects. However, low electronic conductivity and volatility of chromium oxide scale need to be solved to improve interconnect performances. In the field of high temperature oxidation of metals, it is well known that the addition of reactive element into alloys or as thin film coatings, improves their oxidation resistance at high temperature. The elements of beginning of the lanthanide group and yttrium are the most efficient. The goal of this study is to make reactive element oxides (La 2O 3, Nd 2O 3 and Y 2O 3) coatings by metal organic chemical vapour deposition (MOCVD) on Crofer 22 APU, AL 453 and Haynes 230 in order to form perovskite oxides which present a good conductivity at high temperature. The coatings were analysed after 100 h ageing at 800 °C in air under atmospheric pressure by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analyses, X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Area-specific resistance (ASR) was measured in air for the same times and temperature, using a sandwich technique with Pt paste for electrical contacts between surfaces. The ASR values for the best coating were estimated to be limited to 0.035 Ω cm 2, even after 40,000 h use.

Using High Performance Computing to Understand Roles of Labile and Nonlabile U(VI) on Hanford 300 Area Plume Longevity

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

Lichtner, Peter C.; Hammond, Glenn E.

Evolution of a hexavalent uranium [U(VI)] plume at the Hanford 300 Area bordering the Columbia River is investigated to evaluate the roles of labile and nonlabile forms of U(VI) on the longevity of the plume. A high fidelity, three-dimensional, field-scale, reactive flow and transport model is used to represent the system. Richards equation coupled to multicomponent reactive transport equations are solved for times up to 100 years taking into account rapid fluctuations in the Columbia River stage resulting in pulse releases of U(VI) into the river. The peta-scale computer code PFLOTRAN developed under a DOE SciDAC-2 project is employed inmore » the simulations and executed on ORNL's Cray XT5 supercomputer Jaguar. Labile U(VI) is represented in the model through surface complexation reactions and its nonlabile form through dissolution of metatorbernite used as a surrogate mineral. Initial conditions are constructed corresponding to the U(VI) plume already in place to avoid uncertainties associated with the lack of historical data for the waste stream. The cumulative U(VI) flux into the river is compared for cases of equilibrium and multirate sorption models and for no sorption. The sensitivity of the U(VI) flux into the river on the initial plume configuration is investigated. The presence of nonlabile U(VI) was found to be essential in explaining the longevity of the U(VI) plume and the prolonged high U(VI) concentrations at the site exceeding the EPA MCL for uranium.« less

Methanol Oxidative Dehydrogenation on Oxide Catalysts: Molecular and Dissociative Routes and Hydrogen Addition Energies as Descriptors of Reactivity

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

Deshlahra, Prashant; Iglesia, Enrique

The oxidative dehydrogenation (ODH) of alkanols on oxide catalysts is generally described as involving H-abstraction from alkoxy species formed via O–H dissociation. Kinetic and isotopic data cannot discern between such routes and those involving kinetically-relevant H-abstraction from undissociated alkanols. Here, we combine such experiments with theoretical estimates of activation energies and entropies to show that the latter molecular routes prevail over dissociative routes for methanol reactions on polyoxometalate (POM) clusters at all practical reaction temperatures. The stability of the late transition states that mediate H-abstraction depend predominantly on the stability of the O–H bond formed, making H-addition energies (HAE) accuratemore » and single-valued descriptors of reactivity. Density functional theory-derived activation energies depend linearly on HAE values at each O-atom location on clusters with a range of composition (H3PMo12, H4SiMo12, H3PW12, H4PV1Mo11, and H4PV1W11); both barriers and HAE values reflect the lowest unoccupied molecular orbital energy of metal centers that accept the electron and the protonation energy of O-atoms that accept the proton involved in the H-atom transfer. Bridging O-atoms form O–H bonds that are stronger than those of terminal atoms and therefore exhibit more negative HAE values and higher ODH reactivity on all POM clusters. For each cluster composition, ODH turnover rates reflect the reactivity-averaged HAE of all accessible O-atoms, which can be evaluated for each cluster composition to provide a rigorous and accurate predictor of ODH reactivity for catalysts with known structure. These relations together with oxidation reactivity measurements can then be used to estimate HAE values and to infer plausible structures for catalysts with uncertain active site structures.« less

Serum amyloid A forms stable oligomers that disrupt vesicles at lysosomal pH and contribute to the pathogenesis of reactive amyloidosis

PubMed Central

Gantz, Donald L.; Haupt, Christian; Gursky, Olga

2017-01-01

Serum amyloid A (SAA) is an acute-phase plasma protein that functions in innate immunity and lipid homeostasis. SAA is a protein precursor of reactive AA amyloidosis, the major complication of chronic inflammation and one of the most common human systemic amyloid diseases worldwide. Most circulating SAA is protected from proteolysis and misfolding by binding to plasma high-density lipoproteins. However, unbound soluble SAA is intrinsically disordered and is either rapidly degraded or forms amyloid in a lysosome-initiated process. Although acidic pH promotes amyloid fibril formation by this and many other proteins, the molecular underpinnings are unclear. We used an array of spectroscopic, biochemical, and structural methods to uncover that at pH 3.5–4.5, murine SAA1 forms stable soluble oligomers that are maximally folded at pH 4.3 with ∼35% α-helix and are unusually resistant to proteolysis. In solution, these oligomers neither readily convert into mature fibrils nor bind lipid surfaces via their amphipathic α-helices in a manner typical of apolipoproteins. Rather, these oligomers undergo an α-helix to β-sheet conversion catalyzed by lipid vesicles and disrupt these vesicles, suggesting a membranolytic potential. Our results provide an explanation for the lysosomal origin of AA amyloidosis. They suggest that high structural stability and resistance to proteolysis of SAA oligomers at pH 3.5–4.5 help them escape lysosomal degradation, promote SAA accumulation in lysosomes, and ultimately damage cellular membranes and liberate intracellular amyloid. We posit that these soluble prefibrillar oligomers provide a missing link in our understanding of the development of AA amyloidosis. PMID:28743750

Chemical Methods for the Direct Detection and Labeling of S-Nitrosothiols

PubMed Central

Bechtold, Erika

2012-01-01

Abstract Significance: Posttranslational modification of proteins through phosphorylation, glycosylation, and oxidation adds complexity to the proteome by reversibly altering the structure and function of target proteins in a highly controlled fashion. Recent Advances: The study of reversible cysteine oxidation highlights a role for this oxidative modification in complex signal transduction pathways. Nitric oxide (NO), and its respective metabolites (including reactive nitrogen species), participates in a variety of these cellular redox processes, including the reversible oxidation of cysteine to S-nitrosothiols (RSNOs). RSNOs act as endogenous transporters of NO, but also possess beneficial effects independent of NO-related signaling, which suggests a complex and versatile biological role. In this review, we highlight the importance of RSNOs as a required posttranslational modification and summarize the current methods available for detecting S-nitrosation. Critical Issues: Given the limitations of these indirect detection methods, the review covers recent developments toward the direct detection of RSNOs by phosphine-based chemical probes. The intrinsic properties that dictate this phosphine/RSNO reactivity are summarized. In general, RSNOs (both small molecule and protein) react with phosphines to yield reactive S-substituted aza-ylides that undergo further reactions leading to stable RSNO-based adducts. Future Directions: This newly explored chemical reactivity forms the basis of a number of exciting potential chemical methods for protein RSNO detection in biological systems. Antioxid. Redox Signal. 17, 981–991. PMID:22356122

Copper-Hydroperoxo Mediated N-Debenzylation Chemistry Mimicking Aspects of Copper Monoxygenases

PubMed Central

Maiti, Debabrata; Narducci Sarjeant, Amy A.; Karlin, Kenneth D.

2008-01-01

Substantial oxidative N-debenzylation reaction along with PhCH=O formation occurs from a hydroperoxo copper(II) complex which has a dibenzylamino substrate (-N(CH2Ph)2 appended as a substituent on one pyridyl group of its tripodal tetradentate TMPA {≡ TPA ≡ tris(2-pyridylmethyl)amine)} ligand framework. During the course of the (LN(CH2Ph)2)CuII(−OOH) reactivity, formation of a substrate and −OOH (an oxygen atom) derived alkoxo CuII(−OR) complex occurs. The observation that the same CuII(−OR) species occurs from CuI/PhIO chemistry suggests the possibility that a copper-oxo (cupryl) reactive intermediate forms during alkoxo species formation, and new ESI-MS data obtained provides some further support for this high-valent intermediate. Net H-atom abstraction chemistry is proposed, based on kinetic isotope effect studies provided here and that previously published for a closely related CuII(−OOH) species incorporating dimethylamine (-N(CH3)2) as the internal substrate (J. Am. Chem. Soc. 2007, 129, 6720-6721); the CuI/PhIO reactivity, with similar isotope effect results, provides further support. The reactivity of these chemical systems closely resembles proposed oxidative N-dealkylation mechanisms effected by the copper-monooxygenases dopamine β-monooxygenase (DβM) or peptidylglycine-α-hydroxylating monooxygenase (PHM). PMID:18783212

Introduction to Pits and Weapons Systems (U)

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

Kautz, D.

2012-07-02

A Nuclear Explosive Package includes the Primary, Secondary, Radiation Case and related components. This is the part of the weapon that produces nuclear yield and it converts mechanical energy into nuclear energy. The pit is composed of materials that allow mechanical energy to be converted to electromagnetic energy. Fabrication processes used are typical of any metal fabrication facility: casting, forming, machining and welding. Some of the materials used in pits include: Plutonium, Uranium, Stainless Steel, Beryllium, Titanium, and Aluminum. Gloveboxes are used for three reasons: (1) Protect workers and public from easily transported, finely divided plutonium oxides - (a) Plutoniummore » is very reactive and produces very fine particulate oxides, (b) While not the 'Most dangerous material in the world' of Manhattan Project lore, plutonium is hazardous to health of workers if not properly controlled; (2) Protect plutonium from reactive materials - (a) Plutonium is extremely reactive at ambient conditions with several components found in air: oxygen, water, hydrogen, (b) As with most reactive metals, reactions with these materials may be violent and difficult to control, (c) As with most fabricated metal products, corrosion may significantly affect the mechanical, chemical, and physical properties of the product; and (3) Provide shielding from radioactive decay products: {alpha}, {gamma}, and {eta} are commonly associated with plutonium decay, as well as highly radioactive materials such as {sup 241}Am and {sup 238}Pu.« less

Dynein-ADP as a force-generating intermediate revealed by a rapid reactivation of flagellar axoneme.

PubMed Central

Tani, T; Kamimura, S

1999-01-01

Fragmented flagellar axonemes of sand dollar spermatozoa were reactivated by rapid photolysis of caged ATP. After a time lag of 10 ms, axonemes treated with protease started sliding disintegration. Axonemes without protease digestion started nanometer-scale high-frequency oscillation after a similar time lag. Force development in the sliding disintegration was measured with a flexible glass needle and its time course was corresponded well to that of the dynein-ADP intermediate production estimated using kinetic rates previously reported. However, with a high concentration ( approximately 80 microM) of vanadate, which binds to the dynein-ADP intermediate and forms a stable complex of dynein-ADP-vanadate, the time course of force development in sliding disintegration was not affected at all. In the case of high frequency oscillation, the time lag to start the oscillation, the initial amplitude, and the initial frequency were not affected by vanadate, though the oscillation once started was damped more quickly at higher concentrations of vanadate. These results suggest that during the initial turnover of ATP hydrolysis, force generation of dynein is not blocked by vanadate. A vanadate-insensitive dynein-ADP is postulated as a force-generating intermediate. PMID:10465762

Catalases Are NAD(P)H-Dependent Tellurite Reductases

PubMed Central

Calderón, Iván L.; Arenas, Felipe A.; Pérez, José Manuel; Fuentes, Derie E.; Araya, Manuel A.; Saavedra, Claudia P.; Tantaleán, Juan C.; Pichuantes, Sergio E.; Youderian, Philip A.; Vásquez, Claudio C.

2006-01-01

Reactive oxygen species damage intracellular targets and are implicated in cancer, genetic disease, mutagenesis, and aging. Catalases are among the key enzymatic defenses against one of the most physiologically abundant reactive oxygen species, hydrogen peroxide. The well-studied, heme-dependent catalases accelerate the rate of the dismutation of peroxide to molecular oxygen and water with near kinetic perfection. Many catalases also bind the cofactors NADPH and NADH tenaciously, but, surprisingly, NAD(P)H is not required for their dismutase activity. Although NAD(P)H protects bovine catalase against oxidative damage by its peroxide substrate, the catalytic role of the nicotinamide cofactor in the function of this enzyme has remained a biochemical mystery to date. Anions formed by heavy metal oxides are among the most highly reactive, natural oxidizing agents. Here, we show that a natural isolate of Staphylococcus epidermidis resistant to tellurite detoxifies this anion thanks to a novel activity of its catalase, and that a subset of both bacterial and mammalian catalases carry out the NAD(P)H-dependent reduction of soluble tellurite ion (TeO3 2−) to the less toxic, insoluble metal, tellurium (Te°), in vitro. An Escherichia coli mutant defective in the KatG catalase/peroxidase is sensitive to tellurite, and expression of the S. epidermidis catalase gene in a heterologous E. coli host confers increased resistance to tellurite as well as to hydrogen peroxide in vivo, arguing that S. epidermidis catalase provides a physiological line of defense against both of these strong oxidizing agents. Kinetic studies reveal that bovine catalase reduces tellurite with a low Michaelis-Menten constant, a result suggesting that tellurite is among the natural substrates of this enzyme. The reduction of tellurite by bovine catalase occurs at the expense of producing the highly reactive superoxide radical. PMID:17183702

Catalases are NAD(P)H-dependent tellurite reductases.

PubMed

Calderón, Iván L; Arenas, Felipe A; Pérez, José Manuel; Fuentes, Derie E; Araya, Manuel A; Saavedra, Claudia P; Tantaleán, Juan C; Pichuantes, Sergio E; Youderian, Philip A; Vásquez, Claudio C

2006-12-20

Reactive oxygen species damage intracellular targets and are implicated in cancer, genetic disease, mutagenesis, and aging. Catalases are among the key enzymatic defenses against one of the most physiologically abundant reactive oxygen species, hydrogen peroxide. The well-studied, heme-dependent catalases accelerate the rate of the dismutation of peroxide to molecular oxygen and water with near kinetic perfection. Many catalases also bind the cofactors NADPH and NADH tenaciously, but, surprisingly, NAD(P)H is not required for their dismutase activity. Although NAD(P)H protects bovine catalase against oxidative damage by its peroxide substrate, the catalytic role of the nicotinamide cofactor in the function of this enzyme has remained a biochemical mystery to date. Anions formed by heavy metal oxides are among the most highly reactive, natural oxidizing agents. Here, we show that a natural isolate of Staphylococcus epidermidis resistant to tellurite detoxifies this anion thanks to a novel activity of its catalase, and that a subset of both bacterial and mammalian catalases carry out the NAD(P)H-dependent reduction of soluble tellurite ion (TeO(3)(2-)) to the less toxic, insoluble metal, tellurium (Te(o)), in vitro. An Escherichia coli mutant defective in the KatG catalase/peroxidase is sensitive to tellurite, and expression of the S. epidermidis catalase gene in a heterologous E. coli host confers increased resistance to tellurite as well as to hydrogen peroxide in vivo, arguing that S. epidermidis catalase provides a physiological line of defense against both of these strong oxidizing agents. Kinetic studies reveal that bovine catalase reduces tellurite with a low Michaelis-Menten constant, a result suggesting that tellurite is among the natural substrates of this enzyme. The reduction of tellurite by bovine catalase occurs at the expense of producing the highly reactive superoxide radical.

Reactivity of hydropersulfides toward the hydroxyl radical unraveled: disulfide bond cleavage, hydrogen atom transfer, and proton-coupled electron transfer.

PubMed

Anglada, Josep M; Crehuet, Ramon; Adhikari, Sarju; Francisco, Joseph S; Xia, Yu

2018-02-14

Hydropersulfides (RSSH) are highly reactive as nucleophiles and hydrogen atom transfer reagents. These chemical properties are believed to be key for them to act as antioxidants in cells. The reaction involving the radical species and the disulfide bond (S-S) in RSSH, a known redox-active group, however, has been scarcely studied, resulting in an incomplete understanding of the chemical nature of RSSH. We have performed a high-level theoretical investigation on the reactions of the hydroxyl radical (˙OH) toward a set of RSSH (R = -H, -CH 3 , -NH 2 , -C(O)OH, -CN, and -NO 2 ). The results show that S-S cleavage and H-atom abstraction are the two competing channels. The electron inductive effect of R induces selective ˙OH substitution at one sulfur atom upon S-S cleavage, forming RSOH and ˙SH for the electron donating groups (EDGs), whereas producing HSOH and ˙SR for the electron withdrawing groups (EWGs). The H-Atom abstraction by ˙OH follows a classical hydrogen atom transfer (hat) mechanism, producing RSS˙ and H 2 O. Surprisingly, a proton-coupled electron transfer (pcet) process also occurs for R being an EDG. Although for RSSH having EWGs hat is the leading channel, S-S cleavage can be competitive or even dominant for the EDGs. The overall reactivity of RSSH toward ˙OH attack is greatly enhanced with the presence of an EDG, with CH 3 SSH being the most reactive species found in this study (overall rate constant: 4.55 × 10 12 M -1 s -1 ). Our results highlight the complexity in RSSH reaction chemistry, the extent of which is closely modulated by the inductive effect of the substituents in the case of the oxidation by hydroxyl radicals.

Reactive multilayer synthesis of hard ceramic foils and films

DOEpatents

Makowiecki, D.M.; Holt, J.B.

1996-02-13

A method is disclosed for synthesizing hard ceramic materials such as carbides, borides and aluminides, particularly in the form of coatings provided on another material so as to improve the wear and abrasion performance of machine tools, for example. The method involves the sputter deposition of alternating layers of reactive metals with layers of carbon, boron, or aluminum and the subsequent reaction of the multilayered structure to produce a dense crystalline ceramic. The material can be coated on a substrate or formed as a foil which can be coiled as a tape for later use.

Dreaming and Offline Memory Consolidation

PubMed Central

Wamsley, Erin J.

2015-01-01

Converging evidence suggests that dreaming is influenced by the consolidation of memory during sleep. Following encoding, recently formed memory traces are gradually stabilized and reorganized into a more permanent form of long-term storage. Sleep provides an optimal neurophysiological state to facilitate this process, allowing memory networks to be repeatedly reactivated in the absence of new sensory input. The process of memory reactivation and consolidation in the sleeping brain appears to influence conscious experience during sleep, contributing to dream content recalled on awakening. This article outlines several lines of evidence in support of this hypothesis, and responds to some common objections. PMID:24477388

T cell reactivity with allergoids: influence of the type of APC.

PubMed

Kahlert, H; Grage-Griebenow, E; Stüwe, H T; Cromwell, O; Fiebig, H

2000-08-15

The use of allergoids for allergen-specific immunotherapy has been established for many years. The characteristic features of these chemically modified allergens are their strongly reduced IgE binding activity compared with the native form and the retained immunogenicity. T cell reactivity of chemically modified allergens is documented in animals, but in humans indirect evidence of reactivity has been concluded from the induction of allergen-specific IgG during immunotherapy. Direct evidence of T cell reactivity was obtained recently using isolated human T cells. To obtain further insight into the mechanism of action of allergoids, we compared the Ag-presenting capacity of different APC types, including DC and macrophages, generated from CD14+ precursor cells from the blood of grass pollen allergic subjects, autologous PBMC, and B cells. These APC were used in experiments together with Phl p 5-specific T cell clones under stimulation with grass pollen allergen extract, rPhl p 5b, and the respective allergoids. Using DC and macrophages, allergoids exhibited a pronounced and reproducible T cell-stimulating capacity. Responses were superior to those with PBMC, and isolated B cells failed to present allergoids. Considerable IL-12 production was observed only when using the DC for Ag presentation of both allergens and allergoids. The amount of IL-10 in supernatants was dependent on the phenotype of the respective T cell clone. High IL-10 production was associated with suppressed IL-12 production from the DC in most cases. In conclusion, the reactivity of Th cells with allergoids is dependent on the type of the APC.

An Atmospheric Pressure Plasma Setup to Investigate the Reactive Species Formation.

PubMed

Gorbanev, Yury; Soriano, Robert; O'Connell, Deborah; Chechik, Victor

2016-11-03

Non-thermal atmospheric pressure ('cold') plasmas have received increased attention in recent years due to their significant biomedical potential. The reactions of cold plasma with the surrounding atmosphere yield a variety of reactive species, which can define its effectiveness. While efficient development of cold plasma therapy requires kinetic models, model benchmarking needs empirical data. Experimental studies of the source of reactive species detected in aqueous solutions exposed to plasma are still scarce. Biomedical plasma is often operated with He or Ar feed gas, and a specific interest lies in investigation of the reactive species generated by plasma with various gas admixtures (O2, N2, air, H2O vapor, etc.) Such investigations are very complex due to difficulties in controlling the ambient atmosphere in contact with the plasma effluent. In this work, we addressed common issues of 'high' voltage kHz frequency driven plasma jet experimental studies. A reactor was developed allowing the exclusion of ambient atmosphere from the plasma-liquid system. The system thus comprised the feed gas with admixtures and the components of the liquid sample. This controlled atmosphere allowed the investigation of the source of the reactive oxygen species induced in aqueous solutions by He-water vapor plasma. The use of isotopically labelled water allowed distinguishing between the species originating in the gas phase and those formed in the liquid. The plasma equipment was contained inside a Faraday cage to eliminate possible influence of any external field. The setup is versatile and can aid in further understanding the cold plasma-liquid interactions chemistry.

An Atmospheric Pressure Plasma Setup to Investigate the Reactive Species Formation

PubMed Central

Gorbanev, Yury; Soriano, Robert; O'Connell, Deborah; Chechik, Victor

2016-01-01

Non-thermal atmospheric pressure ('cold') plasmas have received increased attention in recent years due to their significant biomedical potential. The reactions of cold plasma with the surrounding atmosphere yield a variety of reactive species, which can define its effectiveness. While efficient development of cold plasma therapy requires kinetic models, model benchmarking needs empirical data. Experimental studies of the source of reactive species detected in aqueous solutions exposed to plasma are still scarce. Biomedical plasma is often operated with He or Ar feed gas, and a specific interest lies in investigation of the reactive species generated by plasma with various gas admixtures (O2, N2, air, H2O vapor, etc.) Such investigations are very complex due to difficulties in controlling the ambient atmosphere in contact with the plasma effluent. In this work, we addressed common issues of 'high' voltage kHz frequency driven plasma jet experimental studies. A reactor was developed allowing the exclusion of ambient atmosphere from the plasma-liquid system. The system thus comprised the feed gas with admixtures and the components of the liquid sample. This controlled atmosphere allowed the investigation of the source of the reactive oxygen species induced in aqueous solutions by He-water vapor plasma. The use of isotopically labelled water allowed distinguishing between the species originating in the gas phase and those formed in the liquid. The plasma equipment was contained inside a Faraday cage to eliminate possible influence of any external field. The setup is versatile and can aid in further understanding the cold plasma-liquid interactions chemistry. PMID:27842375

High throughput assay for evaluation of reactive carbonyl scavenging capacity.

PubMed

Vidal, N; Cavaille, J P; Graziani, F; Robin, M; Ouari, O; Pietri, S; Stocker, P

2014-01-01

Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or decreasing carbonyl stress-associated pathologies. There is no rapid and convenient analytical method available for the assessment of direct carbonyl scavenging capacity, and a very limited number of carbonyl scavengers have been identified to date, their therapeutic potential being highlighted only recently. In this context, we have developed a new and rapid sensitive fluorimetric method for the assessment of reactive carbonyl scavengers without involvement glycoxidation systems. Efficacy of various thiol- and non-thiol-carbonyl scavenger pharmacophores was tested both using this screening assay adapted to 96-well microplates and in cultured cells. The scavenging effects on the formation of Advanced Glycation End-product of Bovine Serum Albumin formed with methylglyoxal, 4-hydroxynonenal and glucose-glycated as molecular models were also examined. Low molecular mass thiols with an α-amino-β-mercaptoethane structure showed the highest degree of inhibitory activity toward both α,β-unsaturated aldehydes and dicarbonyls. Cysteine and cysteamine have the best scavenging ability toward methylglyoxal. WR-1065 which is currently approved for clinical use as a protective agent against radiation and renal toxicity was identified as the best inhibitor of 4-hydroxynonenal.

Internal and external atomic steps in graphite exhibit dramatically different physical and chemical properties.

PubMed

Lee, Hyunsoo; Lee, Han-Bo-Ram; Kwon, Sangku; Salmeron, Miquel; Park, Jeong Young

2015-04-28

We report on the physical and chemical properties of atomic steps on the surface of highly oriented pyrolytic graphite (HOPG) investigated using atomic force microscopy. Two types of step edges are identified: internal (formed during crystal growth) and external (formed by mechanical cleavage of bulk HOPG). The external steps exhibit higher friction than the internal steps due to the broken bonds of the exposed edge C atoms, while carbon atoms in the internal steps are not exposed. The reactivity of the atomic steps is manifested in a variety of ways, including the preferential attachment of Pt nanoparticles deposited on HOPG when using atomic layer deposition and KOH clusters formed during drop casting from aqueous solutions. These phenomena imply that only external atomic steps can be used for selective electrodeposition for nanoscale electronic devices.

In vitro screening of 50 highly prescribed drugs for thiol adduct formation--comparison of potential for drug-induced toxicity and extent of adduct formation.

PubMed

Gan, Jinping; Ruan, Qian; He, Bing; Zhu, Mingshe; Shyu, Wen C; Humphreys, W Griffith

2009-04-01

Reactive metabolite formation has been associated with drug-induced liver, skin, and hematopoietic toxicity of many drugs that has resulted in serious clinical toxicity, leading to clinical development failure, black box warnings, or, in some cases, withdrawal from the market. In vitro and in vivo screening for reactive metabolite formation has been proposed and widely adopted in the pharmaceutical industry with the aim of minimizing the property and thus the risk of drug-induced toxicity (DIT). One of the most common screening methods is in vitro thiol trapping of reactive metabolites. Although it is well-documented that many hepatotoxins form thiol adducts, there is no literature describing the adduct formation potential of safer drugs that are widely used. The objective of this study was to quantitatively assess the thiol adduct formation potential of 50 drugs (10 associated with DIT and 40 not associated) and document apparent differences in adduct formation between toxic and safer drugs. Dansyl glutathione was used as a trapping agent to aid the quantitation of adducts following in vitro incubation of drugs with human liver microsomes in the presence and absence of NADPH. Metabolic turnover of these drugs was also monitored by LC/UV. Overall, 15 out of the 50 drugs screened formed detectable levels of thiol adducts. There were general trends toward more positive findings in the DIT group vs the non-DIT group. These trends became more marked when the relative amount of thiol adducts was taken into account and improved further when dose and total daily reactive metabolite burdens were considered. In conclusion, there appears to be a general trend between the extent of thiol adduct formation and the potential for DIT, which would support the preclinical measurement and minimization of the property through screening of thiol adduct formation as part of an overall discovery optimization paradigm.

Mapping the binding site of aflatoxin B/sub 1/ in DNA: systematic analysis of the reactivity of aflatoxin B/sub 1/ with guanines in different DNA sequences

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

Benasutti, M.; Ejadi, S.; Whitlow, M.D.

The mutagenic and carcinogenic chemical aflatoxin B/sub 1/ (AFB/sub 1/) reacts almost exclusively at the N(7)-position of guanine following activation to its reactive form, the 8,9-epoxide (AFB/sub 1/ oxide). In general N(7)-guanine adducts yield DNA strand breaks when heated in base, a property that serves as the basis for the Maxam-Gilbert DNA sequencing reaction specific for guanine. Using DNA sequencing methods, other workers have shown that AFB/sub 1/ oxide gives strand breaks at positions of guanines; however, the guanine bands varied in intensity. This phenomenon has been used to infer that AFB/sub 1/ oxide prefers to react with guanines inmore » some sequence contexts more than in others and has been referred to as sequence specificity of binding. Herein, data on the reaction of AFB/sub 1/ oxide with several synthetic DNA polymers with different sequences are presented, and (following hydrolysis) adduct levels are determine by high-pressure liquid chromatography. These results reveal that for AFB/sub 1/ oxide (1) the N(7)-guanine adduct is the major adduct found in all of the DNA polymers, (2) adduct levels vary in different sequences, and, thus, sequence specificity is also observed by this more direct method, and (3) the intensity of bands in DNA sequencing gels is likely to reflect adduct levels formed at the N(7)-position of guanine. Knowing this, a reinvestigation of the reactivity of guanines in different DNA sequences using DNA sequencing methods was undertaken. Methods are developed to determine the X (5'-side) base and the Y (3'-side) base are most influential in determining guanine reactivity. These rules in conjunction with molecular modeling studies were used to assess the binding sites that might be utilized by AFB/sub 1/ oxide in its reaction with DNA.« less

The importance of sphingolipids and reactive oxygen species in cardiovascular development.

PubMed

de Faria Poloni, Joice; Chapola, Henrique; Feltes, Bruno César; Bonatto, Diego

2014-06-01

The heart is the first organ in the embryo to form. Its structural and functional complexity is the result of a thorough developmental program, where sphingolipids play an important role in cardiogenesis, heart maturation, angiogenesis, the regulation of vascular tone and vessel permeability. Sphingolipids are necessary for signal transduction and membrane microdomain formation. In addition, recent evidence suggests that sphingolipid metabolism is directly interconnected to the modulation of oxidative stress. However, cardiovascular development is highly sensitive to excessive reactive species production, and disturbances in sphingolipid metabolism can lead to abnormal development and cardiac disease. Therefore, in this review, we address the molecular link between sphingolipids and oxidative stress, connecting these pathways to cardiovascular development and cardiovascular disease. © 2014 Société Française des Microscopies and Société de Biologie Cellulaire de France. Published by John Wiley & Sons Ltd.

The production of concentrated dispersions of few-layer graphene by the direct exfoliation of graphite in organosilanes

PubMed Central

2012-01-01

We report the formation and characterization of graphene dispersions in two organosilanes, 3-glycidoxypropyl trimethoxysilane (GPTMS) and phenyl triethoxysilane (PhTES) as new reactive solvents. The preparation method was mild and easy and does not produce any chemical modification. The dispersions, which exhibit the Tyndall effect, were characterized by TEM and Raman spectroscopy to confirm the presence of few-layer graphene. Concentrations as high as 0.66 and 8.00 mg/ml were found for PhTES and GPTMS, respectively. The latter is one of the highest values reported for a dispersion of graphene obtained by any method. This finding paves the way for the direct synthesis of polymer nanofiller-containing composites consisting of graphene and reactive silanes to be used in sol–gel synthesis, without any need for solvent removal, thus preventing graphene reaggregation to form graphite flakes. PMID:23237423

Final Project Report: Release of aged contaminants from weathered sediments: Effects of sorbate speciation on scaling of reactive transport

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

Jon Chorover, University of Arizona; Peggy O'€™Day, University of California, Merced; Karl Mueller, Penn State University

2012-10-01

Hanford sediments impacted by hyperalkaline high level radioactive waste have undergone incongruent silicate mineral weathering concurrent with contaminant uptake. In this project, we studied the impact of background pore water (BPW) on strontium, cesium and iodine desorption and transport in Hanford sediments that were experimentally weathered by contact with simulated hyperalkaline tank waste leachate (STWL) solutions. Using those lab-weathered Hanford sediments (HS) and model precipitates formed during nucleation from homogeneous STWL solutions (HN), we (i) provided detailed characterization of reaction products over a matrix of field-relevant gradients in contaminant concentration, PCO2, and reaction time; (ii) improved molecular-scale understanding of howmore » sorbate speciation controls contaminant desorption from weathered sediments upon removal of caustic sources; and (iii) developed a mechanistic, predictive model of meso- to field-scale contaminant reactive transport under these conditions.« less

Percolation and criticality in a mitochondrial network

PubMed Central

Aon, Miguel A.; Cortassa, Sonia; O'Rourke, Brian

2004-01-01

Synchronization of mitochondrial function is an important determinant of cell physiology and survival, yet little is known about the mechanism of interorganellar communication. We have recently observed that coordinated cell-wide oscillations in the mitochondrial energy state of heart cells can be induced by a highly localized perturbation of a few elements of the mitochondrial network, indicating that mitochondria represent a complex, self-organized system. Here, we apply percolation theory to explain the mechanism of intermitochondrial signal propagation in response to oxidative stress. A global phase transition (mitochondrial depolarization) is shown to occur when a critical density of mitochondria accumulate reactive oxygen species above a threshold to form an extended spanning cluster. The scaling and fractal properties of the mitochondrial network at the edge of instability agree remarkably well with the idea that mitochondria are organized as a percolation matrix, with reactive oxygen species as a key messenger. PMID:15070738

High temperature cooling system and method

DOEpatents

Loewen, Eric P.

2006-12-12

A method for cooling a heat source, a method for preventing chemical interaction between a vessel and a cooling composition therein, and a cooling system. The method for cooling employs a containment vessel with an oxidizable interior wall. The interior wall is oxidized to form an oxide barrier layer thereon, the cooling composition is monitored for excess oxidizing agent, and a reducing agent is provided to eliminate excess oxidation. The method for preventing chemical interaction between a vessel and a cooling composition involves introducing a sufficient quantity of a reactant which is reactive with the vessel in order to produce a barrier layer therein that is non-reactive with the cooling composition. The cooling system includes a containment vessel with oxidizing agent and reducing agent delivery conveyances and a monitor of oxidation and reduction states so that proper maintenance of a vessel wall oxidation layer occurs.

Synthesis and cathodoluminescence of beta-Ga2O3 nanowires with holes.

PubMed

Zhang, Xitian; Liu, Zhuang; Hark, Suikong

2008-03-01

Gallium oxide nanowires were synthesized on Si (001) substrate by chemical vapor deposition, using a Ga/Ga2O3 mixture as a precursor and Au as a catalyst. The structure of the as-synthesized products was examined by X-ray powder diffraction and high-resolution transmission electron microscopy, and found to be monoclinic beta-Ga2O3. The morphologies of the beta-Ga2O3 nanowires were characterized by scanning electron microscopy. The majority of the nanowires contain holes along their length, but a few were also found without holes. The holes are believed to be formed by the reaction of adsorbed Ga droplets on reactive terminating surfaces of the nanowires. For nanowires where these reactive surfaces are not exposed, the reaction of Ga is retarded. Cathodoluminescence (CL) of the nanowires was measured. Three emission bands centered at 376, 454, and 666 nm, respectively, were observed.

Absolute fragmentation cross sections in atom-molecule collisions: Scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules

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

Chen, T.; Gatchell, M.; Stockett, M. H.

2014-06-14

We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH{sup +}) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH{sup +} + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C{sub 6}H{sub 5}). Thus nonstatistical fragmentation may be an effectivemore » initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.« less

Reactive tunnel junctions in electrically driven plasmonic nanorod metamaterials

NASA Astrophysics Data System (ADS)

Wang, Pan; Krasavin, Alexey V.; Nasir, Mazhar E.; Dickson, Wayne; Zayats, Anatoly V.

2018-02-01

Non-equilibrium hot carriers formed near the interfaces of semiconductors or metals play a crucial role in chemical catalysis and optoelectronic processes. In addition to optical illumination, an efficient way to generate hot carriers is by excitation with tunnelling electrons. Here, we show that the generation of hot electrons makes the nanoscale tunnel junctions highly reactive and facilitates strongly confined chemical reactions that can, in turn, modulate the tunnelling processes. We designed a device containing an array of electrically driven plasmonic nanorods with up to 1011 tunnel junctions per square centimetre, which demonstrates hot-electron activation of oxidation and reduction reactions in the junctions, induced by the presence of O2 and H2 molecules, respectively. The kinetics of the reactions can be monitored in situ following the radiative decay of tunnelling-induced surface plasmons. This electrically driven plasmonic nanorod metamaterial platform can be useful for the development of nanoscale chemical and optoelectronic devices based on electron tunnelling.

A method of producing high quality oxide and related films on surfaces

NASA Technical Reports Server (NTRS)

Ruckman, Mark W.; Strongin, Myron; Gao, Yongli

1991-01-01

Aluminum oxide or aluminum nitride films were deposited on molecular beam epitaxy (MBE) grown GaAS(100) using a novel cryogenic-based reactive thin film deposition technique. The process involves the condensation of molecular oxygen, ammonia, or other gases normally used for reactive thin film deposition on the substrate before the metal is deposited. The metal vapor is deposited into this layer and reacts with the molecular solid to form the desired compound or a precursor that can be thermally decomposed to generate the desired compound. The films produced by this method are free of impurities, and the low temperatures can be used to control the film and interfacial structure. The process can be easily integrated with existing MBE systems. Ongoing research using the same apparatus suggests that photon or electron irradiation could be used to promote the reactions needed to produce the intended material.

Accessing non-natural reactivity by irradiating nicotinamide-dependent enzymes with light

NASA Astrophysics Data System (ADS)

Emmanuel, Megan A.; Greenberg, Norman R.; Oblinsky, Daniel G.; Hyster, Todd K.

2016-12-01

Enzymes are ideal for use in asymmetric catalysis by the chemical industry, because their chemical compositions can be tailored to a specific substrate and selectivity pattern while providing efficiencies and selectivities that surpass those of classical synthetic methods. However, enzymes are limited to reactions that are found in nature and, as such, facilitate fewer types of transformation than do other forms of catalysis. Thus, a longstanding challenge in the field of biologically mediated catalysis has been to develop enzymes with new catalytic functions. Here we describe a method for achieving catalytic promiscuity that uses the photoexcited state of nicotinamide co-factors (molecules that assist enzyme-mediated catalysis). Under irradiation with visible light, the nicotinamide-dependent enzyme known as ketoreductase can be transformed from a carbonyl reductase into an initiator of radical species and a chiral source of hydrogen atoms. We demonstrate this new reactivity through a highly enantioselective radical dehalogenation of lactones—a challenging transformation for small-molecule catalysts. Mechanistic experiments support the theory that a radical species acts as an intermediate in this reaction, with NADH and NADPH (the reduced forms of nicotinamide adenine nucleotide and nicotinamide adenine dinucleotide phosphate, respectively) serving as both a photoreductant and the source of hydrogen atoms. To our knowledge, this method represents the first example of photo-induced enzyme promiscuity, and highlights the potential for accessing new reactivity from existing enzymes simply by using the excited states of common biological co-factors. This represents a departure from existing light-driven biocatalytic techniques, which are typically explored in the context of co-factor regeneration.

Atomistic Simulations of Chemical Reactivity of TATB Under Thermal and Shock Conditions

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

Manaa, M R; Reed, E J; Fried, L E

2009-09-23

The study of chemical transformations that occur at the reactive shock front of energetic materials provides important information for the development of predictive models at the grain-and continuum scales. A major shortcoming of current high explosives models is the lack of chemical kinetics data of the reacting explosive in the high pressure and temperature regimes. In the absence of experimental data, long-time scale atomistic molecular dynamics simulations with reactive chemistry become a viable recourse to provide an insight into the decomposition mechanism of explosives, and to obtain effective reaction rate laws. These rates can then be incorporated into thermo-chemical-hydro codesmore » (such as Cheetah linked to ALE3D) for accurate description of the grain and macro scales dynamics of reacting explosives. In this talk, I will present quantum simulations of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) crystals under thermal decomposition (high density and temperature) and shock compression conditions. This is the first time that condensed phase quantum methods have been used to study the chemistry of insensitive high explosives. We used the quantum-based, self-consistent charge density functional tight binding method (SCC{_}DFTB) to calculate the interatomic forces for reliable predictions of chemical reactions, and to examine electronic properties at detonation conditions for a relatively long time-scale on the order of several hundreds of picoseconds. For thermal decomposition of TATB, we conducted constant volume-temperature simulations, ranging from 0.35 to 2 nanoseconds, at {rho} = 2.87 g/cm{sup 3} at T = 3500, 3000, 2500, and 1500 K, and {rho} = 2.9 g/cm{sup 3} and 2.72 g/cm{sup 3}, at T = 3000 K. We also simulated crystal TATB's reactivity under steady overdriven shock compression using the multi-scale shock technique. We conducted shock simulations with specified shock speeds of 8, 9, and 10 km/s for up to 0.43 ns duration, enabling us to track the reactivity of TATB well into the formation of several stable gas products, such as H{sub 2}O, N{sub 2}, and CO{sub 2}. Although complex chemical transformations are occurring continuously in the dynamical, high temperature, reactive environment of our simulations, a simple overall scheme for the decomposition of TATB emerges: Water is the earliest decomposition products to form, followed by a polymerization (or condensation) process in which several TATB remaining fragments are joined together, initiating the early step in the formation of high-nitrogen clusters, along with stable products such as N{sub 2} and CO{sub 2}. Remarkably, these clusters with high concentration of carbon and nitrogen (and little oxygen) remain dynamically stable for the remaining period of the simulations. Our simulations, thus, reveal a hitherto unidentified region of high concentrations of nitrogen-rich heterocyclic clusters in reacting TATB, whose persistence impede further reactivity towards final products of fluid N{sub 2} and solid carbon. These simulations also predict significant populations of charged species such as NCO{sup -}, H{sup +}, OH{sup -}, H{sub 3}O{sup +}, and O{sup -2}, the first such observation in a reacting explosive. Finally, A reduced four steps, global reaction mechanism with Arrhenius kinetic rates for the decomposition of TATB, along with comparative Cheetah decomposition kinetics at various temperatures has been constructed and will be discussed.« less

Effects of Glycine, Water, Ammonia, and Ammonium Bicarbonate on the Oligomerization of Methionine

NASA Astrophysics Data System (ADS)

Huang, Rui; Furukawa, Yoshihiro; Otake, Tsubasa; Kakegawa, Takeshi

2017-06-01

The abiotic oligomerization of amino acids may have created primordial, protein-like biological catalysts on the early Earth. Previous studies have proposed and evaluated the potential of diagenesis for the amino acid oligomerization, simulating the formation of peptides that include glycine, alanine, and valine, separately. However, whether such conditions can promote the formation of peptides composed of multiple amino acids remains unclear. Furthermore, the chemistry of pore water in sediments should affect the oligomerization and degradation of amino acids and oligomers, but these effects have not been studied extensively. In this study, we investigated the effects of water, ammonia, ammonium bicarbonate, pH, and glycine on the oligomerization and degradation of methionine under high pressure (150 MPa) and high temperature conditions (175 °C) for 96 h. Methionine is more difficult to oligomerize than glycine and methionine dimer was formed in the incubation of dry powder of methionine. Methionine oligomers as long as trimers, as well as methionylglycine and glycylmethionine, were formed under every condition with these additional compounds. Among the compounds tested, the oligomerization reaction rate was accelerated by the presence of water and by an increase in pH. Ammonia also increased the oligomerization rate but consumed methionine by side reactions and resulted in the rapid degradation of methionine and its peptides. Similarly, glycine accelerated the oligomerization rate of methionine and the degradation of methionine, producing water, ammonia, and bicarbonate through its decomposition. With Gly, heterogeneous dimers (methionylglycine and glycylmethionine) were formed in greater amounts than with other additional compounds although smaller amount of these heterogeneous dimers were formed with other additional compounds. These results suggest that accelerated reaction rates induced by water and co-existing reactive compounds promote the oligomerization of less reactive amino acids during diagenesis and enhance the formation of peptides composed of multiple amino acids.

Respiratory Sinus Arrhythmia: A Transdiagnostic Biomarker of Emotion Dysregulation and Psychopathology

PubMed Central

Beauchaine, Theodore P.

2015-01-01

In the past two decades, respiratory sinus arrhythmia (RSA)—an index of parasympathetic nervous system (PNS)-mediated cardiac control—has emerged as a reliable peripheral biomarker of emotion regulation (ER). Reduced RSA and excessive RSA reactivity (i.e., withdrawal) to emotional challenge are observed consistently among individuals with poor ER capabilities, including those with various forms of internalizing and externalizing psychopathology, and those with specific psychopathological syndromes, including anxiety, phobias, attention problems, autism, callousness, conduct disorder, depression, non-suicidal self-injury, panic disorder, and trait hostility. Emerging evidence suggests that low RSA and excessive RSA reactivity index poor ER because they are downstream peripheral markers of prefrontal cortex (PFC) dysfunction. Poorly modulated inhibitory efferent pathways from the medial PFC to the PNS result in reduced RSA and excessive RSA reactivity. According to this perspective, RSA is a non-invasive proxy for poor executive control over behavior, which characterizes most forms of psychopathology. PMID:25866835

Semipermeable polymers and method for producing same

DOEpatents

Buschmann, Wayne E [Boulder, CO

2012-04-03

A polyamide membrane comprising reaction product of an anhydrous solution comprising an anhydrous solvent, at least one polyfunctional secondary amine and a pre-polymer deposition catalyst; and an anhydrous, organic solvent solution comprising a polyfunctional aromatic amine-reactive reactant comprising one ring. A composite semipermeable membrane comprising the polyamide membrane on a porous support. A method of making a composite semipermeable membrane by coating a porous support with an anhydrous solution comprising an anhydrous solvent, a polyfunctional secondary amine and a pre-polymer deposition catalyst, to form an activated pre-polymer layer on the porous support and contacting the activated pre-polymer layer with an anhydrous, organic solvent solution comprising a polyfunctional amine-reactive reactant to interfacially condense the amine-reactive reactant with the polyfunctional secondary amine, thereby forming a cross-linked, interfacial polyamide layer on the porous support. A method of impregnating a composite semipermeable membrane with nanoparticles selected from heavy metals and/or oxides of heavy metals.

Photoluminescent silicon nanocrystals with chlorosilane surfaces - synthesis and reactivity

NASA Astrophysics Data System (ADS)

Höhlein, Ignaz M. D.; Kehrle, Julian; Purkait, Tapas K.; Veinot, Jonathan G. C.; Rieger, Bernhard

2014-12-01

We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place.We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place. Electronic supplementary information (ESI) available: Detailed experimental procedures and additional NMR, PL, EDX, DLS and TEM data. See DOI: 10.1039/C4NR05888G

PYRIDOXAMINE ANALOGS SCAVENGE LIPID-DERIVED γ-KETOALDEHYDES AND PROTECT AGAINST H2O2-MEDIATED CYTOTOXICITY†

PubMed Central

Davies, Sean S.; Brantley, Eric J.; Voziyan, Paul A.; Amarnath, Venkataraman; Zagol-Ikapitte, Irene; Boutaud, Olivier; Hudson, Billy G.; Oates, John A.; Jackson Roberts, L.

2008-01-01

Isoketals and levuglandins are highly reactive γ-ketoaldehydes formed by oxygenation of arachidonic acid in settings of oxidative injury and cyclooxygenase activation, respectively. These compounds rapidly adduct to proteins via lysyl residues, which can alter protein structure/function. We examined whether pyridoxamine, which has been shown to scavenge α-ketoaldehydes formed by carbohydrate or lipid peroxidation, could also effectively protect proteins from the more reactive γ-ketoaldehydes. Pyridoxamine prevented adduction of ovalbumin and also prevented inhibition of RNase A and glutathione reductase activity by the synthetic γ-ketoaldehyde, 15-E2-isoketal. We identified the major products of the reaction of pyridoxamine with the 15-E2-isoketal, including a stable lactam adduct. Two lipophilic analogs of pyridoxamine, salicylamine and 5’O-pentylpyridoxamine, also formed lactam adducts when reacted with 15-E2-isoketal. When we oxidized arachidonic acid in the presence of pyridoxamine or its analogs, pyridoxamine-isoketal adducts were found in significantly greater abundance than the pyridoxamine-N-acyl adducts formed by α-ketoaldehyde scavenging. Therefore, pyridoxamine and its analogs appear to preferentially scavenge γ-ketoaldehydes. Both pyridoxamine and its lipophilic analogs inhibited the formation of lysyl-levuglandin adducts in platelets activated ex vivo with arachidonic acid. The two lipophilic pyridoxamine analogs provided significant protection against H2O2-mediated cytotoxicity in HepG2 cells. These results demonstrate the utility of pyridoxamine and lipophilic pyridoxamine analogs to assess the potential contributions of isoketals and levuglandins in oxidant injury and inflammation and suggest their potential utility as pharmaceutical agents in these conditions. PMID:17176098

Hypoglycemic drugs induce antioxidant aldehyde dehydrogenase activity and remain high in patients with glycemic control in type 2 diabetes.

PubMed

Picazo, Alejandra; Jiménez-Osorio, Angélica S; Zúñiga-Mejía, Porfirio; Pedraza-Chaverri, José; Monroy, Adriana; Rodríguez-Arellano, M Eunice; Barrera-Oviedo, Diana

2017-04-05

The antioxidant system results essential to control and prevent lipid peroxidation due to stress damage in type 2 diabetes. An example is aldehyde dehydrogenase (ALDH), an enzyme that is involved in the detoxification of aldehydes formed during lipid peroxidation. This study was conducted to evaluate ALDH activity and to determine their association with hypoglycemic treatment in type 2 diabetes patients. The study population consisted of 422 Mexican subjects: a control group and type 2 diabetes patients. Type 2 diabetes patients were re-classified as those with or without hypoglycemic treatment and those with or without glycemic control (according to glycated hemoglobin (HbA1c)). Clinical parameters, antioxidant enzyme activities (ALDH, superoxide dismutase (SOD), catalase and glutathione peroxidase) and oxidative markers (reactive oxygen species and thiobarbituric acid reactive substances (TBARS)) were evaluated. The activity of antioxidant enzymes and oxidative stress markers were higher in type 2 diabetes patients with hypoglycemic treatment and without glycemic control than control group. The activity of ALDH and SOD remained high in type 2 diabetes patients with moderate glycemic control while only ALDH's remained high in type 2 diabetes patients with tight glycemic control. Increased ALDH and SOD activities were associated with hypoglycemic therapy. TBARS levels were associated with glycemic control. The persistence of high ALDH and SOD activities in type 2 diabetes patients with glycemic control may be to avoid a significant damage due to the increase in reactive oxygen species and TBARS. It is possible that this new oxidative status prevented the development the classical complications of diabetes. Copyright © 2017 Elsevier B.V. All rights reserved.

Myeloperoxidase scavenges peroxynitrite: A novel anti-inflammatory action of the heme enzyme

PubMed Central

Koyani, Chintan N.; Flemmig, Joerg; Malle, Ernst; Arnhold, Juergen

2015-01-01

Peroxynitrite, a potent pro-inflammatory and cytotoxic species, interacts with a variety of heme containing proteins. We addressed the question whether (i) the interaction of myeloperoxidase (MPO, an enzyme generating hypochlorous acid from hydrogen peroxide and chloride ions) with peroxynitrite affects the clearance of peroxynitrite, and (ii) if peroxynitrite could modulate the chlorinating activity of MPO. Our results show that this interaction promotes the decomposition of the highly reactive pro-inflammatory oxidant, whereby MPO Compound II (but not Compound I) is formed. The efficiency of MPO to remove peroxynitrite was enhanced by l-tyrosine, nitrite and (−)-epicatechin, substances known to reduce Compound II with high reaction rate. Next, peroxynitrite (added as reagent) diminished the chlorinating activity of MPO in the presence of hydrogen peroxide. Alternatively, SIN-1, a peroxynitrite donor, reduced hypochlorous acid formation by MPO, as measured by aminophenyl fluorescein oxidation (time kinetics) and taurine chloramine formation (end point measurement). At inflammatory loci, scavenging of peroxynitrite by MPO may overcome the uncontrolled peroxynitrite decomposition and formation of reactive species, which lead to cell/tissue damage. PMID:25731855

Boron deactivation in heavily boron-doped Czochralski silicon during rapid thermal anneal: Atomic level understanding

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

Gao, Chao; Dong, Peng; Yi, Jun

The changes in hole concentration of heavily boron (B)-doped Czochralski silicon subjected to high temperature rapid thermal anneal (RTA) and following conventional furnace anneal (CFA) have been investigated. It is found that decrease in hole concentration, namely, B deactivation, is observed starting from 1050 °C and increases with RTA temperature. The following CFA at 300–500 °C leads to further B deactivation, while that at 600–800 °C results in B reactivation. It is supposed that the interaction between B atoms and silicon interstitials (I) thus forming BI pairs leads to the B deactivation during the high temperature RTA, and, moreover, the formation of extendedmore » B{sub 2}I complexes results in further B deactivation in the following CFA at 300–500 °C. On the contrary, the dissociation of BI pairs during the following CFA at 600–800 °C enables the B reactivation. Importantly, the first-principles calculation results can soundly account for the above-mentioned supposition.« less

Colloidal paradigm in supercapattery electrode systems

NASA Astrophysics Data System (ADS)

Chen, Kunfeng; Xue, Dongfeng

2018-01-01

Among decades of development, electrochemical energy storage systems are now sorely in need of a new design paradigm at the nano size and ion level to satisfy the higher energy and power demands. In this review paper, we introduce a new colloidal electrode paradigm for supercapattery that integrates multiple-scale forms of matter, i.e. ion clusters, colloidal ions, and nanosized materials, into one colloid system, coupled with multiple interactions, i.e. electrostatic, van der Waals forces, and chemical bonding, thus leading to the formation of many redox reactive centers. This colloidal electrode not only keeps the original ionic nature in colloidal materials, but also creates a new attribute of high electroactivity. Colloidal supercapattery is a perfect application example of the novel colloidal electrode, leading to higher specific capacitance than traditional electrode materials. The high electroactivity of the colloidal electrode mainly comes from the contribution of exposed reactive centers, owing to the confinement effect of carbon and a binder matrix. Systematic and thorough research on the colloidal system will significantly promote the development of fundamental science and the progress of advanced energy storage technology.

Recombinant human antibody fragment against tetanus toxoid produced by phage display.

PubMed

Neelakantam, B; Sridevi, N V; Shukra, A M; Sugumar, P; Samuel, S; Rajendra, L

2014-03-01

Phage display technology is a powerful in vitro method for the identification of specific monoclonal antibodies (antibody fragments) to an antigenic target and allows the rapid generation and selection of high affinity, fully human antibodies directed toward any disease target appropriate for antibody therapy. In the present study, we exploited the phage display technology for the selection of an antigen binding fragment (Fabs) toward tetanus toxoid using human naïve phage antibody library constructed from peripheral blood lymphocytes of naïve human donors. The phages displaying Fab were subjected to three rounds of bio-panning with tetanus toxoid as antigen on a solid phase. The high affinity antibody fragments were expressed in HB2151 strain of Escherichia coli and purified by immobilized metal affinity chromatography. The binding activity and specificity of the antibody fragment was established by its reactivity toward tetanus toxoid and non-reactivity toward other related toxins as determined by enzyme-linked immunosorbent assay and immunoblot analysis. The selected Fab fragment forming the antigen-binding complexes with the toxoid in flocculation assay indicates that the Fab may have a potential neutralizing ability toward antigen.

Long Time Evolution of Sequestered CO2 in Porous Media

NASA Astrophysics Data System (ADS)

Cohen, Y.; Rothman, D.

2013-12-01

CO2 sequestration is important for mitigating climate change and reducing atmospheric CO2 concentration. However, a complete physical picture able to predict both the pattern formation and the structure developing within the porous medium is lacking. We propose a theoretical model that couples transport, reaction, and the intricate geometry of the rock, in order to study the long time evolution of carbon in the brine-rock environment. As CO2 is injected into a brine-rock environment, it becomes initially trapped, and isolated bubbles are formed. Within the high CO2 phase, minerals dissolve and migrate from high concentration to low concentration regions, along with other carbonate species. The change in the concentrations at the interface moves the system out of equilibrium, drives up the saturation level, and leads to mineral precipitation. We argue that mineral precipitation in a small boundary layer may lead to lower diffusivity, slower kinetics, and eventually to a mechanical trapping of the CO2 bubbles. We investigate the reactive transport model and study the conditions that cause the mechanical separation of these two reactive fluids in porous media.

Electron beams in research and technology

NASA Astrophysics Data System (ADS)

Mehnert, R.

1995-11-01

Fast electrons lose their energy by inelastic collisions with electrons of target molecules forming secondary electrons and excited molecules. Coulomb interaction of secondary electrons with valence electrons of neighboring molecules leads to the formation of radical cations, thermalized electrons, excited molecular states and radicals. The primary reactive species initiate chemical reactions in the materials irradiated. Polymer modifications using accelerated electrons such as cross-linking of cable insulation, tubes, pipes and moldings, vulcanization of elastomers, grafting of polymer surfaces, processing of foamed plastics and heat shrinkable materials have gained wide industrial acceptance. A steadily growing electron beam technology is curing of paints, lacquers, printing inks and functional coatings. Electron beam processing offers high productivity, the possibility to treat the materials at normal temperature and pressure, excellent process control and clean production conditions. On an industrial scale the most important application of fast electrons is curing of 100% reactive monomer/prepolymer systems. Mainly acrylates and epoxides are used to formulate functional coatings on substrates such as paper, foil, wood, fibre board and high pressure laminates. A survey is given about the reaction mechanism of curing, the characterization of cured coatings, and of some industrial application.

40 CFR 63.4541 - How do I demonstrate initial compliance with the emission limitations?

Code of Federal Regulations, 2010 CFR

2010-07-01

... PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR... volatile matter and use that value as a substitute for mass fraction of organic HAP. For reactive adhesives... not have to count it. For reactive adhesives in which some of the HAP react to form solids and are not...

VARIABLE BOUND-SITE CHARGING CONTRIBUTIONS TO SURFACE COMPLEXATION MASS ACTION EXPRESSIONS

EPA Science Inventory

One and two pK models of surface complexation reactions between reactive surface sites (>SOH) and the proton (H+) use mass action expressions of the form: Ka={[>SOHn-1z-1]g>SOH(0-1)aH+EXP(-xeY/kT)}/{[>SOHnz]g>SOH(n)} where Ka=the acidity constant, [ ]=reactive species concentrati...

The Affective Reactivity Index: A Concise Irritability Scale for Clinical and Research Settings

ERIC Educational Resources Information Center

Stringaris, Argyris; Goodman, Robert; Ferdinando, Sumudu; Razdan, Varun; Muhrer, Eli; Leibenluft, Ellen; Brotman, Melissa A.

2012-01-01

Background: Irritable mood has recently become a matter of intense scientific interest. Here, we present data from two samples, one from the United States and the other from the United Kingdom, demonstrating the clinical and research utility of the parent- and self-report forms of the Affective Reactivity Index (ARI), a concise dimensional measure…

A Runge-Kutta discontinuous Galerkin approach to solve reactive flows: The hyperbolic operator

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

Billet, G., E-mail: billet@onera.f; Ryan, J., E-mail: ryan@onera.f

2011-02-20

A Runge-Kutta discontinuous Galerkin method to solve the hyperbolic part of reactive Navier-Stokes equations written in conservation form is presented. Complex thermodynamics laws are taken into account. Particular care has been taken to solve the stiff gaseous interfaces correctly with no restrictive hypothesis. 1D and 2D test cases are presented.

Smooth Interfacial Scavenging for Resistive Switching Oxide via the Formation of Highly Uniform Layers of Amorphous TaOx.

PubMed

Tsurumaki-Fukuchi, Atsushi; Nakagawa, Ryosuke; Arita, Masashi; Takahashi, Yasuo

2018-02-14

We demonstrate that the inclusion of a Ta interfacial layer is a remarkably effective strategy for forming interfacial oxygen defects at metal/oxide junctions. The insertion of an interfacial layer of a reactive metal, that is, a "scavenging" layer, has been recently proposed as a way to create a high concentration of oxygen defects at an interface in redox-based resistive switching devices, and growing interest has been given to the underlying mechanism. Through structural and chemical analyses of Pt/metal/SrTiO 3 /Pt structures, we reveal that the rate and amount of oxygen scavenging are not directly determined by the formation free energies in the oxidation reactions of the scavenging metal and unveil the important roles of oxygen diffusibility. Active oxygen scavenging and highly uniform oxidation via scavenging are revealed for a Ta interfacial layer with high oxygen diffusibility. In addition, the Ta scavenging layer is shown to exhibit a highly uniform structure and to form a very flat interface with SrTiO 3 , which are advantageous for the fabrication of a steep metal/oxide contact.

Peer Relations and Peer Deviance as Predictors of Reactive and Proactive Aggression among High School Girls

ERIC Educational Resources Information Center

Uz Bas, Asli; Öz Soysal, Fatma Selda

2016-01-01

This study aimed to investigate associations between reactive and proactive aggression and peer relations and peer deviance among high school girls. A total of 442 high school students participated in this study. Reactive-Proactive Aggression Questionnaire, the Peer Relations Scale, and the Peer Deviance Scale were used to collect data. Results…

Selective Targeting of High-Affinity LFA-1 Does Not Augment Costimulation Blockade in a Nonhuman Primate Renal Transplantation Model

PubMed Central

Samy, KP; Anderson, DA; Lo, DJ; Mulvihill, MS; Song, M; Farris, AB; Parker, BS; MacDonald, AL; Lu, C; Springer, TA; Kachlany, SC; Reimann, KA; How, T; Leopardi, FV; Franke, KS; Williams, KD; Collins, BH; Kirk, AD

2016-01-01

Costimulation blockade (CoB) via belatacept is a lower morbidity alternative to calcineurin inhibitor (CNI)-based immunosuppression. However, it has higher rates of early acute rejection. These early rejections are mediated in part by memory T cells, which have reduced dependence on the pathway targeted by belatacept, and increased adhesion molecule expression. One such molecule is Leukocyte Function Associated Antigen (LFA)-1. LFA-1 exists in two forms, a commonly expressed, low-affinity form, and a transient, high-affinity form, expressed only during activation. We have shown that antibodies reactive with LFA-1 irrespective of its configuration are effective in eliminating memory T cells, but at the cost of impaired protective immunity. Here we test two novel agents, Leukotoxin A and AL-579, each of which targets the high affinity form of LFA-1, to determine whether this more precise targeting prevents belatacept-resistant rejection. Despite evidence of ex vivo and in vivo ligand-specific activity, neither agent when combined with belatacept proved superior to belatacept monotherapy. Leukotoxin A approached a ceiling of toxicity prior to efficacy, while AL-579 failed to significantly alter the peripheral immune response. These data, and prior studies, suggest that LFA-1 blockade may not be a suitable adjuvant agent for CoB resistant rejection. PMID:27888551

Transport equations for partially ionized reactive plasma in magnetic field

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

Zhdanov, V. M.; Stepanenko, A. A.

2016-06-08

Transport equations for partially ionized reactive plasma in magnetic field taking into account the internal degrees of freedom and electronic excitation of plasma particles are derived. As a starting point of analysis the kinetic equation with a binary collision operator written in the Wang-Chang and Uhlenbeck form and with a reactive collision integral allowing for arbitrary chemical reactions is used. The linearized variant of Grad’s moment method is applied to deduce the systems of moment equations for plasma and also full and reduced transport equations for plasma species nonequilibrium parameters.

The effect of micellization on the EPR spectra and reactivity of 2,2,4,4-tetramethylpiperidinoxyl (TEMPO) radicals.

PubMed

Aliaga, Carolina; Rezende, Marcos Caroli; Mena, Geraldine

2016-11-01

A series of 4-alkanoyloxy-2,2,6,6-tetramethylpiperidinoxyl radicals was prepared, and their reactivity in water vis-à-vis antioxidant Trolox was compared. Spectral (electron paramagnetic resonance) and dynamic-light-scattering measurements suggested the formation of micelles for the more hydrophobic members of the series. The observed increase in reactivity for the micelle-forming radicals reflected the increased local concentration of the radical fragment on the micellar interface. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Sequencing the extrachromosomal circular mobilome reveals retrotransposon activity in plants

PubMed Central

Llauro, Christel; Jobet, Edouard; Robakowska-Hyzorek, Dagmara; Lasserre, Eric; Ghesquière, Alain; Panaud, Olivier

2017-01-01

Retrotransposons are mobile genetic elements abundant in plant and animal genomes. While efficiently silenced by the epigenetic machinery, they can be reactivated upon stress or during development. Their level of transcription not reflecting their transposition ability, it is thus difficult to evaluate their contribution to the active mobilome. Here we applied a simple methodology based on the high throughput sequencing of extrachromosomal circular DNA (eccDNA) forms of active retrotransposons to characterize the repertoire of mobile retrotransposons in plants. This method successfully identified known active retrotransposons in both Arabidopsis and rice material where the epigenome is destabilized. When applying mobilome-seq to developmental stages in wild type rice, we identified PopRice as a highly active retrotransposon producing eccDNA forms in the wild type endosperm. The mobilome-seq strategy opens new routes for the characterization of a yet unexplored fraction of plant genomes. PMID:28212378

Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

NASA Technical Reports Server (NTRS)

Dingemans, Theodorus J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

2009-01-01

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

Sequencing the extrachromosomal circular mobilome reveals retrotransposon activity in plants.

PubMed

Lanciano, Sophie; Carpentier, Marie-Christine; Llauro, Christel; Jobet, Edouard; Robakowska-Hyzorek, Dagmara; Lasserre, Eric; Ghesquière, Alain; Panaud, Olivier; Mirouze, Marie

2017-02-01

Retrotransposons are mobile genetic elements abundant in plant and animal genomes. While efficiently silenced by the epigenetic machinery, they can be reactivated upon stress or during development. Their level of transcription not reflecting their transposition ability, it is thus difficult to evaluate their contribution to the active mobilome. Here we applied a simple methodology based on the high throughput sequencing of extrachromosomal circular DNA (eccDNA) forms of active retrotransposons to characterize the repertoire of mobile retrotransposons in plants. This method successfully identified known active retrotransposons in both Arabidopsis and rice material where the epigenome is destabilized. When applying mobilome-seq to developmental stages in wild type rice, we identified PopRice as a highly active retrotransposon producing eccDNA forms in the wild type endosperm. The mobilome-seq strategy opens new routes for the characterization of a yet unexplored fraction of plant genomes.

The role of porosity and annealing in the impact fragmentation of an aluminum reactive material

NASA Astrophysics Data System (ADS)

Hooper, Joseph

2017-06-01

A reactive fragment has a unique structural requirement to survive explosive launch but then fragment catastrophically and combust upon impact. Suitable materials for this application tend to be metal composites with high ductility in compression but elastic-brittle behavior in tension. Characterizing the dynamic fragmentation of such materials is key for understanding their lethality. Here we consider a prototypical aluminum reactive frag material, formed via cold isostatic pressing of micron-scale powder followed by annealing. Samples were gun-launched into a target and recovered in a soft-catch medium of artificial snow, allowing for excellent recovery down to micron sizes and minimal contamination. Recovered fragment distributions were analyzed and compared to standard energy-balance theories. We study the effect of compaction pressure and annealing conditions on the fragmentation behavior at 500-800 m/s impacts, and find a particularly strong effect from short annealing periods. Though dynamic fracture occurs entirely along original particle boundaries in this material, recovery processes within the Al microstructure during annealing lead to a rapid decrease in the extent of fragmentation. This work was funded by the Office of Naval Research, program director Cliff Bedford.

Evaporite Caprock Integrity. An experimental study of reactive mineralogy and pore-scale heterogeneity during brine-CO 2 exposure

DOE PAGES

Smith, Megan M.; Sholokhova, Yelena; Hao, Yue; ...

2012-07-25

Characterization and geochemical data are presented from a core-flooding experiment on a sample from the Three Fingers evaporite unit forming the lower extent of caprock at the Weyburn-Midale reservoir, Canada. This low-permeability sample was characterized in detail using X-ray computed microtomography before and after exposure to CO 2-acidified brine, allowing mineral phase and voidspace distributions to be quantified in three dimensions. Solution chemistry indicated that CO 2-acidified brine preferentially dissolved dolomite until saturation was attained, while anhydrite remained unreactive. Dolomite dissolution contributed to increases in bulk permeability through the formation of a localized channel, guided by microfractures as well asmore » porosity and reactive phase distributions aligned with depositional bedding. An indirect effect of carbonate mineral reactivity with CO 2-acidified solution is voidspace generation through physical transport of anhydrite freed from the rock matrix following dissolution of dolomite. The development of high permeability fast pathways in this experiment highlights the role of carbonate content and potential fracture orientations in evaporite caprock formations considered for both geologic carbon sequestration and CO 2-enhanced oil recovery operations.« less

Effect of reactive element oxide coating on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; El Messki, S.

2004-05-01

The influence of yttrium oxide coating (processed by the sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373 K. The scale growth kinetics of the uncoated alloy obey a parabolic rate law during the whole oxidation test, whereas the kinetic curves of the Y-coated specimen exhibit an initial transient stage for the first few hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not provide the beneficial effect usually ascribed to reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constant values are strictly identical for both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen comprised, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO 3, Y 3Al 5O 12) located in the outermost part of the layer.

Inert gas enhanced laser-assisted purification of platinum electron-beam-induced deposits

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

Stanford, Michael G.; Lewis, Brett B.; Noh, Joo Hyon

Electron-beam-induced deposition patterns, with composition of PtC 5, were purified using a pulsed laser-induced purification reaction to erode the amorphous carbon matrix and form pure platinum deposits. Enhanced mobility of residual H 2O molecules via a localized injection of inert Ar–H 2 (4%) is attributed to be the reactive gas species for purification of the deposits. Surface purification of deposits was realized at laser exposure times as low as 0.1 s. The ex situ purification reaction in the deposit interior was shown to be rate-limited by reactive gas diffusion into the deposit, and deposit contraction associated with the purification processmore » caused some loss of shape retention. To circumvent the intrinsic flaws of the ex situ anneal process, in situ deposition and purification techniques were explored that resemble a direct write atomic layer deposition (ALD) process. First, we explored a laser-assisted electron-beam-induced deposition (LAEBID) process augmented with reactive gas that resulted in a 75% carbon reduction compared to standard EBID. Lastly, a sequential deposition plus purification process was also developed and resulted in deposition of pure platinum deposits with high fidelity and shape retention.« less

Phytomonas serpens, a tomato parasite, shares antigens with Trypanosoma cruzi that are recognized by human sera and induce protective immunity in mice.

PubMed

Breganó, José Wander; Picão, Renata Cristina; Graça, Viviane Krominski; Menolli, Rafael Andrade; Itow Jankevicius, Shiduca; Pinge Filho, P; Jankevicius, José Vítor

2003-12-05

The immune cross-reactivity between Trypanosoma cruzi, the protozoan that causes Chagas' disease, and Phytomonas serpens, a trypanosomatid that infects tomatoes, was studied. Sera from patients with Chagas' disease presented a strong reactivity with P. serpens antigens by conventional serological assays such as indirect immunofluorescence (IIF) and direct agglutination test (DAT), confirmed after cross-absorption experiments. The results show that this protozoan is highly immunogenic and that rabbit and mouse hyperimmune serum raised against T. cruzi or P. serpens was able to recognize both T. cruzi and P. serpens antigens in immunofluorescence and agglutination assays. The antigenic cross-reactivity between T. cruzi and P. serpens was also demonstrated in vivo. BALB/c mice immunized by the intraperitoneal or oral route with P. serpens and later challenged with a lethal inoculum of T. cruzi blood forms showed a significant decrease in parasitemia and increase in survival compared to controls. A practical implication of these findings is that the ingestion by humans or animals of living plant trypanosomatids present in naturally infected edible fruits could potentially prime the immune response to T. cruzi antigens and interfere with the development of T. cruzi infection.

Asymmetric catalytic formation of quaternary carbons by iminium ion trapping of radicals

NASA Astrophysics Data System (ADS)

Murphy, John J.; Bastida, David; Paria, Suva; Fagnoni, Maurizio; Melchiorre, Paolo

2016-04-01

An important goal of modern organic chemistry is to develop new catalytic strategies for enantioselective carbon-carbon bond formation that can be used to generate quaternary stereogenic centres. Whereas considerable advances have been achieved by exploiting polar reactivity, radical transformations have been far less successful. This is despite the fact that open-shell intermediates are intrinsically primed for connecting structurally congested carbons, as their reactivity is only marginally affected by steric factors. Here we show how the combination of photoredox and asymmetric organic catalysis enables enantioselective radical conjugate additions to β,β-disubstituted cyclic enones to obtain quaternary carbon stereocentres with high fidelity. Critical to our success was the design of a chiral organic catalyst, containing a redox-active carbazole moiety, that drives the formation of iminium ions and the stereoselective trapping of photochemically generated carbon-centred radicals by means of an electron-relay mechanism. We demonstrate the generality of this organocatalytic radical-trapping strategy with two sets of open-shell intermediates, formed through unrelated light-triggered pathways from readily available substrates and photoredox catalysts—this method represents the application of iminium ion activation (a successful catalytic strategy for enantioselective polar chemistry) within the realm of radical reactivity.

Extended asymmetric hot region formation due to shockwave interactions following void collapse in shocked high explosive

NASA Astrophysics Data System (ADS)

Shan, Tzu-Ray; Wixom, Ryan R.; Thompson, Aidan P.

2016-08-01

In both continuum hydrodynamics simulations and also multimillion atom reactive molecular dynamics simulations of shockwave propagation in single crystal pentaerythritol tetranitrate (PETN) containing a cylindrical void, we observed the formation of an initial radially symmetric hot spot. By extending the simulation time to the nanosecond scale, however, we observed the transformation of the small symmetric hot spot into a longitudinally asymmetric hot region extending over a much larger volume. Performing reactive molecular dynamics shock simulations using the reactive force field (ReaxFF) as implemented in the LAMMPS molecular dynamics package, we showed that the longitudinally asymmetric hot region was formed by coalescence of the primary radially symmetric hot spot with a secondary triangular hot zone. We showed that the triangular hot zone coincided with a double-shocked region where the primary planar shockwave was overtaken by a secondary cylindrical shockwave. The secondary cylindrical shockwave originated in void collapse after the primary planar shockwave had passed over the void. A similar phenomenon was observed in continuum hydrodynamics shock simulations using the CTH hydrodynamics package. The formation and growth of extended asymmetric hot regions on nanosecond timescales has important implications for shock initiation thresholds in energetic materials.

Inert gas enhanced laser-assisted purification of platinum electron-beam-induced deposits

DOE PAGES

Stanford, Michael G.; Lewis, Brett B.; Noh, Joo Hyon; ...

2015-06-30

Electron-beam-induced deposition patterns, with composition of PtC 5, were purified using a pulsed laser-induced purification reaction to erode the amorphous carbon matrix and form pure platinum deposits. Enhanced mobility of residual H 2O molecules via a localized injection of inert Ar–H 2 (4%) is attributed to be the reactive gas species for purification of the deposits. Surface purification of deposits was realized at laser exposure times as low as 0.1 s. The ex situ purification reaction in the deposit interior was shown to be rate-limited by reactive gas diffusion into the deposit, and deposit contraction associated with the purification processmore » caused some loss of shape retention. To circumvent the intrinsic flaws of the ex situ anneal process, in situ deposition and purification techniques were explored that resemble a direct write atomic layer deposition (ALD) process. First, we explored a laser-assisted electron-beam-induced deposition (LAEBID) process augmented with reactive gas that resulted in a 75% carbon reduction compared to standard EBID. Lastly, a sequential deposition plus purification process was also developed and resulted in deposition of pure platinum deposits with high fidelity and shape retention.« less

Non-focusing active warhead

DOEpatents

Hornig, H.C.

1998-12-22

A non-nuclear, non-focusing, active warhead that comprises a high explosive charge contained within a casing of reactive metal is disclosed. When the high explosive is detonated, the reactive metal is dispersed and reacts with the air, which significantly increases the explosive yield of the warhead. The active warhead produces therefore much higher blast effects with significantly reduced weight compared to conventional munitions. The warhead is highly effective against such targets as aircraft which typically have thin fuselages, for example. The explosiveness of this warhead can be enhanced further by elevating the temperature and therefore the reactivity of the reactive metal before or during the explosion. New methods of enhancing the reactivity of the metal are also taught. 4 figs.

Non-focusing active warhead

DOEpatents

Hornig, Howard C.

1998-01-01

A non-nuclear, non-focusing, active warhead that comprises a high explosive charge contained within a casing of reactive metal. When the high explosive is detonated, the reactive metal is dispersed and reacts with the air, which significantly increases the explosive yield of the warhead. The active warhead produces therefore much higher blast effects with significantly reduced weight compared to conventional munitions. The warhead is highly effective against such targets as aircraft which typically have thin fuselages, for example. The explosiveness of this warhead can be enhanced further by elevating the temperature and therefore the reactivity of the reactive metal before or during the explosion. New methods of enhancing the reactivity of the metal are also taught.

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J.; Dai, Sheng; Oyola, Yatsandra

2016-09-06

A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

DOEpatents

Janke, Christopher J; Dai, Sheng; Oyola, Yatsandra

2014-05-13

A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

Combining Ambient Measurements of OH Radicals and OH Reactivity in a Tropical Rainforest during the OP-3 Project: Resolving the Magnitude of the Missing OH Sources and Sinks

NASA Astrophysics Data System (ADS)

Whalley, L. K.; Edwards, P.; Furneaux, K. L.; Goddard, A.; George, I. J.; Evans, M. J.; Heard, D. E.; Team Op-3

2010-12-01

The self cleansing capacity of the troposphere and the lifetime of key greenhouse gases are controlled to a large extent by the OH radical. In environments where biogenic VOC emissions are high and NOx concentrations are low, for example in tropical rainforests, the current understanding of tropospheric chemistry suggests that OH radical concentrations should be suppressed. OH measurements made in such regions, however, have highlighted higher than expected OH radical concentrations that cannot be replicated by chemical models constrained with the currently known OH formation pathways [1]. Here we report OH and OH reactivity measurements made during the OP-3 project that took place in the Borneo rainforest in 2008. Concentrations of OH displayed a clear diurnal cycle, peaking at solar noon, with significant concentrations observed: up to 8.7×106 molecule cm-3 (60 min average). Although j(O1D) levels and humidity were high, low O3 concentrations limited the rate of primary OH production from ozone photolysis. OH reactivity measurements were made using a sliding injector flow-tube reactor technique, with OH detection by LIF. Mean OH reactivities of 15.5 s-1 were observed with daily maximum OH reactivity of 24.7 ± 11.1 s-1 shortly after local solar noon, coinciding with peak isoprene concentrations. Minimum values of 7.2 ± 2.2 s-1 were observed just before sun rise. Using the measured OH and OH reactivity in a constrained box model containing detailed MCM chemistry we are able to fully resolve the magnitude of the missing OH source. We find that significant OH sources must be present - in addition to primary production - in order to maintain the elevated levels of OH levels recorded. Inclusion of an additional OH source formed as a recycled product of isoprene oxidation [2] improves the modelled OH agreement but reduces the modelled to measured HO2 agreement. To replicate both OH and HO2, a process that recycles HO2 to OH is required; equivalent to the OH recycling effect of 0.74 ppbv of NO. The model is unable to account for all of the OH reactivity; to simulate the OH reactivity a range of unmeasured sinks must be invoked. In general we believe that the simultaneous measurement of OH reactivity and OH concentration enables the separation of OH sources and sinks, allowing a more comprehensive test of our understanding of the radical chemistry occurring in this chemically complex environment. [1] J. Lelieveld, T. M. Butler, J. N. Crowley et al.: Nature, 2008, 452, p.737 - 740 [2] J. Peeters, T. L. Nguyen & L. Vereecken, PCCP, 2009, 11, p.5935 - 5939

Evaluation of the furosine and homoarginine methods for determining reactive lysine in rumen-undegraded protein.

PubMed

Boucher, S E; Pedersen, C; Stein, H H; Schwab, C G

2009-08-01

Three samples of soybean meal (SBM), 3 samples of expeller SBM (SoyPlus, West Central Cooperative, Ralston, IA), 5 samples of distillers dried grains with solubles (DDGS), and 5 samples of fish meal were used to evaluate the furosine and homoarginine procedures to estimate reactive Lys in the rumen-undegraded protein fraction (RUP-Lys). One sample each of SBM, expeller SBM, and DDGS were subjected to additional heat treatment in the lab to ensure there was a wide range in reactive RUP-Lys content among the samples. Furosine is a secondary product of the initial stages of the Maillard reaction and can be used to calculate blocked Lys. Homoarginine is formed via the reaction of reactive Lys with O-methylisourea and can be used to calculate the concentration of reactive Lys. In previous experiments, each sample was ruminally incubated in situ for 16 h, and standardized RUP-Lys digestibility of the samples was determined in cecectomized roosters. All rumen-undegraded residue (RUR) samples were analyzed for furosine and Lys; however, only 9 of the 16 samples contained furosine, and only the 4 unheated DDGS samples contained appreciable amounts of furosine. Blocked RUP-Lys was calculated from the furosine and Lys concentrations of the RUR. Both the intact feed and RUR samples were evaluated using the homoarginine method. All samples were incubated with an O-methylisourea/BaOH solution for 72 h and analyzed for Lys and homoarginine concentrations. Reactive Lys concentrations of the intact feeds and RUR were calculated. Results of the experiment indicate that blocked RUP-Lys determined via the furosine method was negatively correlated with standardized RUP-Lys digestibility, and reactive RUP-Lys determined via the guanidination method was positively correlated with standardized RUP-Lys digestibility. Reactive Lys concentrations of the intact samples were also highly correlated with RUP-Lys digestibility. In conclusion, the furosine assay is useful in predicting RUP-Lys digestibility of DDGS samples, and the guanidination procedure can be used to predict RUP-Lys digestibility of SBM, expeller SBM, DDGS, and fish meal samples.

Iridium-Catalyzed Kinetic Asymmetric Transformations of Racemic Allylic Benzoates

PubMed Central

Stanley, Levi M.; Bai, Chen; Ueda, Mitsuhiro; Hartwig, John F.

2010-01-01

Versatile methods for iridium-catalyzed, kinetic asymmetric substitution of racemic, branched allylic esters are reported. These reactions occur with a variety of aliphatic, aryl, and heteroaryl allylic benzoates to form the corresponding allylic substitution products in high yields (74–96%) with good to excellent enantioselectivity (84–98% ee) with a scope that encompasses a range of anionic carbon and heteroatom nucleophiles. These kinetic asymmetric processes occur with distinct stereochemical courses for racemic aliphatic and aromatic allylic benzoates, and the high reactivity of branched allylic benzoates enables enantioselective allylic substitutions that are slow or poorly selective with linear allylic electrophiles. PMID:20552969

Molecular line tracers of high-mass star forming regions

NASA Astrophysics Data System (ADS)

Nagy, Zsofia; Van der Tak, Floris; Ossenkopf, Volker; Bergin, Edwin; Black, John; Faure, Alexandre; Fuller, Gary; Gerin, Maryvonne; Goicoechea, Javier; Joblin, Christine; Le Bourlot, Jacques; Le Petit, Franck; Makai, Zoltan; Plume, Rene; Roellig, Markus; Spaans, Marco; Tolls, Volker

2013-07-01

High-mass stars influence their environment in different ways including feedback via their FUV radiation. The penetration of FUV photons into molecular clouds creates Photon Dominated Regions (PDRs) with different chemical layers where the mainly ionized medium changes into mainly molecular. Different chemical layers in PDRs are traced by different species observable at sub-mm and Far Infrared wavelengths. In this poster we present results from two molecular line surveys. One of them is the James Clerk Maxwell Telescope (JCMT) Spectral Legacy Survey (SLS) toward the luminous (>10^7 L_Sun), massive (~10^6 M_Sun), and distant (11.4 kpc) star-forming region W49A. The SLS images a 2x2 arcminute field toward W49A in the 330-373 GHz frequency range. The detected molecular lines reveal a complex chemistry and the importance of FUV-irradiation in the heating and chemistry of the region. The other line survey presented in the poster is part of the HEXOS (Herschel observations of EXtra-Ordinary Sources, PI: E. Bergin) key program using the Herschel Space Observatory and is toward the nearby (~420 pc) prototypical edge-on Orion Bar PDR and the dense molecular condensation Orion S. Reactive ions, such as CH+, SH+, and CO+, detected as a part of this line survey trace the warm (~500-1000 K) surface region of PDRs. Spectrally resolved HIFI and spectrally unresolved PACS spectra give constraints on the chemistry and excitation of reactive ions in these regions.

Relations between temperament and theory of mind development in the United States and China: biological and behavioral correlates of preschoolers' false-belief understanding.

PubMed

Lane, Jonathan D; Wellman, Henry M; Olson, Sheryl L; Miller, Alison L; Wang, Li; Tardif, Twila

2013-05-01

The emotional reactivity hypothesis holds that, over the course of phylogeny, the selection of animals with less reactive temperaments supported the development of sophisticated social-cognitive skills in several species, including humans (Hare, 2007). In the ontogenetic human case, an emotional reactivity hypothesis predicts that children with less reactive temperaments will reach certain milestones in theory-of-mind (ToM) development more quickly. We examined relations between temperament and false-belief understanding in 102 preschool-age children from China and the United States. Temperament was measured via parental ratings of behavior as well as with physiological measures of children's reactivity (hypothalamic-pituitary-adrenocortical axis reactivity gauged via salivary cortisol). In accord with an emotional reactivity hypothesis, children with certain reactive temperaments--specifically, those who were more aggressive and those who were both socially withdrawn and physiologically reactive--evidenced poorer social-cognition. However, our findings also force amendment to the ontogenetic emotional reactivity hypothesis. For the majority of children in both countries, physiological reactivity predicted more advanced ToM, perhaps by facilitating social engagement and attention to social stimuli. Moreover, children who were withdrawn from social interaction yet nonreactive, especially Chinese children of this temperament, evidenced advanced ToM. Thus, some forms of social disengagement may foster social-cognitive development in certain sociocultural contexts.

Persistent latent tuberculosis reactivation risk in United States immigrants.

PubMed

Walter, Nicholas D; Painter, John; Parker, Matthew; Lowenthal, Phillip; Flood, Jennifer; Fu, Yunxin; Asis, Redentor; Reves, Randall

2014-01-01

Current guidelines limit latent tuberculosis infection (LTBI) evaluation to persons in the United States less than or equal to 5 years based on the assumption that high TB rates among recent entrants are attributable to high LTBI reactivation risk, which declines over time. We hypothesized that high postarrival TB rates may instead be caused by imported active TB. Estimate reactivation and imported TB in an immigrant cohort. We linked preimmigration records from a cohort of California-bound Filipino immigrants during 2001-2010 with subsequent TB reports. TB was likely LTBI reactivation if the immigrant had no evidence of active TB at preimmigration examination, likely imported if preimmigration radiograph was abnormal and TB was reported less than or equal to 6 months after arrival, and likely reactivation of inactive TB if radiograph was abnormal but TB was reported more than 6 months after arrival. Among 123,114 immigrants, 793 TB cases were reported. Within 1 year of preimmigration examination, 85% of TB was imported; 6 and 9% were reactivation of LTBI and inactive TB, respectively. Conversely, during Years 2-9 after U.S. entry, 76 and 24% were reactivation of LTBI and inactive TB, respectively. The rate of LTBI reactivation (32 per 100,000) did not decline during Years 1-9. High postarrival TB rates were caused by detection of imported TB through active postarrival surveillance. Among immigrants without active TB at baseline, reported TB did not decline over 9 years, indicating sustained high risk of LTBI reactivation. Revised guidelines should support LTBI screening and treatment more than 5 years after U.S. arrival.

Nitrate formation during ozonation as a surrogate parameter for abatement of micropollutants and the N-nitrosodimethylamine (NDMA) formation potential.

PubMed

Song, Yang; Breider, Florian; Ma, Jun; von Gunten, Urs

2017-10-01

In this study, nitrate formation from ammonium and/or dissolved organic nitrogen (DON) was investigated as a novel surrogate parameter to evaluate the abatement of micropollutants during ozonation of synthetic waters containing natural organic matter (NOM) isolates, a natural water and secondary wastewater effluents. Nitrate formation during ozonation was compared to the changes in UV absorbance at 254 nm (UVA 254 ) including the effect of pH. For low specific ozone doses UVA 254 was abated more efficiently than nitrate was formed. This is due to a relatively slow rate-limiting step for nitrate formation from the reaction between ozone and a proposed nitrogen-containing intermediate. This reaction cannot compete with the fast reactions between ozone and UV-absorbing moieties (e.g., activated aromatic compounds). To further test the kinetics of nitrate formation, two possible intermediates formed during ozonation of DON were tested. At pH 7, nitrate was formed during ozonation of acetone oxime and methyl nitroacetate with second-order rate constants of 256.7 ± 4.7 M -1  s -1 and 149.5 ± 5.8 M -1  s -1 , respectively. The abatement of the selected micropollutants (i.e., 17α-ethinylestradiol (EE2), carbamazepine (CBZ), bezafibrate (BZF), ibuprofen (IBU), and p-chlorobenzoic acid (pCBA)) was investigated for specific ozone doses ≤1.53 mgO 3 /mgDOC and its efficiency depended strongly on the reactivity of the selected compounds with ozone. The relative abatement of micropollutants (i.e., EE2 and CBZ) with high ozone reactivity showed linear relationships with nitrate formation. The abatement of micropollutants with intermediate-low ozone reactivity (BZF, IBU, and pCBA) followed one- and two-phase behaviors relative to nitrate formation during ozonation of water samples containing high and low concentrations of nitrate-forming DON, respectively. During ozonation of a wastewater sample, the N-nitrosodimethylamine formation potential (NDMA-FP) during chloramination decreased with increasing specific ozone doses. A good correlation was obtained between NDMA-FP abatement and nitrate formation. Therefore, nitrate formation after pre-ozonation may be a useful parameter to estimate the reduction of the NDMA-FP during post-chloramination. Overall, the results of this study suggest that nitrate formation (possibly in combination with UVA 254 abatement) during ozonation of DON-containing waters may be a good surrogate for assessing the abatement of micropollutants and the NDMA-FP. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carbon cluster formation during thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine and 1,3,5-triamino-2,4,6-trinitrobenzene high explosives from ReaxFF reactive molecular dynamics simulations.

PubMed

Zhang, Luzheng; Zybin, Sergey V; van Duin, Adri C T; Dasgupta, Siddharth; Goddard, William A; Kober, Edward M

2009-10-08

We report molecular dynamics (MD) simulations using the first-principles-based ReaxFF reactive force field to study the thermal decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) at various densities and temperatures. TATB is known to produce a large amount (15-30%) of high-molecular-weight carbon clusters, whereas detonation of nitramines such as HMX and RDX (1,3,5-trinitroperhydro-1,3,5-triazine) generate predominantly low-molecular-weight products. In agreement with experimental observation, these simulations predict that TATB decomposition quickly (by 30 ps) initiates the formation of large carbonaceous clusters (more than 4000 amu, or approximately 15-30% of the total system mass), and HMX decomposition leads almost exclusively to small-molecule products. We find that HMX decomposes readily on this time scale at lower temperatures, for which the decomposition rate of TATB is about an order of magnitude slower. Analyzing the ReaxFF MD results leads to the detailed atomistic structure of this carbon-rich phase of TATB and allows characterization of the kinetics and chemistry related to this phase and their dependence on system density and temperature. The carbon-rich phase formed from TATB contains mainly polyaromatic rings with large oxygen content, leading to graphitic regions. We use these results to describe the initial reaction steps of thermal decomposition of HMX and TATB in terms of the rates for forming primary and secondary products, allowing comparison to experimentally derived models. These studies show that MD using the ReaxFF reactive force field provides detailed atomistic information that explains such macroscopic observations as the dramatic difference in carbon cluster formation between TATB and HMX. This shows that ReaxFF MD captures the fundamental differences in the mechanisms of such systems and illustrates how the ReaxFF may be applied to model complex chemical phenomena in energetic materials. The studies here illustrate this for modestly sized systems and modest periods; however, ReaxFF calculations of reactive processes have already been reported on systems with approximately 10(6) atoms. Thus, with suitable computational facilities, one can study the atomistic level chemical processes in complex systems under extreme conditions.

Identification and characterization of B cell precursors in rat lymphoid tissues. I. Adoptive transfer assays for precursors of TI-1, TI-2, and TD antigen-reactive B cells.

PubMed

Whalen, B J; Goldschneider, I

1993-10-01

Quantitative adoptive transfer assays were developed to detect the precursors of TI-1, TI-2, and TD antigen-reactive B cells in rat lymphoid tissues. Studies on the immune responses in normal and athymic nude rats validate the use of TNP-lipopolysaccharide as a TI-1 antigen, TNP-Ficoll as a TI-2 antigen, and SRBC as a TD antigen in rats. The precursors to these immunologically competent B cells are detected, following transfer into irradiated histocompatible recipients, by their ability to generate expanded populations of antigen-reactive B cells capable of mounting antibody responses (splenic IgM plaque-forming cells) to these antigens. Maximal numbers of antigen-reactive B cells emerge in antigenically naive rats after an interval of 7-12 days following transfer of donor lymphoid cells and decline rapidly thereafter. The delayed responses in adoptive recipients reconstituted with spleen cells are proportional to the numbers of spleen cells transferred and are shown to be primarily donor derived using histocompatible Ig kappa chain alloantigen disparate rat strain combinations. The precursors of TI-1, TI-2, and TD antigen-reactive B cells are present in both donor spleen and bone marrow. However, precursor cells to TI-1 and TD antigens are largely absent from donor lymph node cells, whereas precursors to the TI-2 antigen are as prevalent in donor lymph node as in donor spleen. These results support the hypothesis that newly formed virginal B cells represent transient populations of precursor cells that undergo further proliferation and differentiation in the spleen before acquiring immunological competence. The results also suggest that the precursors of TI-2 antigen-reactive B cells differ developmentally from those of TI-1 and TD antigen-reactive B cells, and that the antigen-reactive progeny of these precursors require additional stimulation in order to join the pool of long-lived peripheral B cells.

The Influence of Lithology on the Formation of Reaction Infiltration Instabilities in Mantle Rocks

NASA Astrophysics Data System (ADS)

Pec, M.; Holtzman, B. K.; Zimmerman, M. E.; Kohlstedt, D. L.

2017-12-01

The formation of oceanic plates requires extraction of large volumes of melt from the mantle. Several lines of evidence suggest that melt extraction is rapid and, therefore, necessitates high-permeability pathways. Such pathways may form as a result of melt-rock reactions. We report the results of a series of Darcy-type experiments designed to study the development of channels due to melt-solid reactions in mantle lithologies. We sandwiched a partially molten rock between a melt source and a porous sink and annealed it at high pressure (P = 300 MPa) and high temperatures (T = 1200° or 1250°C) with a controlled pressure gradient (∂P/∂z = 0-100 MPa/mm). To study the influence of lithology on the channel formation, we synthesized partially molten rocks of harzburgitic (40:40:20 Ol - Opx - basalt), wehrlitic (40:40:20 Ol - Cpx - basalt) and lherzolitic (65:25:10 Ol - Opx - Cpx) composition. The melt source was a disk of alkali basalt. In all experiments, irrespective of the exact mineralogy, melt - undersaturated in silica - from the source dissolved pyroxene in the partially molten rock and precipitated olivine ( Fo82), thereby forming a dunite reaction layer at the interface between the source and the partially molten rock. In samples annealed under a small pressure gradient, the reaction layer was roughly planar. However, if the velocity of melt due to porous flow exceeded 0.1 µm/s, the reaction layer locally protruded into the partially molten rock forming finger-like, melt-rich channels in rocks of wehrlitic and harzburgitic composition. The lherzolitic rocks were generally impermeable to the melt except at highest-pressure gradients where a narrow fracture developed, forming a dyke which drained the melt reservoir. Three-dimensional reconstructions using micro-CT images revealed clear differences between the dyke (a narrow, through-going planar feature) and the channels formed by reactive infiltration (multiple sinuous finger-like features). Apparently, the fraction of soluble minerals together with the melt fraction in the partially molten rock control whether dykes or reactive channels develop. Our experiments demonstrate that melt-rock reactions can lead to channelization in mantle lithologies, and the observed lithological transformations broadly agree with those observed in nature

Organic chloramines in drinking water: An assessment of formation, stability, reactivity and risk.

PubMed

How, Zuo Tong; Linge, Kathryn L; Busetti, Francesco; Joll, Cynthia A

2016-04-15

Although organic chloramines are known to form during the disinfection of drinking water with chlorine, little information is currently available on their occurrence or toxicity. In a recent in vitro study, some organic chloramines (e.g. N-chloroglycine) were found to be cytotoxic and genotoxic even at micromolar concentrations. In this paper, the formation and stability of 21 different organic chloramines, from chlorination of simple amines and amino acids, were studied, and the competition between 20 amino acids during chlorination was also investigated. For comparison, chlorination of two amides was also conducted. The formation and degradation of selected organic chloramines were measured using either direct UV spectroscopic or colorimetric detection. Although cysteine, methionine and tryptophan were the most reactive amino acids towards chlorination, they did not form organic chloramines at the chlorine to precursor molar ratios that were tested. Only 6 out of the 21 organic chloramines formed had a half-life of more than 3 h, although this group included all organic chloramines formed from amines. A health risk assessment relating stability and reactivity data from this study to toxicity and precursor abundance data from the literature indicated that only N-chloroglycine is likely to be of concern due to its stability, toxicity and abundance in water. However, given the stability of organic chloramines formed from amines, more information about the toxicity and precursor abundance for these chloramines is desirable. Copyright © 2016 Elsevier Ltd. All rights reserved.

Star-shaped PHB-PLA block copolymers: immortal polymerization with dinuclear indium catalysts.

PubMed

Yu, I; Ebrahimi, T; Hatzikiriakos, S G; Mehrkhodavandi, P

2015-08-28

The first example of a one-component precursor to star-shaped polyesters, and its utilization in the synthesis of previously unknown star-shaped poly(hydroxybutyrate)-poly(lactic acid) block copolymers, is reported. A series of such mono- and bis-benzyl alkoxy-bridged complexes were synthesized, fully characterized, and their solvent dependent solution structures and reactivity were examined. These complexes were highly active catalysts for the controlled polymerization of β-butyrolactone to form poly(hydroxybutyrate) at room temperature. Solution studies indicate that a mononuclear propagating species formed in THF and that the dimer-monomer equilibrium affects the rates of BBL polymerization. In the presence of linear and branched alcohols, these complexes catalyze well-controlled immortal polymerization and copolymerization of β-butyrolactone and lactide.

Reactivation of organophosphate-inhibited human acetylcholinesterase by isonitrosoacetone (MINA): a kinetic analysis.

PubMed

Worek, Franz; Thiermann, Horst

2011-11-15

Treatment of poisoning by highly toxic organophosphorus compounds (OP) with atropine and an acetylcholinesterase (AChE) reactivator (oxime) is of limited effectiveness in case of different nerve agents and pesticides. One challenge is the reactivation of OP-inhibited brain AChE which shows inadequate success with charged pyridinium oximes. Recent studies with high doses of the tertiary oxime isonitrosoacetone (MINA) indicated a beneficial effect on central and peripheral AChE and on survival in nerve agent poisoned guinea pigs. Now, an in vitro study was performed to determine the reactivation kinetics of MINA with tabun-, sarin-, cyclosarin-, VX- and paraoxon-inhibited human AChE. MINA showed an exceptionally low affinity to inhibited AChE but, with the exception of tabun-inhibited AChE, a moderate to high reactivity. In comparison to the pyridinium oximes obidoxime, 2-PAM and HI-6 the affinity and reactivity of MINA was in most cases lower and in relation to the most effective reactivators, the second order reactivation constant of MINA was 500 to 3400-fold lower. Hence, high in vivo MINA concentrations would be necessary to achieve at least partial reactivation. This assumption corresponds to in vivo data showing a dose-dependent effect on reactivation and survival in animals. In view, of the toxic potential of MINA in animals human studies would be necessary to determine the tolerability and pharmacokinetics of MINA in order to enable a proper assessment of the value of this oxime as an antidote in OP poisoning. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Utilization of Microwave Spectroscopy to Identify and Probe Reaction Dynamics of Hsno, a Crucial Biological Signaling Molecule

NASA Astrophysics Data System (ADS)

Nava, Matthew; Martin-Drumel, Marie-Aline; Stanton, John F.; Cummins, Christopher; McCarthy, Michael C.

2016-06-01

Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H2S biochemistries. Its existence and stability in vivo, however, remain controversial. By means of Fourier-transform microwave spectroscopy, we establish that HSNO is spontaneously formed in high concentration when NO and H2S gases are simply mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed with high efficiency by the reaction H2S and N2O3 to produce HSNO and HNO2, where N2O3 is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H2S may form HNO and HSSH. The length of the S--N bond has been derived to high precision from isotopic studies, and is found to be unusually long, 1.84 Å -- the longest S--N bond reported to date for an SNO compound. The present structural and reactivity investigations of this elusive molecule provide a firm fundation to better understand its physiological chemistry and propensity to undergo S--N bond homolysis in vivo.

Basement control of structure in the Gettysburg rift basin, Pennsylvania and Maryland

NASA Astrophysics Data System (ADS)

Root, Samuel I.

1989-09-01

Jurassic faulting formed the 93 km long Gettysburg basin as an extensional half graben paralleling the basement structural grain. Preserved in the basin are rift-related Carnian to Rhaetian strata that were tilted 20-30° NW into a SE dipping, listric normal fault at the northwest border of the basin. Vertical displacement on the border fault approaches 10 km. The border fault developed parallel to the trend of the terminal Paleozoic Alleghenian South Mountain cleavage of the Blue Ridge basement along 80% of its extent. However, it is only roughly parallel to discordant to dip of the cleavage. Relationship of cleavage and later border faulting may be the result of persistent reactivation of the original Appalachian continental margin. Local complex structures in the half graben are related to reactivation of two subvertical, pre-Mesozoic faults that transect basement structural grain (cleavage) at a large angle. The northern Shippensburg fault was reactivated during basin normal faulting, offsetting the border fault in a right-lateral sense by 3.5 km and forming within the basin a fold and a fault sliver of basement. The southern Carbaugh-Marsh Creek fault was not reactivated, but is the locus of a 20°-30° change of trend of both the basement cleavage and later border fault. However, two large, NW trending, left-lateral wrench faults, antithetic to the Carbaugh-March Creek fault, developed here offsetting the border fault and forming en echelon folds and horst blocks of basement rock within the basin.

The Dynamics of the Human Leukocyte Antigen Head Domain Modulates Its Recognition by the T-Cell Receptor.

PubMed

García-Guerrero, Estefanía; Pérez-Simón, José Antonio; Sánchez-Abarca, Luis Ignacio; Díaz-Moreno, Irene; De la Rosa, Miguel A; Díaz-Quintana, Antonio

2016-01-01

Generating the immune response requires the discrimination of peptides presented by the human leukocyte antigen complex (HLA) through the T-cell receptor (TCR). However, how a single amino acid substitution in the antigen bonded to HLA affects the response of T cells remains uncertain. Hence, we used molecular dynamics computations to analyze the molecular interactions between peptides, HLA and TCR. We compared immunologically reactive complexes with non-reactive and weakly reactive complexes. MD trajectories were produced to simulate the behavior of isolated components of the various p-HLA-TCR complexes. Analysis of the fluctuations showed that p-HLA binding barely restrains TCR motions, and mainly affects the CDR3 loops. Conversely, inactive p-HLA complexes displayed significant drop in their dynamics when compared with its free versus ternary forms (p-HLA-TCR). In agreement, the free non-reactive p-HLA complexes showed a lower amount of salt bridges than the responsive ones. This resulted in differences between the electrostatic potentials of reactive and inactive p-HLA species and larger vibrational entropies in non-elicitor complexes. Analysis of the ternary p-HLA-TCR complexes also revealed a larger number of salt bridges in the responsive complexes. To summarize, our computations indicate that the affinity of each p-HLA complex towards TCR is intimately linked to both, the dynamics of its free species and its ability to form specific intermolecular salt-bridges in the ternary complexes. Of outstanding interest is the emerging concept of antigen reactivity involving its interplay with the HLA head sidechain dynamics by rearranging its salt-bridges.

Omega-3 (ω-3) and social skills interventions for reactive aggression and childhood externalizing behavior problems: a randomized, stratified, double-blind, placebo-controlled, factorial trial.

PubMed

Raine, Adrian; Ang, Rebecca P; Choy, Olivia; Hibbeln, Joseph R; Ho, Ringo M-H; Lim, Choon Guan; Lim-Ashworth, Nikki S J; Ling, Shichun; Liu, Jean C J; Ooi, Yoon Phaik; Tan, Yi Ren; Fung, Daniel S S

2018-05-10

While studies suggest that nutritional supplementation may reduce aggressive behavior in children, few have examined their effects on specific forms of aggression. This study tests the primary hypothesis that omega-3 (ω-3), both alone and in conjunction with social skills training, will have particular post-treatment efficacy for reducing childhood reactive aggression relative to baseline. In this randomized, double-blind, stratified, placebo-controlled, factorial trial, a clinical sample of 282 children with externalizing behavior aged 7-16 years was randomized into ω-3 only, social skills only, ω-3 + social skills, and placebo control groups. Treatment duration was 6 months. The primary outcome measure was reactive aggression collected at 0, 3, 6, 9, and 12 months, with antisocial behavior as a secondary outcome. Children in the ω-3-only group showed a short-term reduction (at 3 and 6 months) in self-report reactive aggression, and also a short-term reduction in overall antisocial behavior. Sensitivity analyses and a robustness check replicated significant interaction effects. Effect sizes (d) were small, ranging from 0.17 to 0.31. Findings provide some initial support for the efficacy of ω-3 in reducing reactive aggression over and above standard care (medication and parent training), but yield only preliminary and limited support for the efficacy of ω-3 in reducing overall externalizing behavior in children. Future studies could test further whether ω-3 shows promise in reducing more reactive, impulsive forms of aggression.

Reaction of 2-acetylaminofluorene-N-sulfate with RNA and glutathione: evidence for the generation of two reactive intermediates with different reactivities towards RNA and glutathione.

PubMed

van den Goorbergh, J A; Meerman, J H; de Wit, H; Mulder, G J

1985-11-01

The sulfate ester of N-hydroxy-2-acetylaminofluorene (AAF-N-sulfate) is one of the reactive intermediates of this carcinogen. This ester breaks down spontaneously to a very reactive nitrenium ion, which reacts with nucleophilic groups in protein, DNA, RNA and glutathione (GSH). Reactions involving the nitrenium ion with several nucleophiles under various conditions were studied. The adduct formation to RNA was much higher in Tris-HCI buffer than in phosphate buffer (at pH 7.4), while adduct formation to deoxy-guanosine monomers was the same in both buffers. The presence of 150 mM KCI had the same decreasing effect in both cases. Ionic strength effects may be involved in these phenomena. GSH decreased RNA adduct formation by 20-45%, while other thiols were much more effective. On the other hand, RNA did not decrease the formation of GSH conjugates from AAF-N-sulfate. The decrease in RNA adduct formation by thiols corresponded with an increase in the formation of 2-acetylaminofluorene (AAF) from AAF-N-sulfate, while no N-hydroxy-AAF was formed. These results suggest that two independent reactive intermediates are formed from AAF-N-sulfate, with different reactivities towards RNA and glutathione. Possibly these intermediates are the 'hard' triplet state nitrenium ion and the 'soft' singlet state nitrenium ion. Cysteine, cysteamine and penicillamine were most effective in the inhibition of RNA adduct formation; the extent of inhibition correlated with the extent of AAF formation. The mechanisms involved are discussed.

Transition Metal Ions in Zeolites: Coordination and activation of O2

PubMed Central

Smeets, Pieter J.; Woertink, Julia S.; Sels, Bert F.; Solomon, Edward I.; Schoonheydt, Robert A.

2010-01-01

Zeolites containing transition metal ions (TMI) often show promising activity as heterogeneous catalysts in pollution abatement and selective oxidation reactions. In this paper, two aspects of research on the TMI Cu, Co and Fe in zeolites are discussed: (i) coordination to the lattice and (ii) activated oxygen species. At low loading, TMI preferably occupy exchange sites in six-membered oxygen rings (6MR) where the TMI preferentially coordinate with the oxygen atoms of Al tetrahedra. High TMI loadings result in a variety of TMI species formed at the zeolite surface. Removal of the extra-lattice oxygens during high temperature pretreatments can result in auto-reduction. Oxidation of reduced TMI sites often results in the formation of highly reactive oxygen species. In Cu-ZSM-5, calcination with O2 results in the formation of a species, which was found to be a crucial intermediate in both the direct decomposition of NO and N2O and the selective oxidation of methane into methanol. An activated oxygen species, called α-oxygen, is formed in Fe-ZSM5 and reported to be the active site in the partial oxidation of methane and benzene into methanol and phenol, respectively. However, this reactive α-oxygen can only be formed with N2O, not with O2. O2 activated Co intermediates in Faujasite (FAU) zeolites can selectively oxidize α-pinene and epoxidize styrene. In Co-FAU, CoIII superoxo and peroxo complexes are suggested to be the active cores, whereas in Cu and Fe-ZSM-5 various monomeric and dimeric sites have been proposed, but no consensus has been obtained. Very recently, the active site in Cu-ZSM-5 was identified as a bent [Cu-O-Cu]2+ core (Proc. Natl. Acad. Sci. USA 2009, 106, 18908-18913). Overall, O2 activation depends on the interplay of structural factors such as type of zeolite, size of the channels and cages and chemical factors such as Si/Al ratio and the nature, charge and distribution of the charge balancing cations. The presence of several different TMI sites hinders the direct study of the spectroscopic features of the active site. Spectroscopic techniques capable of selectively probing these sites, even if they only constitute a minor fraction of the total amount of TMI sites, are thus required. Fundamental knowledge of the geometric and electronic structure of the reactive active site can help in the design of novel selective oxidation catalysts. PMID:20380459

Borderline personality features as a predictor of forms and functions of aggression during middle childhood: examining the roles of gender and physiological reactivity.

PubMed

Banny, Adrienne M; Tseng, Wan-Ling; Murray-Close, Dianna; Pitula, Clio E; Crick, Nicki R

2014-08-01

The present longitudinal investigation examined borderline personality features as a predictor of aggression 1 year later. Moderation by physiological reactivity and gender was also explored. One hundred ninety-six children (M = 10.11 years, SD = 0.64) participated in a laboratory stress protocol in which their systolic blood pressure, diastolic blood pressure, and skin conductance reactivity to recounting a relational stressor (e.g., threats to relationships or exclusion) were assessed. Teachers provided reports on subtypes of aggressive behavior (i.e., reactive relational, proactive relational, reactive physical, and proactive physical), and children completed a self-report measure of borderline personality features. Path analyses indicated that borderline personality features predicted increases in reactive relational aggression and proactive relational aggression among girls who evinced heightened physiological reactivity to interpersonal stress. In contrast, borderline personality features predicted decreases in proactive physical aggression in girls. Findings suggest that borderline personality features promote engagement in relationally aggressive behaviors among girls, particularly in the context of emotional dysregulation.

78 FR 11101 - Air Quality: Revision to Definition of Volatile Organic Compounds-Exclusion of trans

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-15

... form of encryption and be free of any defects or viruses. For additional information about the EPA's... radical (OH); (ii) the maximum incremental reactivity (MIR) on a reactivity per unit mass basis; and (iii... discussed below. The k OH is the reaction rate constant of the compound with the OH radical in the air. This...

All kinds of reactivity: recent breakthroughs in metal-catalyzed alkyne chemistry.

PubMed

Anaya de Parrodi, Cecilia; Walsh, Patrick J

2009-01-01

Alkynes of reactions: Recent breakthroughs in metal-catalyzed alkyne reactions, which expand the synthetic utility of alkynes, have been achieved. These approaches broaden the range of alkynes that are accessible by C--N and C--C bond-forming reactions and demonstrate that the use of bifunctional heterobimetallic catalysts can lead to new reactivity and excellent enantioselectivity (see scheme).

Comparison of high-sensitivity C-reactive protein and fetuin-A levels before and after treatment for subjects with subclinical hyperthyroidism.

PubMed

Bilgir, Oktay; Bilgir, Ferda; Topcuoglu, Tuba; Calan, Mehmet; Calan, Ozlem

2014-03-01

This study was designed to show the effect of propylthiouracil treatment on sCD40L, high-sensitivity C-reactive protein, and fetuin-A levels on subjects with subclinical hyperthyroidism. After checking sCD40L, high-sensitivity C-reactive protein, and fetuin-A levels of 35 patients with subclinical hyperthyroidism, each was given 50 mg tablets of propylthiouracil three times daily. After 3 months, sCD40L, high-sensitivity C-reactive protein, and fetuin-A levels were then compared to the levels before treatment. Although high-sensitivity C-reactive protein and sCD40L levels were normal in the subclinical hyperthyroidism patients compared to the healthy controls, fetuin-A levels were statistically significantly higher (*p = 0.022). After treatment, fetuin-A levels of subclinical hyperthyroidism patients decreased statistically significantly compared to the levels before treatment (**p = 0.026). sCD40L and high-sensitivity C-reactive protein levels did not have a statistically significant difference compared to the control group and post-propylthiouracil treatment. In subclinical hyperthyroidism patients, high fetuin-A levels before propylthiouracil treatment and decreases in these levels after treatment in cases with subclinical hyperthyroidism indicated the possibility of preventing long-term cardiac complications with propylthiouracil treatment.

Substrate doping: A strategy for enhancing reactivity on gold nanocatalysts by tuning sp bands

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

Mammen, Nisha; Narasimhan, Shobhana; Gironcoli, Stefano de

2015-10-14

We suggest that the reactivity of Au nanocatalysts can be greatly increased by doping the oxide substrate on which they are placed with an electron donor. To demonstrate this, we perform density functional theory calculations on a model system consisting of a 20-atom gold cluster placed on a MgO substrate doped with Al atoms. We show that not only does such substrate doping switch the morphology of the nanoparticles from the three-dimensional tetrahedral form to the two-dimensional planar form, but it also significantly lowers the barrier for oxygen dissociation by an amount proportional to the dopant concentration. At a dopingmore » level of 2.78%, the dissociation barrier is reduced by more than half, which corresponds to a speeding up of the oxygen dissociation rate by five orders of magnitude at room temperature. This arises from a lowering in energy of the s and p states of Au. The d states are also lowered in energy, however, this by itself would have tended to reduce reactivity. We propose that a suitable measure of the reactivity of Au nanoparticles is the difference in energy of sp and d states.« less

Is reactivation of toxoplasmic retinochoroiditis associated to increased annual rainfall?

PubMed Central

Rudzinski, Marcelo; Meyer, Alejandro; Khoury, Marina; Couto, Cristóbal

2013-01-01

Background: Reactivation of toxoplasmic retinochoroiditis is the most frequent form of uveitis in Misiones, Argentina. Fluctuations in the number of patients consulting with this type of uveitis were detected during the last decade. Since the province was consecutively exposed to rainy and dry periods over the last years, we decided to explore whether a relationship between reactivation of toxoplasmic retinochoroiditis and rain might be established according to the data registered during the 2004–2010 period. Results: The frequency of toxoplasmic reactivation episodes increases when precipitation increases (mostly in second and fourth trimesters of each year). Analysis of the independent variables demonstrates that precipitation is a significant predictor of the frequency of reactivation episodes. Although registered toxoplasmic reactivations were more frequent during the third trimester of the year, the association between the third trimester and the reactivation episodes did not reach statistical significance. Conclusion: Prolonged and intense rainfall periods were significantly associated with the reactivation of toxoplasmic retinochoroiditis. Changes promoted by this climatic condition on both the parasite survival in the soil as well as a putative effect on the host immune response due to other comorbidities are discussed. PMID:24225023

Stability and Reactivity: Positive and Negative Aspects for Nanoparticle Processing.

PubMed

Xu, Liang; Liang, Hai-Wei; Yang, Yuan; Yu, Shu-Hong

2018-04-11

Nanoparticles exist far from the equilibrium state due to their high surface energy. Nanoparticles are therefore extremely unstable and easily change themselves or react with active substances to reach a relatively stable state in some cases. This causes desired changes or undesired changes to nanoparticles and thus makes them exhibit a high reactivity and a poor stability. Such dual nature (poor stability and high reactivity) of nanoparticles may result in both negative and positive effects for nanoparticle processing. However, the existing studies mainly focus on the high reactivity of nanoparticles, whereas their poor stability has been neglected or considered inconsequential. In fact, in some cases the unstable process, which is derived from the poor stability of nanoparticles, offers an opportunity to design and fabricate unique nanomaterials, such as by chemically transforming the "captured" intermediate nanostructures during a changing process, assembling destabilized nanoparticles into larger ordered assemblies, or shrinking/processing pristine materials into the desired size or shape via selective etching. In this review, we aim to present the stability and reactivity of nanoparticles on three levels: the foundation, concrete manifestations, and applications. We start with a brief introduction of dangling bonds and the surface chemistry of nanoparticles. Then, concrete manifestations of the poor stability and high reactivity of nanoparticles are presented from four perspectives: dispersion stability, thermal stability, structural stability, and chemical stability/reactivity. Next, we discuss some issues regarding the stability and reactivity of nanomaterials during applications. Finally, conclusions and perspectives on this field are presented.

Combining lymphovascular invasion with reactive stromal grade predicts prostate cancer mortality.

PubMed

Saeter, Thorstein; Vlatkovic, Ljiljana; Waaler, Gudmund; Servoll, Einar; Nesland, Jahn M; Axcrona, Karol; Axcrona, Ulrika

2016-09-01

Previous studies suggest that lymphovascular invasion (LVI) has a weak and variable effect on prognosis. It is uncertain whether LVI, determined by diagnostic prostate biopsy, predicts prostate cancer death. Data from experimental studies have indicated that carcinoma-associated fibroblasts in the reactive stroma could promote LVI and progression to metastasis. Thus, combining LVI with reactive stromal grade may identify prostate cancer patients at high risk of an unfavorable outcome. The purpose of the present study was to examine if LVI, determined by diagnostic biopsy, alone and in combination with reactive stromal grade could predict prostate cancer death. This population-based study included 283 patients with prostate cancer diagnosed by needle biopsy in Aust-Agder County (Norway) from 1991 to 1999. Clinical data were obtained by medical charts review. Two uropathologists evaluated LVI and reactive stromal grade. The endpoint was prostate cancer death. Patients with LVI had marginally higher risk of prostate cancer death compared to patients without LVI (hazard ratio: 1.8, P-value = 0.04). LVI had a stronger effect on prostate cancer death risk when a high reactive stromal grade was present (hazard ratio: 16.0, P-value <0.001). Therefore, patients with concomitant LVI and high reactive stromal grade were at particularly high risk for prostate cancer death. Evaluating LVI together with reactive stromal grade on diagnostic biopsies could be used to identify patients at high risk of death from prostate cancer. Prostate 76:1088-1094, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Glyoxal administration induces formation of high molecular weight aggregates of hemoglobin exhibiting amyloidal nature in experimental rats: An in vivo study.

PubMed

Banerjee, Sauradipta; Chakraborti, Abhay Sankar

2016-12-01

Glyoxal, a highly reactive α-oxoaldehyde, increases in diabetic condition and reacts with proteins to form advanced glycation end products (AGEs). In the present study, we have investigated the effect of glyoxal on experimental rat hemoglobin in vivo after external administration of the α-dicarbonyl compound in animals. Gel electrophoretic profile of hemolysate collected from glyoxal-treated rats (32mg/kg body wt. dose) after one week exhibited the presence of some high molecular weight protein bands that were found to be absent for control, untreated rats. Mass spectrometric and absorption studies indicated that the bands represented hemoglobin. Further studies revealed that the fraction exhibited the presence of intermolecular cross β-sheet structure. Thus glyoxal administration induces formation of high molecular weight aggregates of hemoglobin with amyloid characteristics in rats. Aggregated hemoglobin fraction was found to exhibit higher stability compared to glyoxal-untreated hemoglobin. As evident from mass spectrometric studies, glyoxal was found to modify Arg-30β and Arg-31α of rat hemoglobin to hydroimidazolone adducts. The modifications thus appear to induce amyloid-like aggregation of hemoglobin in rats. Considering the increased level of glyoxal in diabetes mellitus as well as its high reactivity, the above findings may be physiologically significant. Copyright © 2016 Elsevier B.V. All rights reserved.

Nanosilicon dot arrays with a bit pitch and a track pitch of 25 nm formed by electron-beam drawing and reactive ion etching for 1 Tbit/in.{sup 2} storage

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

Hosaka, Sumio; Sano, Hirotaka; Shirai, Masumi

2006-11-27

The formation of very fine Si dots with a bit pitch and a track pitch of less than 25 nm using electron-beam (EB) lithography on ZEP520 and calixarene EB resists and CF{sub 4} reactive ion etching has been demonstrated. The experimental results indicate that the calixarene resist is very suitable for forming an ultrahigh-packed bit array pattern of Si dots. This result promises to open the way toward 1 Tbit/in.{sup 2} storage using patterned media with a dot size of <15 nm.

Peptide Reactivity of Isothiocyanates - Implications for Skin Allergy

NASA Astrophysics Data System (ADS)

Karlsson, Isabella; Samuelsson, Kristin; Ponting, David J.; Törnqvist, Margareta; Ilag, Leopold L.; Nilsson, Ulrika

2016-02-01

Skin allergy is a chronic condition that affects about 20% of the population of the western world. This disease is caused by small reactive compounds, haptens, able to penetrate into the epidermis and modify endogenous proteins, thereby triggering an immunogenic reaction. Phenyl isothiocyanate (PITC) and ethyl isothiocyanate (EITC) have been suggested to be responsible for allergic skin reactions to chloroprene rubber, the main constituent of wetsuits, orthopedic braces, and many types of sports gear. In the present work we have studied the reactivity of the isothiocyanates PITC, EITC, and tetramethylrhodamine-6-isothiocyanate (6-TRITC) toward peptides under aqueous conditions at physiological pH to gain information about the types of immunogenic complexes these compounds may form in the skin. We found that all three compounds reacted quickly with cysteine moieties. For PITC and 6-TRITC the cysteine adducts decomposed over time, while stable adducts with lysine were formed. These experimental findings were verified by DFT calculations. Our results may suggest that the latter are responsible for allergic reactions to isothiocyanates. The initial adduct formation with cysteine residues may still be of great importance as it prevents hydrolysis and facilitates the transport of isothiocyanates into epidermis where they can form stable immunogenic complexes with lysine-containing proteins.

EGCG inhibit chemical reactivity of iron through forming an Ngal-EGCG-iron complex.

PubMed

Bao, Guan-Hu; Xu, Jie; Hu, Feng-Lin; Wan, Xiao-Chun; Deng, Shi-Xian; Barasch, Jonathan

2013-12-01

Accumulated evidence indicates that the interconversion of iron between ferric (Fe(3+)) and ferrous (Fe(2+)) can be realized through interaction with reactive oxygen species in the Fenton and Haber-Weiss reactions and thereby physiologically effects redox cycling. The imbalance of iron and ROS may eventually cause tissue damage such as renal proximal tubule injury and necrosis. Many approaches were exploited to ameliorate the oxidative stress caused by the imbalance. (-)-Epigallocatechin-3-gallate, the most active and most abundant catechin in tea, was found to be involved in the protection of a spectrum of renal injuries caused by oxidative stress. Most of studies suggested that EGCG works as an antioxidant. In this paper, Multivariate analysis of the LC-MS data of tea extracts and binding assays showed that the tea polyphenol EGCG can form stable complex with iron through the protein Ngal, a biomarker of acute kidney injury. UV-Vis and Luminescence spectrum methods showed that Ngal can inhibit the chemical reactivity of iron and EGCG through forming an Ngal-EGCG-iron complex. In thinking of the interaction of iron and ROS, we proposed that EGCG may work as both antioxidant and Ngal binding siderphore in protection of kidney from injuries.